TWI815989B - Colored curable resin compositions, color filters, display elements and solid-state imaging elements - Google Patents

Abstract

The present invention provides a colored curable resin composition capable of forming a colored coating film with excellent light resistance. A colored curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the resin (B) contains a resin represented by formula (B1) .

Description

Colored curable resin compositions, color filters, display elements

The present invention relates to a colored curable resin composition, and further relates to a color filter, a display element and a solid-state imaging element.

As a colored curable resin composition for forming a color filter included in a display device, a solid-state imaging element, etc., a colored curable resin composition containing a colorant, a binder resin, a polymerizable compound, and a polymerization initiator is known thing (Patent Document 1).

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2016-108288

An object of the present invention is to provide a colored curable resin composition capable of forming a colored coating film with excellent light resistance.

The present invention provides the colored curable resin composition, color filter, display element and solid-state imaging element shown below.

[1] A colored curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the resin (B) contains the following formula Resin represented by (B1).

[In the formula, Z represents a residue of a tetracarboxylic acid having an alicyclic skeleton.

G represents a hydrogen atom or -CO-X-(CO ₂ H)x, X represents a residue of a (x+1)-valent polycarboxylic acid, and x represents an integer from 1 to 3.

R ¹ represents a hydrogen atom or a methyl group, and a plurality of R ¹ may be the same as or different from each other.

R ² represents an alkyl group or a halogen atom having from 1 to 5 carbon atoms, and when there are multiple R ^2s , the multiple R ^2s may be the same as each other, or they may be different.

k represents an integer from 0 to 10, n represents an integer from 0 to 4, and m represents an integer from 1 to 50]

[2] The colored curable resin composition according to [1], wherein in the formula (B1), Z is a residue of a tetracarboxylic acid having an alicyclic skeleton having 4 to 10 carbon atoms.

[3] The colored curable resin composition according to [1] or [2], wherein in the formula (B1), Z is a tetracarboxylic acid having a saturated alicyclic skeleton having 4 to 6 carbon atoms. residue.

[4] A color filter composed of the colored filter according to any one of [1] to [3] A curable resin composition is formed.

[5] A display element including the color filter according to [4].

[6] A solid-state imaging element including the color filter according to [5].

According to the present invention, there is provided a colored curable resin composition capable of forming a colored coating film with excellent light resistance.

[1]Coloring agent (A)

The colored curable resin composition contains a colorant (A). The coloring agent (A) contains at least one selected from the group consisting of dyes and pigments. The colorant (A) preferably contains a combination of two dyes or a combination of at least one dye and at least one pigment, more preferably a combination of two dyes or a combination of one dye and one pigment.

[dye]

As the dye, well-known dyes can be used, including solvent dyes, acid dyes, direct dyes, mordant dyes, etc., for example, Color Index (The Society of Dyers and Colourists) Publishing) dyes classified as solvent, acid, basic, reactive, direct, disperse, mordant, or vat, etc. compound; or a well-known dye described in the Dyeing Notes (Shikisensha Co., Ltd.). The dye only needs to be matched with the desired color filter Just choose the appropriate spectroscopic spectrum. These dyes may be used alone, or two or more types may be used in combination. The dye is preferably an organic solvent-soluble dye.

Specific examples of the dye include: C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230 , 245, 247; C.I. Solvent Orange (Solvent Orange) 2, 7, 11, 15, 26, 56, 77, 86; C.I. Solvent Violet (Solvent Violet) 11, 13, 14, 26, 31, 36, 37, 38 , 45, 47, 48, 51, 59, 60; C.I. Solvent Blue (Solvent Blue) 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Solvent Green 1 , 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. C.I. solvent dye, C.I. acid yellow (Acid Yellow) 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66 ,73,76,80,87,88,91,92,94,95,97,98,103,106,111,114,129,133,134,138,143,145,150,151,155,158 ,160,172,176,182,183,195,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277 , 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; C.I. acid orange (Acid Orange) 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; C.I. Acid Violet )6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; C.I. Acid Blue (Acid Blue) 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187,192,199,203,204,205,210,213,229,234,236,242,243,256,259,267,269,278,280,285,290,296,315,324: 1, 335, 340; C.I. Acid Green (Acid Green) 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1 , 58, 63, 65, 80, 104, 105, 106, 109, etc. C.I. acid dyes, C.I. Direct Yellow (Direct Yellow) 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; C.I. Direct Red 79, 82, 83, 84, 91, 92 ,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233 , 234, 241, 243, 246, 250; C.I. Direct Orange (Direct Orange) 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Violet (Direct Violet) 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. Direct Blue (Direct Blue) 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. Direct Green (Direct Green) 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. direct dye, C.I. disperse yellow (Disperse Yellow) 51, 54, 76; C.I. Disperse Violet (Disperse Violet) 26, 27; C.I. Disperse Blue (Disperse Blue) 1, 14, 56, 60, etc. C.I. Disperse dye, C.I. Basic Red (Basic Red) 1, 10; C.I. Basic Blue (Basic Blue) 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; C.I. Basic Violet (Basic Violet) 2; C.I. Basic Red (Basic Red) 9; C.I. Basic Green (Basic Green) 1, etc. C.I. Basic dyes, C.I. Reactive Yellow (Reactive Yellow) 2, 76, 116; C.I. Reactive Orange (Reactive Orange) 16; C.I. Reactive Red (Reactive Red) 36, etc. C.I. Reactive dyes, C.I. Mordant Yellow (Mordant Yellow) 5, 8 ,10,16,20,26,30,31,33,42,43,45,56,61,62,65; C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36 , 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; C.I. Mordant Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24 , 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; C.I. Mordant Blue (Mordant Blue) 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; C.I. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41 , 43, 53 and other C.I. mordant dyes, C.I. Vat Green (Vat Green) 1 and other C.I. vat dyes, etc.

In addition, examples of dyes based on their chemical structures include triarylmethane dyes, xanthene dyes, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, and quinone dyes. Amine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes , porphyrazine dyes, etc.

The dye is preferably the following dye (A1) to dye (A4).

[Dye(A1)]

The dye (A1) contains a salt represented by formula (A-VI). The dye (A1) also includes its tautomer.

[In formula (A-VI), R ^1A ~ R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or a saturated hydrocarbon group with 1 to 20 carbon atoms, and may also be used to form the saturated hydrocarbon group There are oxygen atoms inserted between the methylene groups.

R ^9A to R ^12A each independently represent a hydrogen atom, an optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or a saturated hydrocarbon group having 1 to 20 carbon atoms, The aryl group and the aralkyl group may have -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , and oxygen may be inserted between the methylene groups constituting the saturated hydrocarbon group. Atom, the hydrogen atom contained in the saturated hydrocarbon group may also be substituted by a halogen atom or an amino group which may have a substituent. R ^9A and R ^10A can also be bonded and form a ring together with the bonded nitrogen atoms. R ^11A and R ^12A can also be bonded and form a ring together with the bonded nitrogen atoms.

A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent or an aromatic heterocyclic group having 3 to 20 carbon atoms that may have a substituent, and the substituents that the aromatic hydrocarbon group and the aromatic heterocyclic group may have It can also be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

[Y] ^(mn)- represents an anion with any (mn) valence.

m represents any natural number.

n represents the number of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f it has as a substituent, and is 0 or 1.

R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^1A to R ^12A may be linear, branched, or cyclic. Examples include: methyl, ethyl, propyl, isopropyl, Pentyl, hexyl, 2-ethylhexyl, decyl, dodecyl, eicosanyl, cyclohexyl, adamantyl.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^1A to R ^12A and having an oxygen atom inserted between the methylene groups constituting the saturated hydrocarbon group include groups represented by the following formula. In the following formula, * represents a bond with a carbon atom or a nitrogen atom.

Among them, a saturated hydrocarbon group having 1 to 10 carbon atoms and an oxygen atom inserted between the methylene groups constituting the saturated hydrocarbon group is preferable, and a saturated hydrocarbon group having 1 to 6 carbon atoms and a group having an oxygen atom inserted between the methylene groups constituting the saturated hydrocarbon group is more preferable. A group with an oxygen atom inserted between the methylene groups of a saturated hydrocarbon group.

Examples of the aryl group having 6 to 20 carbon atoms in R ^9A to R ^12A include phenyl, toluyl, xylyl, naphthyl, anthracenyl, phenanthrenyl, phenylphenyl, and the like.

Examples of the aralkyl group having 7 to 20 carbon atoms in R ^9A to R ^12A include benzyl group, phenylethyl group, methylpropylethyl group, and the like.

Examples of the optionally substituted amino group in R ^9A to R ^12A include: methylamino group, ethylamino group, and other amino groups having one alkyl group having 1 to 4 carbon atoms; dimethylamino group, dimethylamino group, etc. Ethylamine group, ethylmethylamino group, and other amine groups having two alkyl groups with 1 to 4 carbon atoms; amine group, etc.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms having a halogen atom or an amine group which may have a substituent in R ^9A to R ^12A include trifluoromethyl, trifluoroethyl, chloroethyl, and bromoethyl. , iodoethyl, N,N-dimethylaminoethyl, pentafluoropropyl, chlorohexyl, bromohexyl, iodohexyl, N,N-dimethylaminohexyl.

In the optionally substituted aryl group and the optionally substituted aralkyl group represented by R ^9A to R ^12A , as the substituent, in addition to the above-mentioned -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R In addition to ^f , examples include: halogen atoms such as fluorine atoms, chlorine atoms, and iodine atoms; alkoxy groups with 1 to 6 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; sulfo groups; sulfamide groups; and methylsulfonyl groups. Alkyl sulfonyl groups with 1 to 6 carbon atoms, etc.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f include trifluoromethyl, 2,2,2-trifluoroethyl, and the like.

Specific examples of the aryl group which may have a substituent and the aralkyl group which may have a substituent include groups represented by the following formulas. In the following formula, * represents a bond with a nitrogen atom.

Examples of a ring in which R ^9A and R ^10A are bonded together with the bonded nitrogen atoms and a ring in which R ^11A and R ^12A are bonded together with the bonded nitrogen atoms are formed: pyrrole Dydine ring, morpholine ring, piperidine ring, piperazine ring, etc.

In terms of ease of synthesis, R ^1A to R ^8A are preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently a hydrogen atom, a methyl group, Fluorine atom or chlorine atom.

In terms of ease of synthesis, R ^9A to R ^12A are preferably each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or an optionally substituted carbon group. The aryl group having 6 to 20 carbon atoms is more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 15 carbon atoms that may have a substituent, or an aryl group having 6 to 12 carbon atoms that may be substituted. group, and the hydrogen atoms contained in the aralkyl group and the aryl group can also be replaced by halogen atoms, haloalkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, hydroxyl groups, sulfo groups or 1 carbon group. ~4 alkylsulfonyl groups are substituted, preferably independently alkyl groups, phenyl groups or benzyl groups with 1 to 8 carbon atoms, and the hydrogen atoms contained in the phenyl group and the benzyl group can also be replaced by halogen. Atom, haloalkyl group with 1 to 4 carbon atoms, alkoxy group with 1 to 4 carbon atoms, hydroxyl group, sulfo group or alkylsulfonyl group with 1 to 4 carbon atoms. Examples of the phenyl group or benzyl group include groups represented by the following formulas. In the following formula, * represents a bond with a nitrogen atom.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms in A include: phenyl group, Toluyl, xylyl, naphthyl, anthracenyl, phenanthrenyl, phenylphenyl, etc.

Examples of the optionally substituted aromatic hydrocarbon group represented by A include groups represented by the following formulas. *Indicates the bond with the carbon atom.

The aromatic heterocyclic group representing A means an aromatic group having at least one heteroatom as a ring constituent. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, and the like.

A is preferably an aromatic heterocyclic group having at least one nitrogen atom as a ring constituent. Examples of the aromatic heterocyclic group include pyrrolyl, imidazolyl, 5-membered aromatic heterocyclic groups with nitrogen atoms, such as pyrazolyl, oxazolyl, thiazolyl, and triazolyl; 6-membered aromatic heterocyclic groups with nitrogen atoms, such as pyridyl, pyridinyl, and pyridazinyl Aromatic heterocyclic groups; condensed ring aromatic heterocyclic groups such as benzimidazolyl and indolyl groups.

Examples of the substituent in A include: a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a sulfo group, an amide sulfonyl group, an alkyl sulfonyl group having 1 to 6 carbon atoms, and those which may have a substituent. Specific examples of the amino group and the like include the same substituents as those exemplified for R ^9A to R ^12A .

A is preferably a group represented by formula (t1).

[In formula (t1), R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

X2 represents -O-, -N(R ⁵⁷ )- or -S-.

R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a saturated hydrocarbon group having 7 to 20 carbon atoms which may have a substituent. 30 aralkyl group, when the carbon number of the saturated hydrocarbon group is 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group can also be substituted with at least one of -O- and -CO-. Among them, in the saturated hydrocarbon group with 2 to 20 carbon atoms, the adjacent -CH ₂ - will not be substituted with -O- at the same time, and the terminal -CH ₂ - will not be substituted with -O- or -CO-. R ⁴⁵ and R ⁴⁶ may also be bonded and form a ring together with the bonded nitrogen atoms.

*Indicates bond with carbocation]

Examples of the optionally substituted aromatic heterocyclic group representing A include groups represented by the following formulas. *Indicates the bond with the carbon atom.

X2 is preferably -S-.

R ⁵⁶ is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and more preferably a phenyl group which may have a substituent.

R ⁴⁵ and R ⁴⁶ are preferably each independently a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and more preferably they are a substituent. An alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. More preferably, one of them is an alkyl group having 1 to 6 carbon atoms which may have a substituent, and the other is an alkyl group having 1 to 6 carbon atoms which may have a substituent. The substituent is an aromatic hydrocarbon group having 6 to 12 carbon atoms.

A is preferably a group represented by formula (A1-12) and formula (A1-13).

[Y] ^m- can include known anions. In terms of heat resistance, preferred are boron-containing anions, aluminum-containing anions, fluorine-containing anions, and groups selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus. At least one of the elements is an anion of oxygen.

Examples of boron-containing anions and aluminum-containing anions include anions represented by the following formula (4).

[In formula (4), W ¹ and W ² each independently represent a group having at least two monovalent proton-donating substituents and two substituents releasing protons from the group. M represents boron atom or aluminum atom]

Examples of the group having at least two monovalent proton-donating substituents and having two substituents in which protons are released from the group include at least two monovalent proton-donating substituents. (e.g., hydroxyl, carboxyl, etc.) compounds In a substance, a group formed by releasing protons from two proton-donating substituents. Preferable examples of the compound include catechol 2,3-dihydroxynaphthalene, 2,2'-biphenol, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1- Hydroxy-2-naphthoic acid, binaphthol, salicylic acid, benzilic acid or mandelic acid, these may also have substituents.

Examples of the substituent include: halogen atom; alkyl group having 1 to 6 carbon atoms; alkoxy group having 1 to 6 carbon atoms; nitro group; hydroxyl group; and amino group.

Examples of the anion represented by formula (4) include anions represented by the following formula.

[In the formula, R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a halogen atom, an alkyl group with 1 to 4 carbon atoms, and a halogenated alkyl group with 1 to 4 carbon atoms. Or alkoxy group with 1 to 4 carbon atoms]

For example, the following anion (BC-1) to anion (BC-28) can be mentioned. M represents a boron atom or an aluminum atom. tBu in Table 1 represents tertiary butyl group.

Examples of fluorine-containing anions include anions represented by the following formula (6), formula (7), formula (8), or formula (9).

[In formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ are bonded to form a fluorinated alkyl group having 1 to 4 carbon atoms. base]

[In formula (7), W ⁵ , W ⁶ and W ⁷ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms]

[In formula (8), Y ¹ represents a fluorinated alkyldiyl group having 1 to 4 carbon atoms]

[In formula (9), Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms]

In formula (6) and formula (7), the fluorinated alkyl group having 1 to 4 carbon atoms represented by W ³ to W ⁷ respectively is preferably a perfluoroalkyl group, for example, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , etc.

In the formula (6), the fluorinated alkyldiyl group having 2 to 4 carbon atoms formed by bonding W ³ and W ⁴ is preferably a perfluoroalkyldiyl group, for example, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, etc.

In the formula (8), the fluorinated alkyldiyl group having 1 to 4 carbon atoms represented by Y ¹ is preferably a perfluoroalkyldiyl group, and examples thereof include: -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, etc.

In the formula (9), the fluorinated alkyl group having 1 to 4 carbon atoms represented by Y ² is preferably a perfluoroalkyl group, and examples thereof include: -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , etc.

Examples of the anion represented by formula (6) (hereinafter, may be referred to as "anion (6)") include the following anions (6-1) to anions (6-6).

Examples of the anion represented by formula (7) (hereinafter sometimes referred to as "anion (7)") include the following anion (7-1).

Examples of the anion represented by formula (8) (hereinafter, may be referred to as "anion (8)") include the following anions (8-1) to anions (8-4).

Examples of the anion represented by formula (9) (hereinafter, may be referred to as "anion (9)") include the following anions (9-1) to anions (9-4).

[Y] ^m- may include anions containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen. The [Y] ^m- containing tungsten is preferably an anion of a heteropoly acid or an isopolyacid, more preferably an anion of a phosphotungstic acid, a silicotungstic acid and a tungsten-based isopoly acid.

The anions of such tungsten-containing heteropoly acid or homopoly acid include: Keggin type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- , Dawson type phosphotungstic acid ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin type silicotungstic acid ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ-[SiW ₁₂ O ₄₀ ] ^4- , further, other examples can be listed: [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- , etc.

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

In particular, in terms of ease of synthesis and post-processing, hybrids such as Keggin-type phosphotungstic acid ions, Dawson-type phosphotungstic acid ions, and Keggin-type silicotungstic acid ions are preferred. Polyacid anion, [W ₁₀ O ₃₂ ] ^4- identical to polyacid anion.

Specific examples of the salt represented by formula (A-VI) include salts represented by the following formulas (A-VI-1) to formula (A-VI-27).

The dye (A1) preferably contains a salt represented by formula (A-VI-27).

When having a sulfo group (-SO ₃ H) as a substituent, a salt can also be formed by exchanging hydrogen cations with any cation. Examples of arbitrary cations include alkali metal ions, organic ammonium ions, imidazolium ions which may have a substituent, and the like. When it has a plurality of sulfo groups, it can also form a salt with a metal ion having a divalent or higher valence.

[Dye(A2)]

The dye (A2) contains a xanthene dye. Known xanthene dyes can be used. Hereinafter, dye (A2) is also called xanthene dye (A2).

The xanthene dye (A2) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of xanthene dyes (A2) include: C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red will be omitted and only the number will be described. The same applies to others), 52, 87, 92, 94, 289, 388, C.I. Acid Violet 9 , 30, 102, C.I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. Basic Red 10, 11, C.I. Basic Violet 10 (Rhodamine B), 11, C.I. Solvent Red 218, C.I. Mordant Red 27, C.I. Reactive Red 36 (rose Bengal B), sulforhodamine G, xanthene dye described in Japanese Patent Laid-Open No. 2010-32999 and Japanese Patent No. 4492760 Xanthene dyes described in the gazette, etc. Dyes dissolved in organic solvents are preferred.

Among these, as the xanthene dye (A2), a dye containing a compound represented by formula (1a) (hereinafter, may be referred to as "compound (1a)") is preferred. Compound (1a) may also be a tautomer thereof. When compound (1a) is used, the content of compound (1a) in the xanthene dye (A2) is preferably 50 mass% or more, more preferably 70 mass% or more, and still more preferably 90 mass% or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye (A2).

[In formula (1a), R ^1a to R ^4a independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic group having 6 to 10 carbon atoms which may have a substituent. Hydrocarbon group, the -CH ₂ - contained in the saturated hydrocarbon group can also be substituted by -O-, -CO- or -NR ^11a -. R ^1a and R ^2a may together form a ring containing nitrogen atoms, and R ^3a and R ^4a may together form a ring containing nitrogen atoms.

R ^5a represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za ⁺ , -CO ₂ H, -CO ₂ ^- Za ⁺ , -CO ₂ R ^8a , -SO ₃ R ^8a or -SO ₂ NR ^9a R ^10a .

R ^6a and R ^7a independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ^5a may be the same or different.

a represents the integer 0 or 1.

Xa represents a halogen atom.

Za ⁺ represents ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , and the four R ^11a may be the same or different.

R ^8a represents a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms. The hydrogen atoms contained in the saturated hydrocarbon group may also be substituted by halogen atoms.

R ^9a and R ^10a independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. -CH ₂ - contained in the saturated hydrocarbon group may also be represented by -O-, -CO-, -NH- or -NR ^8a -substitution, R ^9a and R ^10a can also bond with each other to form a 3- to 10-membered heterocyclic ring containing nitrogen atoms.

R ^11a represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms]

In the formula (1a), when -SO ₃ ^- is present, the number is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^1a to R ^4a include phenyl, tolylyl, xylyl, mesityl, propylphenyl and butylphenyl. wait.

Examples of substituents that the aromatic hydrocarbon group may have include: halogen atom, carboxyl group, -R ^8a , -OH, -OR ^8a , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za ⁺ , -CO ₂ H, -CO ₂ R ^8a , -SR ^8a , -SO ₂ R ^8a , -SO ₃ R ^8a or -SO ₂ NR ^9a R ^10a . Among these, as the substituent, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za ⁺ and -SO ₂ NR ^9a R ^10a are preferred, and -SO ₃ ^- Za ⁺ and -SO ₂ NR are more preferred. ^{9aR 10a} . -SO ₃ ^- Za ⁺ in this case is preferably -SO ₃ ^-+ N(R ^11a ) ₄ . When R ^1a to R ^4a are these groups, a color filter with less generation of foreign matter and excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (1a).

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^1a to R ^4a and R ^8a to R ^11a include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl Linear alkyl groups such as base, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; branched chains such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl alkyl groups; alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl.

The hydrogen atom contained in the saturated hydrocarbon group in R ^1a to R ^4a may, for example, be substituted by a carboxyl group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom.

The hydrogen atom contained in the saturated hydrocarbon group in R ^9a and R ^10a may also be substituted by a hydroxyl group or a halogen atom, for example.

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

Examples of -OR ^8a include: methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and 2-ethylhexyloxy base and eicosyloxy group, etc.

Examples of -CO ₂ R ^8a include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, eicosyloxycarbonyl, and the like.

Examples of -SR ^8a include methylmercapto, ethylmercapto, butylmercapto, hexylmercapto, decylmercapto, eicosylmercapto, and the like.

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

Examples of -SO ₃ R ^8a include methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group and eicosanyl group. Oxygen sulfonyl group, etc.

Examples of -SO ₂ NR ^9a R ^10a include: sulfamic acid group; N-methyl sulfamic acid group, N-ethyl sulfamic acid group, N-propyl sulfamic acid group, and N-isopropyl group Aminesulfonyl, N-butylaminesulfonyl, N-isobutylaminesulfonyl, N-second butylaminesulfonyl, N-tert-butylaminesulfonyl, N-pentyl Sulfonamide group, N-(1-ethylpropyl) sulfonamide group, N-(1,1-dimethylpropyl) sulfonamide group, N-(1,2-dimethylpropyl group) )Amosulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)amine Sulfonyl, N-(3-methylbutyl)aminesulfonyl, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N-(1,3-dimethylbutyl) Aminosulfonyl, N-(3,3-dimethylbutyl)aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N-(1 ,4-dimethylpentyl)aminesulfonyl, N-octylaminesulfonyl, N-(2-ethylhexyl)aminesulfonyl, N-(1,5-dimethyl)hexylamine N-1 substituted sulfonamide group, N-(1,1,2,2-tetramethylbutyl)sulfonamide group, etc.; N,N-dimethylsulfonamide group, N,N -Ethylmethylmethanesulfonyl, N,N-diethylmethaminesulfonyl, N,N-propylmethylmethaminesulfonyl, N,N-isopropylmethylmethaminesulfonyl, N ,N-tert-butylmethylmethanesulfonyl, N,N-butylethylaminesulfonyl, N,N-bis(1-methylpropyl)aminesulfonyl, N,N-heptylmethyl N,N-2 substituted aminesulfonyl group, etc.

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

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

Examples of the alkyl group having 1 to 6 carbon atoms in R ^6a and R ^7a include those listed above.

An alkyl group with 1 to 6 carbon atoms in the alkyl group.

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

Za ⁺ is ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^11a ) ₄ .

As the ⁺ N(R ^11a ) ₄ , it is preferred that at least two of the four R ^11a be monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total carbon number of four R ^11a is preferably 20 to 80, more preferably 20 to 60. When ⁺ N(R ^11a ) ₄ is present in the compound (1a), and if R ^11a is these groups, the colored curable resin composition of the present invention containing the compound (1a) can form a color with few foreign matter. Filters.

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

[In the formula (2a), R ^21a to R ^24a independently represent a hydrogen atom, -R ^26a or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R ^21a and R ^22a may together form a ring containing nitrogen atoms, and R ^23a and R ^24a may together form a ring containing nitrogen atoms.

R ^25a represents -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ^26a .

m1 represents an integer from 0 to 5. When m1 is 2 or more, a plurality of R ^25a may be the same or different.

a1 represents the integer 0 or 1.

X1 represents a halogen atom.

R ^26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom or a carboxyl group.

Z1 ⁺ represents ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , and the four R ^27a can be the same or different.

R ^27a represents a monovalent saturated hydrocarbon group or benzyl group with 1 to 20 carbon atoms]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^21a to R ^24a include the same groups as those exemplified as the aromatic hydrocarbon group in R ^1a to R ^4a . The hydrogen atom contained in the aromatic hydrocarbon group may also be substituted by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ^26a or -SO ₂ NHR ^26a .

As a combination of R ^21a to R ^24a , it is preferable that R ^21a and R ^23a are independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms (the saturated hydrocarbon group may also have a halogen atom or a carboxyl group), and R ^22a and R ^24a is a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group is -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ^26a or - Replaced by SO ₂ NHR ^26a . A further preferred combination is: R ^21a and R ^23a are independently hydrogen atoms or an alkyl group having 1 to 8 carbon atoms (the alkyl group may also have a halogen atom or a carboxyl group), and R ^22a and R ^24a are each having 6 to 6 carbon atoms. 10 is a monovalent aromatic hydrocarbon group in which the hydrogen atoms contained in the aromatic hydrocarbon group are substituted by -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ^26a . When R ^21a to R ^24a are these groups, a color filter excellent in heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

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

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

When R ^21a to R ^24a are -R ^26a , -R ^26a is preferably each independently a methyl group or an ethyl group. In addition, R ^26a in -SO ₃ R ^26a and -SO ₂ NHR ^26a is preferably a branched chain alkyl group having 3 to 20 carbon atoms, more preferably a branched chain alkyl group having 6 to 12 carbon atoms, and further Preferred is 2-ethylhexyl. When R ^26a is one of these groups, a color filter with less generation of foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Z1 ⁺ is ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^27a ) ₄ .

As the ⁺ N(R ^27a ) ₄ , it is preferred that at least two of the four R ^27a be monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total carbon number of four R ^27a is preferably 20 to 80, more preferably 20 to 60. When ⁺ N(R ^27a ) ₄ is present in the compound (2a), if R ^27a is one of these groups, the colored curable resin composition of the present invention containing the compound (2a) can form a resin composition with less foreign matter generation. Color filters.

m1 is preferably 1 to 4, more preferably 1 or 2.

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

[In formula (3a), R ^31a and R ^32a independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may also be passed through an aromatic hydrocarbon group or carboxyl group having 6 to 10 carbon atoms. or halogen atom, the hydrogen atom contained in the aromatic hydrocarbon group can also be substituted by an alkoxy group with 1 to 3 carbon atoms, and the -CH ₂ - contained in the saturated hydrocarbon group can also be substituted by -O-, -CO -or-NR ^11a -substituted.

R ^33a and R ^34a independently represent an alkyl group having 1 to 4 carbon atoms, an alkylmercapto group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

R ^31a and R ^33a may together form a ring containing nitrogen atoms, and R ^32a and R ^34a may together form a ring containing nitrogen atoms.

p and q independently represent integers from 0 to 5. When p is 2 or more, the plurality of R ^33a may be the same or different. When q is 2 or more, the plurality of R ^34a may be the same or different.

R ^11a means the same meaning as stated]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ^31a and R ^32a include groups having 1 to 10 carbon atoms in the saturated hydrocarbon group in R ^8a .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that may be used as a substituent include the same groups as the aromatic hydrocarbon group in R ^1a .

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

R ^31a and R ^32a are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (the saturated hydrocarbon group may also have a halogen atom or a carboxyl group).

Examples of the alkyl group having 1 to 4 carbon atoms in R ^33a and R ^34a include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, second butyl, third butyl, etc. .

Examples of the alkylmercapto group having 1 to 4 carbon atoms in R ^33a and R ^34a include a methylmercapto group, an ethylmercapto group, a propylmercapto group, a butylmercapto group, an isopropylmercapto group, and the like.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ^33a and R ^34a include: methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group and isopropyl group Sulfonyl group, etc.

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

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

Examples of the compound (1a) include compounds represented by formula (1-1) to formula (1-43). Furthermore, in the formula, R ^40a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. R ^26a has the same meaning as R ^26a in formula (2a).

Among the compounds, compounds represented by formula (1-1) to formula (1-23), formula (1-37) to formula (1-85) and formula (1-102) to formula (1-107) It is equivalent to compound (2a), and the compounds represented by formula (1-24) to formula (1-36) and formula (1-86) to formula (1-101) are equivalent to compound (3a).

Among these, the sulfonamide compound of C.I. Acid Red 289, the quaternary ammonium salt of C.I. Acid Red 289, the sulfonamide compound of C.I. Acid Violet 102, or the quaternary ammonium salt of C.I. Acid Violet 102 are preferred. Examples of such compounds include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12).

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

In addition, from the viewpoint of improving the chromaticity range and transmittance of the obtained coating film, In addition, compounds represented by formula (1-32), formula (1-44) and formula (1-97) are also preferred.

As the xanthene dye (A2), commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Kasei Co., Ltd., "Rhodamin 6G" manufactured by Tagoka Chemical Industry Co., Ltd.) can be used ). In addition, commercially available xanthene dyes can also be used as starting materials and can be synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999.

[Dye(A3)]

The dye (A3) contains an anthraquinone dye. As the anthraquinone dye, publicly known ones can also be used. Examples of anthraquinone dyes include: C.I. Solvent Yellow 117 (hereinafter, description of C.I. Solvent Yellow, etc. will be omitted, and only numbers will be described), 163, 167, 189, C.I. Solvent Orange 77, 86, C.I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. Solvent Blue (Solvent Blue) 14, 18, 35, 36, 45, 58, 59, 59 : 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, C.I. solvent green (Solvent Green)3, 28, 29, 32, 33, C.I. Acid Red (Acid Red) 80, C.I. Acid Green (Acid Green) 25, 27, 28, 41, C.I. Acid Violet (Acid Violet) 34, C.I. Acid Blue (Acid Blue) 25, 27, 40, 45, 78, 80, 112, C.I. Disperse Yellow (Disperse Yellow) 51, C.I. Disperse Violet (Disperse Violet) 26, 27, C.I. Disperse Blue 1, 14, 56, 60, C.I. Direct Blue 40, C.I. Mordant Red 3, 11, C.I. Mordant Blue 8, etc. The anthraquinone dye is preferably a dye dissolved in an organic solvent.

[Dye(A4)]

The dye (A4) contains porphyrazine dye. Porphyrazine dye is a compound with a porphyrazine skeleton in the molecule. In addition, when the porphyrazine dye is an acid dye or a basic dye, it can also form a salt with any cation or anion.

[Pigment]

Examples of the pigment include organic pigments and inorganic pigments, and examples include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

The pigments can be used alone or in combination of two or more.

Examples of pigments include: C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117 , 125, 128, 137, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; C.I. Pigment Orange (Pigment Orange) 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Red (Pigment Red) 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 269 and other red pigments; C.I. Pigment Blue (Pigment Blue) 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. Pigment Violet (Pigment Violet) 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. Pigment Green (Pigment Green) 7, 36, 58, 59 and other green pigments; C.I. Pigment Brown (Pigment Brown) 23, 25 and other brown pigments; C.I. Pigment Black (Pigment Black) 1, 7 and other black pigments, etc.

If necessary, the pigment may be subjected to rosin treatment, surface treatment using a pigment derivative introducing an acidic group or a basic group, grafting treatment on the pigment surface using a polymer compound, etc., or micronization using a sulfuric acid micronization method, etc. treatment, or cleaning treatment using an organic solvent or water to remove impurities, removal treatment of ionic impurities using an ion exchange method, etc. The particle size of the pigment is preferably uniform.

By containing a pigment dispersant and performing a dispersion treatment, the pigment can be prepared into a pigment dispersion liquid in a state of being uniformly dispersed in the pigment dispersant solution. The pigments can be dispersed individually, or a plurality of pigments can be mixed and dispersed.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and the like pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. Examples of pigment dispersants by trade name include: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyeisha Chemical Co., Ltd.), Solsperse (Zeneca (Zeneca) Zeneca) (manufactured by BASF Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-chemie), etc.

When a pigment dispersant is used, the usage amount is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. When the usage amount of the pigment dispersant is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content rate of the colorant (A) in the colored curable resin composition is preferably 5 mass % or more and 70 mass % or less, more preferably 5 mass % with respect to the total solid content in the colored curable resin composition. % or more and 60 mass% or less, more preferably 5 mass% or more and 50 mass% or less. If the content rate of the colorant (A) is within the above range, desired spectrum or color density can be obtained.

In this specification, the "total amount of solid content in the colored curable resin composition" refers to the total amount of components after removing the solvent (E) from the colored curable resin composition. The total amount of solid content and the content of each component relative thereto can be measured by a known analysis method such as liquid chromatography or gas chromatography.

The coloring agent (A) preferably contains a dye (A1) to a dye (A4) selected from the group consisting of At least one of the formed groups preferably includes dye (A1) and dye (A2).

In other embodiments, the colorant (A) preferably contains the salt represented by the formula (A-VI), and more preferably contains the salt represented by the formula (A-VI-27).

When the colorant (A) contains the dye (A1), the colorant (A) can contain the dye (A1) in the form of a dispersion liquid in which the dye (A1) is dispersed in a solvent.

Furthermore, in another embodiment, the coloring agent (A) preferably contains a xanthene dye (A2), more preferably contains a compound represented by the formula (1a), and further preferably contains a compound represented by the formula (2a). The compound represented by the formula (3a) is particularly preferably a compound selected from a compound represented by the formula (1-32), a compound represented by the formula (1-44), and a compound represented by the formula (1-44). At least one member from the group of compounds represented by formula (1-97).

In other embodiments, the colorant (A) preferably contains the salt represented by the formula (A-VI) and the compound represented by the formula (1a), and more preferably contains the salt represented by the formula (A-VI). The compound represented by -27) and the group selected from the compound represented by the formula (1-32), the compound represented by the formula (1-44) and the compound represented by the formula (1-97) at least one of them.

Furthermore, in other embodiments, the colorant (A) preferably includes a combination of at least one selected from the group consisting of dyes (A1) to dyes (A4) and at least one pigment, and more preferably includes dye (A1). ) or a combination of dye (A2) and at least one pigment, further preferably including a compound represented by the formula (1a) and at least one red pigment, particularly preferably a compound selected from the group represented by the formula (1-32) Compounds, compounds represented by formula (1-44) and compounds represented by formula (1-97) The combination of at least one member of the group and C.I. Pigment Red is more particularly preferably a combination including a compound represented by formula (1-97) and C.I. Pigment Red 269.

When the colorant (A) contains a pigment, the colorant (A) can contain the pigment in the form of a dispersion liquid in which the pigment is dispersed in a solvent.

When the colorant (A) contains the dye (A1), the content rate of the dye (A1) in the colorant (A) is preferably 0.5 mass% or more and 100 mass% or less, more preferably 61 mass% or more and 99.5 mass % or less, more preferably 81 mass % or more and 99 mass % or less.

When the colorant (A) contains the dye (A2), the content rate of the dye (A2) in the colorant (A) is preferably 0.1 mass% or more and 80 mass% or less, more preferably 0.3 mass% or more and 40 mass % or less, more preferably 0.5 mass % or more and 20 mass % or less.

When the colorant (A) contains the dye (A1) and the dye (A2), the mass ratio of the dye (A1) and the dye (A2) in the colorant (A) [(A1): (A2)] can be, for example, It is 0.01:99.99~99.99:0.01, preferably 50:50~99.95:0.05, more preferably 90:10~99.9:0.1.

When the colorant (A) contains a dye (A2) and a pigment, the mass ratio [(A1): pigment] of the dye (A2) and the pigment in the colorant (A) may be, for example, 1:99~99:1 , preferably 5:95~50:50, more preferably 10:90~30:70.

When the colored curable resin composition contains a solvent (hereinafter also referred to as the solvent (E)), a colorant-containing liquid containing the colorant (A) and the solvent (E) may be prepared in advance, and then the colorant may be used. Containing liquid to prepare colored curable resin composition. When the colorant (A) is insoluble in the solvent (E), the colorant-containing liquid can be prepared in the form of a dispersion liquid by dispersing the colorant (A) in the solvent (E) and mixing. The colorant-containing liquid may contain part or all of the solvent (E) contained in the colored curable resin composition.

The solid content content of the colorant-containing liquid is preferably 0.1 mass % or more and 99.9 mass % or less, more preferably 1 mass % or more and 90 mass % or less, and still more preferably It is 1 mass % or more and 60 mass % or less, especially preferably 3 mass % or more and 50 mass % or less.

The content rate of the colorant (A) in the colorant-containing liquid is preferably 0.01 mass% or more and 100 mass% or less, and more preferably 0.1 mass% or more and 99.9 mass% based on the total solid content in the colorant-containing liquid. % or less, more preferably 1 mass % or more and 99 mass % or less, particularly preferably 10 mass % or more and 90 mass % or less.

In this specification, "the total amount of solid content in the colorant-containing liquid" refers to the total amount of components after removing the solvent (E) from the colorant-containing liquid. The total amount of solid content and the content of each component relative thereto can be measured by a known analysis method such as liquid chromatography or gas chromatography.

The colorant (A) can be in a state in which the colorant (A) is uniformly dispersed in the colorant-containing liquid by containing a dispersant and performing a dispersion treatment.

Examples of the dispersing agent include surfactants, and the dispersing agent may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specific examples thereof include polyester-based, polyamine-based, and acrylic-based surfactants. These dispersants can be used alone or in combination of two or more. As a dispersant, if it is sold under the trade name means: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyeisha Chemical Co., Ltd.), Solsperse (registered trademark) (Zeneca ) (manufactured by BASF Co., Ltd.), EFKA (registered trademark) (manufactured by BASF Co., Ltd.), Ajisper (registered trademark) (Ajinomoto Fine-Techno ) (manufactured by BYK-chemie Co., Ltd.) and Disperbyk (registered trademark) (manufactured by BYK-chemie Co., Ltd.), BYK (registered trademark) (BYK-chemie) chemie) (stock manufacturing), etc.

In order to prepare the colorant-containing liquid, when a dispersant is used, the usage amount of the dispersant (solid content) is preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the colorant (A). , more preferably not less than 5 parts by mass and not more than 50 parts by mass. When the usage amount of the dispersant is within the above range, a colorant-containing liquid in a more uniform dispersed state tends to be obtained.

[2]Resin(B)

The resin (B) of the colored curable resin composition contains a resin represented by the following formula [hereinafter also referred to as resin (B1)].

[In the formula,

Z represents the residue of a tetracarboxylic acid having an alicyclic skeleton.

G represents a hydrogen atom or -CO-X-(CO ₂ H)x, X represents a residue of a (x+1)-valent polycarboxylic acid, and x represents an integer from 1 to 3.

R ¹ represents a hydrogen atom or a methyl group, and a plurality of R ¹ may be the same as or different from each other.

R ² represents an alkyl group or a halogen atom having from 1 to 5 carbon atoms, and when there are multiple R ^2s , the multiple R ^2s may be the same as each other, or they may be different.

k represents an integer from 0 to 10, n represents an integer from 0 to 4, and m represents an integer from 1 to 50]

Examples of the tetracarboxylic acid having an alicyclic skeleton in Z include a tetracarboxylic acid having at least one alicyclic skeleton having at least one carbon number of 4 or more and 12 or less. Specific examples thereof include 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid. Carboxylic acids and other cycloalkanes tetracarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, dicyclohexyl 3,3'-4,4'-tetracarboxylic acid and These positional isomers, etc.

The residue of a tetracarboxylic acid having an alicyclic skeleton in Z is preferably a residue of a tetracarboxylic acid having an alicyclic skeleton having 4 to 10 carbon atoms, and more preferably a residue of a tetracarboxylic acid having an alicyclic skeleton of 4 to 6 carbon atoms. The residue of the tetracarboxylic acid of the cyclic skeleton is more preferably a structure represented by the following formula (Z-1) to formula (Z-5), and more preferably a saturated alicyclic skeleton having a carbon number of 4 to 6 The tetracarboxylic acid residue is particularly preferably a structure represented by formula (Z-1). In the formula, * represents the bond with -CO(O)- in the main chain, and ** represents the bond with the carboxyl group.

In a preferred form, Z is a structure represented by formula (Z-1).

In G, examples of the (x+1)-valent polycarboxylic acid in X include malonic acid, succinic acid, glutaric acid, adipic acid, and 1,2,3-propanetricarboxylic acid (tricarballylic acid). , trans-aconitic acid, trimellitic acid. x represents an integer from 1 to 3.

Examples of X include structures represented by the following formulas. In the formula, * represents the bond with the carbon atom of -CO-, and ** represents the bond with the carboxyl group.

Examples of -CO-X-(CO ₂ H)x in G include structures represented by the following formulas (G-1) to (G-7). In the formula, * represents the bond with the oxygen atom, and R represents the carboxyl group.

Examples of the alkyl group having 1 to 5 carbon atoms in R ² include: methyl, ethyl, propyl, isopropyl, butyl, second butyl, isobutyl, third butyl, Pentyl etc.

Examples of the halogen atom in R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

k represents an integer from 0 to 10.

n represents an integer from 0 to 4, preferably from 0 to 2, and more preferably from 0.

m represents an integer from 1 to 50.

Specific examples of the resin (B1) include resins represented by formulas (B1-1) to (B1-19) shown in the following tables.

[Table 2]

As the resin (B1), formula (B1-1), formula (B1-6) to formula (B1-19) are preferred. The resin represented.

The acid value of the resin (B1) in terms of solid content may be, for example, 80 mg-KOH/g or more and 140 mg-KOH/g or less, or may be 100 mg-KOH/g or more and 130 mg-KOH/g or less, 100 mg-KOH /g or more and 120 mg-KOH/g or less, or 120 mg-KOH/g or more and 130 mg-KOH/g or less.

Regarding the molecular weight of the resin (B1), the weight average molecular weight (Mw) in terms of polystyrene may be, for example, 1,000 or more and 15,000 or less, and the weight average molecular weight (Mw) may be 5,000 or more and 13,000 or less. It may be 6000 or more and 8000 or less, and the weight average molecular weight (Mw) may be 9000 or more and 12000 or less.

[Manufacturing method of resin (B1)]

Resin (B1) is produced by combining bisphenol A type epoxy (meth)acrylate or its modified product (α) of divalent to tetravalent carboxylic acid [hereinafter, also referred to as "(α)"] and a lipid. It is obtained by reacting tetracarboxylic dianhydride (β) [hereinafter, also abbreviated as "(β)"] with a cyclic skeleton. In this specification, "(meth)acrylate" means at least one selected from the group consisting of acrylate and methacrylate. The same is true for other terms with "(methyl)".

Examples of divalent to tetravalent carboxylic acids include the (x+1)-valent polycarboxylic acids exemplified in the description of G in the formula (B1), such as malonic acid, succinic acid, glutaric acid, and hexane. Diacid, 1,2,3-propanetricarboxylic acid, trans-aconitic acid, trimellitic acid, etc.

Specific examples of (β) include anhydrides of tetracarboxylic acids having an alicyclic skeleton exemplified for Z in the formula (1). Specific examples include: 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Equicycloalkane tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl 3,3',4,4'-tetracarboxylic Acid dianhydrides and their positional isomers, etc.

Examples of a method for producing resin (B1) include a method of placing predetermined amounts of (α) and (β), a solvent, and the like in a reaction vessel, and performing stirring, heating, and heat preservation in a deoxygenated environment. The solvent may be one that dissolves (α) and (β), and examples thereof include propylene glycol monomethyl ether and the like.

The obtained resin (B1) can be used directly as a reacted solution, as a concentrated or diluted solution, or as a solid (powder) taken out by reprecipitation or other methods. In particular, during the polymerization, by using the solvent (E) described below as a solvent, the solution after the reaction can be directly used, thereby simplifying the production steps.

The reaction can be performed by adding, for example, 1 to 50 parts by mass of (β) to 100 parts by mass of (α).

The weight average molecular weight (Mw) of the resin (B1) in terms of polystyrene is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000, further preferably from 3,000 to 30,000, particularly preferably from 5,000 to 15,000. the following. When the weight average molecular weight (Mw) is within the above range, the solubility of the unexposed portion with respect to the developer tends to be high, and the residual film rate or hardness of the resulting pattern also tends to be high.

The acid value of the resin (B1) in terms of solid content is preferably 5 mg-KOH/g or more and 200 mg-KOH/g or less, more preferably 50 mg-KOH/g or more and 180 mg-KOH/g or less, and still more preferably 80mg-KOH/g or more and 150 mg-KOH/g or less. The acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin, and can be determined by titration using a potassium hydroxide aqueous solution, for example.

The content of the resin (B1) is preferably 5 mass% or more and 50 mass% or less in 100 mass% of the solid content of the colored curable resin composition, more preferably 10 mass% or more and 45 mass% or less, and still more preferably 15 mass% Mass% or more and 40 mass% or less. When the content of the resin (B1) is within the above range, the solubility of the unexposed portion with respect to the developer tends to be high.

Resin (B) may further include one or more resins different from resin (B1) (hereinafter, also referred to as resin (B2)).

The resin (B2) is preferably an alkali-soluble resin. Alkali solubility refers to the property of dissolving in an aqueous solution of an alkali compound, that is, a developer. Examples of the resin (B2) include the following resin [K1] to resin [K6].

Resin [K1]: At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride [hereinafter, sometimes referred to as "monomer (a)"], and a resin having 2 to 4 carbon atoms A copolymer of a monomer (hereinafter, sometimes referred to as "monomer (b)") with a cyclic ether structure and an ethylenically unsaturated bond.

Resin [K2]: monomer (a), monomer (b), and monomer copolymerizable with monomer (a) (different from monomer (a) and monomer (b) ) [hereinafter, sometimes referred to as "monomer (c)"] copolymer.

Resin [K3]: copolymer of monomer (a) and monomer (c).

Resin [K4]: copolymer of monomer (a) and monomer (c) and monomer (b) Resin obtained by reaction.

Resin [K5]: a resin obtained by reacting the copolymer of the monomer (b) and the monomer (c) with the monomer (a).

Resin [K6]: A resin obtained by reacting a copolymer of a monomer (b) and a monomer (c) with a monomer (a) and further reacting a carboxylic acid anhydride.

Specific examples of the monomer (a) include: (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic 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 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic 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, 5-carboxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2- Bicyclic unsaturated compounds containing carboxyl groups such as ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalate Anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride Phthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (himic anhydride) and other unsaturated dicarboxylic anhydrides; succinic acid mono[2-(methyl) Acryloxyethyl] ester, mono[2-(methyl) phthalate unsaturated mono[(meth)acryloxyalkyl] esters of divalent or higher polycarboxylic acids such as α-(hydroxymethyl)(meth)acrylic acid Unsaturated (meth)acrylic acid containing hydroxyl and carboxyl groups in the same molecule.

Among them, (a) is preferably (meth)acrylic acid, maleic anhydride, etc. from the viewpoint of copolymerization reactivity or solubility in an alkaline aqueous solution.

In addition, the "(meth)acrylic acid group" in this specification means at least one selected from the group consisting of an acrylic acid group and a methacrylic acid group. The same applies to expressions such as "(meth)acrylyl" and "(meth)acrylate".

The monomer (b) refers to a cyclic ether structure having 2 to 4 carbon atoms (for example, selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring) at least one of the group) and a polymerizable compound with an ethylenically unsaturated bond. The monomer (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloxy group.

Examples of the monomer (b) include: monomers having an oxetane group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as “monomers (b1)”]; monomers having an oxetane group; A monomer having a tetrahydrofuran group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "monomer (b2)"], a monomer having a tetrahydrofuran group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "monomer (b2)"] Measurement body (b3)"] etc.

Examples of (b1) include: monomers having a structure in which unsaturated aliphatic hydrocarbons are epoxidized [hereinafter, sometimes referred to as “monomers (b1-1)”]; monomers having a structure in which unsaturated alicyclic hydrocarbons are epoxidized; Epoxidized structural monomer [hereinafter sometimes referred to as "monomer (b1-2)"].

Examples of the monomer (b1-1) include: (glycidylmeth)acrylate, (meth)acrylic acid β-methylglycidyl ester, (meth)acrylic acid β-ethylglycidyl ester, and glycidyl vinyl benzyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl -m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidoxymethyl) Methyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene Methyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris( Glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

Examples of the monomer (b1-2) include: vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (for example, Celloxide 2000; Daicel ( Daicel) Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer A400; Daicel Chemical Industry Co., Ltd.), (Meth)acrylate base) 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.), compounds represented by formula (I), compounds represented by formula (II) Represented compounds, etc.

[In formula (I) and formula (II), R ^aa and R ^ab independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may also be substituted with a hydroxyl group. X ^a1 and X ^a2 independently represent a single bond, *-R ^ac -, *-R ^ac -O-, *-R ^ac -S-, or *-R ^ac -NH-. R ^ac represents an alkanediyl group having 1 to 6 carbon atoms. *Indicates the bond with O]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, and the like.

Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxy -1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

R ^aa and R ^ab are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkylenediyl group constituting R ^ac include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane. -1,5-diyl, hexane-1,6-diyl, etc.

_{It is preferred} that X ^{a1 and} It is a single bond, *-CH ₂ CH ₂ -O- group.

Specific examples of the compound represented by formula (I) include compounds represented by formula (I-1) to formula (I-15), and preferably, compounds represented by formula (I-1) and formula (I-3) ), compounds represented by formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), more preferably, compounds represented by formula (I- 1), compounds represented by formula (I-7), formula (I-9), and formula (I-15).

Specific examples of the compound represented by formula (II) include compounds represented by formula (II-1) to formula (II-15), and preferably, compounds represented by formula (II-1) and formula (II-3) ), compounds represented by formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), more preferably, compounds represented by formula (II- 1), compounds represented by formula (II-7), formula (II-9), and formula (II-15).

The compound represented by formula (I) and the compound represented by formula (II) can be used individually. These can be mixed in any ratio. In the case of mixing, the mixing ratio is calculated as formula (I): formula (II) [mol ratio], preferably 5:95~95:5, more preferably 10:90~90:10, and further The best time is 20:80~80:20.

The monomer (b2) is preferably a monomer having an oxetanyl group and a (meth)acryloxy group.

Preferable examples of the monomer (b2) include: 3-methyl-3-(meth)acryloxymethyloxetane, 3-ethyl-3-(meth)propene Cyloxymethyloxetane, 3-methyl-3-(meth)acryloxyethyloxetane, 3-ethyl-3-(meth)acryloxyethyl base oxetane.

The monomer (b3) is preferably a monomer having a tetrahydrofuran group and a (meth)acryloxy group. Preferable examples of the monomer (b3) include: tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate wait.

Specific examples of the monomer (c) include: (methyl methacrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl methacrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate Cyclopentyl methacrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-(meth)acrylate [In this technical field, it is called "(meth)acrylic acid dicyclopentyl ester" as a common name. In addition, it is also sometimes called "(meth)acrylic acid tricyclodecyl ester", (meth)acrylic acid tricyclo[5.2.1.0 ^2,6 ]decene-8-yl ester [in this technical field, as Commonly known as "dicyclopentenyl (meth)acrylate"], dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantium (meth)acrylate Alkyl ester, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, etc. (methyl) Acrylates; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; diethyl maleate, diethyl fumarate, Dicarboxylic acid diesters such as diethyl conate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1] Hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[ 2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxy Bicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2 .1]Hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5 -Hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1]Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclo Hexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide Amine, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6 -Dicarbonyl imine derivatives such as maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl) maleimide Materials; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride , acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, (c) is preferably benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, or N-phenylmaleimide , N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc.

In addition, in terms of excellent developability during pattern formation, (c) is more preferably benzyl (meth)acrylate or tricyclodecyl (meth)acrylate.

The ratio of the structural units derived from each of the resin [K1] is preferably in the following range among all the structural units constituting the resin [K1].

Structural unit derived from monomer (a): 2 mol% or more and 50 mol% or less (more preferably 10 mol% or more and 45 mol% or less), structure derived from monomer (b) Units, particularly structural units derived from monomer (b1): 50 mol% or more and 98 mol% or less (more preferably 55 mol% or more and 90 mol% or less).

When the ratio of the structural units of the resin [K1] is within the above range, storage stability, developability, and solvent resistance of the obtained pattern tend to be excellent.

For resin [K1], please refer to the literature "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu It was produced by following the method described in the first edition of Dojin Publishing House (Co., Ltd., first printing issued on March 1, 1972) and the cited documents described in this document.

Specifically, a predetermined amount of the monomer (a) and the monomer (b) (especially the monomer (b1)), a polymerization initiator, a solvent, etc. are put into a reaction vessel, and then deoxidized. Methods for stirring, heating and keeping warm under ambient conditions. In addition, the polymerization initiator, solvent, etc. used here are not particularly limited, and those commonly used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (Benzyl peroxide, etc.). The solvent may be any one that dissolves each monomer. As a solvent for the colored curable resin composition, the solvent (E) described below and the like can be used.

The obtained copolymer can be used directly as a reacted solution, as a concentrated or diluted solution, or as a solid (powder) taken out by reprecipitation or other methods. In particular, during the polymerization, by using the solvent (E) described below as a solvent, the solution after the reaction can be directly used, thereby simplifying the production steps.

The ratio of the structural units derived from each in the resin [K2] is preferably in the following range among all the structural units constituting the resin [K2].

Structural unit derived from monomer (a): 4 mol% or more and 45 mol% or less (more preferably 10 mol% or more and 30 mol% or less), structure derived from monomer (b) Units, particularly structural units derived from a monomer (b1): 2 mol% or more and 95 mol% or less (more preferably 5 mol% or more and 80 mol% or less), derived from a monomer ( Structural unit of c): 1 mol% or more and 65 mol% or less (More preferably, it is 5 mol% or more and 60 mol% or less).

When the ratio of the structural units of the resin [K2] is within the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength of the obtained pattern tend to be excellent.

The resin [K2] can be produced in the same manner as the method described as the production method of the resin [K1]. Specifically, a predetermined amount of the monomer (a), the monomer (b) (especially the monomer (b1)), and the monomer (c), a polymerization initiator, and a solvent are charged. into a reaction vessel, stirring, heating, and keeping warm in a deoxygenated environment. The obtained copolymer can be used directly as a reacted solution, as a concentrated or diluted solution, or as a solid (powder) taken out by reprecipitation or other methods.

The ratio of the structural units derived from each of the resin [K3] is preferably in the following range among all the structural units constituting the resin [K3].

Structural unit derived from monomer (a): 2 mol% or more and 55 mol% or less (more preferably 10 mol% or more and 50 mol% or less), structure derived from monomer (c) Unit: 45 mol% or more and 98 mol% or less (more preferably 50 mol% or more and 90 mol% or less).

The resin [K3] can be produced in the same manner as the method described as the production method of the resin [K1].

Resin [K4] can be produced by obtaining a copolymer of monomer (a) and monomer (c), and converting the cyclic ether structure having 2 to 4 carbon atoms in monomer (b) , especially the oxirane ring possessed by the monomer (b1) is added to the monomer Carboxylic acid and/or carboxylic acid anhydride possessed by body (a). Specifically, first, a copolymer of the monomer (a) and the monomer (c) is produced in the same manner as described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of the monomer (a) and the monomer (c).

Structural unit derived from monomer (a): 5 mol% or more and 50 mol% or less (more preferably 10 mol% or more and 45 mol% or less), structure derived from monomer (c) Unit: 50 mol% or more and 95 mol% or less (more preferably 55 mol% or more and 90 mol% or less).

Next, the cyclic ether structure having 2 to 4 carbon atoms in the monomer (b), particularly the oxirane ring possessed by the monomer (b1), and the cyclic ether structure derived from the monomer in the copolymer are A part of the carboxylic acid and/or carboxylic acid anhydride of the compound (a) is reacted. Specifically, after producing the copolymer of the monomer (a) and the monomer (c), the atmosphere in the flask is replaced from nitrogen to air, and the monomer (b) (especially the monomer (b1) ), the reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether structure (such as tris(dimethylaminomethyl)phenol, etc.) and polymerization inhibitor (such as hydroquinone, etc.) are put into the flask, and Resin [K4] can be obtained by reacting at 60℃~130℃ for 1 hour to 10 hours.

The usage amount of the monomer (b), especially the usage amount of the monomer (b1), is preferably 5 moles or more and 80 moles or less, more preferably 10 moles, based on 100 moles of the monomer body (a). More than 75 moles and less than 75 moles. By setting it as this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to become good. The cyclic ether structure is highly reactive and does not easily allow unreacted monomers to remain. (b), the monomer (b) used in the resin [K4] is preferably a monomer (b1), more preferably a monomer (b1-1).

The usage amount of the reaction catalyst is preferably 0.001% by mass relative to the total amount of the monomer (a), the monomer (b) (especially the monomer (b1)) and the monomer (c). More than 5% by mass. The usage amount of the polymerization inhibitor is preferably 0.001 mass % or more and 5 mass % or less relative to the total amount of the monomer (a), the monomer (b), and the monomer (c).

Reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted taking into consideration the production equipment, the amount of heat generated by polymerization, etc. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like.

Regarding the resin [K5], as a first step, the monomer (b) (especially the monomer (b1)) and the monomer (c) are obtained in the same manner as in the manufacturing method of the resin [K1]. copolymer. In the same manner as described above, the obtained copolymer can be used directly as a reacted solution, a concentrated or diluted solution, or a copolymer taken out as a solid (powder) by a method such as reprecipitation.

The ratio of structural units derived from monomer (b) (especially monomer (b1)) and monomer (c) relative to the total molar number of all structural units constituting the copolymer is preferably in the following range.

Structural unit derived from monomer (b), particularly structural unit derived from monomer (b1): 5 mol% or more and 95 mol% or less (more preferably 10 mol% or more and 90 mol%) %the following), Structural unit derived from monomer (c): 5 mol% or more and 95 mol% or less (more preferably 10 mol% or more and 90 mol% or less).

Furthermore, under the same conditions as the production method of resin [K4], the carboxylic acid or carboxylic acid anhydride contained in the monomer (a) and the monomer (b) (especially the monomer (b1)) are mixed with the monomer (b1). Resin [K5] can be obtained by reacting the cyclic ether structure derived from the monomer (b) that the copolymer of the monomer (c) has. The usage amount of the monomer (a) reacted with the copolymer is preferably 5 moles or more and 80 moles or less based on 100 moles of the monomer (b) (especially the monomer (b1)). . Since the cyclic ether structure has high reactivity and unreacted monomer (b) is unlikely to remain, the monomer (b) used in the resin [K5] is preferably the monomer (b1), and more preferably Single quantity (b1-1).

Resin [K6] is a resin obtained by further reacting carboxylic acid anhydride and resin [K5]. Carboxylic anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether structure with carboxylic acid or carboxylic anhydride.

Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, and 3,4,5,6-tetrahydrophthalic anhydride. Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (Nadic acid anhydride) etc.

Among resin [K1] to resin [K6], a preferred resin as the resin (B) is [K1] or [K2]. Resin (B2) may contain one type of resin or two or more types of resin.

The weight average molecular weight (Mw) of the resin (B2) in terms of polystyrene is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000. below, preferably above 5,000 and below 30,000. When the weight average molecular weight (Mw) is within the above range, the solubility of the unexposed portion with respect to the developer tends to be high, and the residual film rate or hardness of the resulting pattern also tends to be high. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B2) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value of the resin (B2) in terms of solid content is preferably 5 mg-KOH/g or more and 200 mg-KOH/g or less, more preferably 50 mg-KOH/g or more and 180 mg-KOH/g or less, and still more preferably 60 mg-KOH/g or more and 140 mg-KOH/g or less. The acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin, and can be determined by titration using a potassium hydroxide aqueous solution, for example.

When the colored curable resin composition contains the resin (B2), the content of the resin (B2) in the solid content of the colored curable resin composition is preferably 1 mass % or more and 50 mass % or less, and is 3 mass %. More than 40% by mass. When the content of the resin (B2) is within the above range, the solubility of the unexposed portion with respect to the developer tends to be high.

The content of the resin (B) in the solid content of the colored curable resin composition is preferably 7% by mass or more and 65% by mass or less, more preferably 13% by mass or more and 60% by mass or less, and still more preferably 17% by mass. More than 55% by mass. When the content rate of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to be improved.

After preparing a colorant-containing liquid in advance, use the colorant-containing liquid to prepare When preparing a colored curable resin composition, the colorant-containing liquid may previously contain part or all of the resin (B) described below contained in the colored curable resin composition, preferably a part. By containing the resin (B) in advance, the dispersion stability of the colorant-containing liquid can be further improved. It is preferable that the colorant-containing liquid contains resin (B2) in advance.

The content of the resin (B) in the colorant-containing liquid may be, for example, 10,000 parts by mass or less, preferably 5,000 parts by mass or less, more preferably 1,000 parts by mass or less, based on 100 parts by mass of the colorant (A), and still more preferably The amount is from 1 part by mass to 500 parts by mass, particularly preferably from 5 parts by mass to 200 parts by mass, and particularly preferably from 10 parts by mass to 100 parts by mass.

[3]Polymerizable compound (C)

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) due to light irradiation or the like, and examples thereof include polymerizable ethylenically unsaturated compounds. Bonded compounds, etc. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less, more preferably 1,500 or less.

Among these, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and examples thereof include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. ) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate Acrylate, pentaerythritol ten (meth)acrylate, pentaerythritol nona (meth)acrylate, tris (2-(meth)acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol Tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, Propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate ) acrylate, etc. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferred.

The colored curable resin composition of the present invention may contain one or more polymerizable compounds (C). The content of the polymerizable compound (C) is preferably not less than 20 parts by mass and not more than 150 parts by mass, more preferably not less than 40 parts by mass and not more than 110 parts by mass, based on 100 parts by mass of the resin (B) in the colored curable resin composition. the following.

The content rate of the polymerizable compound (C) is preferably not less than 7% by mass and not more than 65% by mass, more preferably not less than 13% by mass and not more than 60% by mass, and still more preferably not less than 17% by mass relative to the total amount of solid content. And less than 55% by mass. When the content rate of the polymerizable compound (C) is within the above range, the residual film rate during formation of the colored pattern and the chemical resistance of the color filter tend to improve.

[4]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 to initiate polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include oxime-based compounds such as O-acyl oxime compounds, phenylalkyl ketone compounds, biimidazole compounds, triazine compounds, acyl phosphine oxide compounds, and the like.

In consideration of sensitivity, formation of precise pattern shapes, etc., two or more types of polymerization initiators (D) may be used in combination. To produce the desired line with sensitivity and precision From the viewpoint of a wide pattern shape, the polymerization initiator (D) preferably contains an oxime-based compound such as an O-acyl oxime compound.

The O-acyl oxime compound is a compound having a structure represented by formula (d). In the following, * indicates a bonding key.

Examples of such O-benzyl oxime compounds include: N-benzyloxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzyloxy Base-1-(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylmercaptophenyl)-3-cyclopentyl Propan-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane -1-imine, N-ethyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolane) methyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-(2-methyl Benzylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, etc., wherein the O-acyl oxime compound is preferably selected from N- Benzyloxy-1-(4-phenylmercaptophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylmercaptophenyl)octane -The group consisting of 1-keto-2-imine and N-benzyloxy-1-(4-phenylmercaptophenyl)-3-cyclopentylpropane-1-one-2-imine at least one of them. You can also use Irgacure OXE01, Commercially available products such as OXE02 and OXE03 (above, manufactured by BASF Co., Ltd.), N-1919 (manufactured by ADEKA Co., Ltd.). If these O-acyl oxime compounds are used, a color filter excellent in photolithography performance tends to be obtained.

The phenylalkyl ketone compound is a compound having a structure represented by formula (d4) or a structure represented by formula (d5). * indicates bonding. In these structures, the benzene ring may have a substituent.

Examples of compounds having a structure represented by formula (d4) include: 2-methyl-2-morpholinyl-1-(4-methylmercaptophenyl)propan-1-one and 2-dimethylamine Base-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- 1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. Commercially available products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Co., Ltd.) can also be used.

Examples of compounds having a structure represented by formula (d5) include: 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-( 2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomers, α,α-diethoxyacetophenone, benzyldimethyl ketal, etc.

In terms of sensitivity, the phenylalkyl ketone compound is preferably one having the formula (d4) compound of the structure represented.

Examples of the biimidazole compound include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-bis Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis (Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62 -174204, etc.), a biimidazole compound in which the phenyl group at the 4,4', 5,5'-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913, etc.), etc. Among them, compounds represented by the following formula or mixtures thereof are preferred.

Examples of triazine compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) base)-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, etc.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, and methyl o-benzoyl benzoate. , 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)diphenyl Methyl ketone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2- Chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization starting aid (D1) (especially an amine) described below.

The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and less, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 20 parts by mass or less. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to become high and the exposure time tends to be shortened. Therefore, the productivity of the color filter tends to be improved.

[5]Polymerization starting aid (D1)

The polymerization starting aid (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound started by the polymerization initiator. Contains aggregate starting helper In the case of agent (D1), it is used in combination with the polymerization initiator (D).

Examples of the polymerization starting aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like. Among these, thioxanthone compounds are preferred. Two or more polymerization starting aids (D1) may be used in combination.

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

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

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

Examples of carboxylic acid compounds include: phenylthioglycolic acid, methylphenylthioglycolic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylmercaptoacetic acid, and methoxyphenylmercaptoacetic acid. Acetic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, Naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.

The content of the polymerization starting aid (D1) is preferably not less than 0.1 parts by mass and not more than 30 parts by mass, more preferably not less than 1 part by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). And less than 20 parts by mass. If the content of the polymerization starting aid (D1) is within the above range, a blue pattern can be formed with further high sensitivity, and the productivity of the color filter tends to be improved.

[6]Solvent (E)

The colored curable resin composition of the present invention preferably contains one or more solvents (E). Examples of the solvent (E) include ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), and ether ester solvents (solvents containing -COO- and -O-). , ketone solvents other than ester solvents (solvents including -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, Isopropyl butyrate, Ethyl butyrate, Butyl butyrate, Methyl pyruvate, Ethyl pyruvate, Propyl pyruvate, Methyl acetate acetate, Ethyl acetate acetate, Ring Hexanol acetate and γ-butyrolactone, etc.

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

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyethyl acetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropylpropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl 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 acid ester and dipropylene glycol methyl ether acetate, etc.

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

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, and the like. Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

In terms of coating properties and drying properties, the solvent (E) preferably contains an organic solvent having a boiling point at 1 atm of 120° C. or more and 180° C. or less. Among them, the solvent (E) is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol Alcohol monomethyl ether, 3-ethoxyethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3- At least one of the group consisting of methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide, preferably one selected from the group consisting of propylene glycol Monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and 3-ethoxy At least one of the group consisting of ethyl propionate.

The content of the solvent (E) in the colored curable resin composition is preferably 70 mass% or more and 95 mass% or less, more preferably 75 mass% or more and 92 mass% or less. In other words, the solid content of the colored curable resin composition is preferably 5 mass% or more and 30 mass% or less, more preferably 8 mass% or more and 25 mass% or less. When the content of the solvent (E) is within the above range, the flatness during coating tends to be good, and the color density will not be insufficient when forming a color filter, so the display characteristics tend to be good.

[7]Leveling agent (F)

The colored curable resin composition of the present invention may contain one or more leveling agents (F). Examples of the leveling agent (F) include silicone surfactants (not having fluorine atoms), fluorine surfactants, silicone surfactants having fluorine atoms, and the like. These may have a polymerizable group in a side chain.

Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Toray Dow Corning (Toray Dow Corning) ), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Japanese Momentive High-tech materials (Momentive Performance Materials Japan) Co., Ltd.), etc.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac )F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Co., Ltd.), 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 (Asahi Glass (Manufactured by Daikin Fine Chemicals Research Institute) and E5844 (manufactured by Daikin Fine Chemicals Research Institute), etc.

Examples of silicone-based surfactants having fluorine atoms include those having fluorine atoms in the molecule. Surfactants with siloxane bonds and fluorocarbon chains. Specifically, examples include: Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477 and Megafac F443 (DIC). ) (shares, manufacturing), etc.

The content of the leveling agent (F) in the colored curable resin composition is usually 0.001 mass% or more and 0.6 mass% or less, preferably 0.002 mass% or more and 0.4 mass% or less, more preferably 0.005 mass% or more and 0.3 mass% mass% or less. Furthermore, the content of the pigment dispersant is not included in the content.

[8]Other ingredients

The colored curable resin composition of the present invention may contain one or more fillers, polymer compounds other than resin (B), adhesion accelerator, ultraviolet absorber, antioxidant, anti-aggregation agent, organic acid, Organic amine compounds, hardeners and other additives.

<Production method of colored curable resin composition>

The colored curable resin composition of the present invention can be obtained by leveling the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the optional solvent (E). Agent (F), polymerization starting aid (D1), and other ingredients are mixed and prepared.

<Color filter, manufacturing method thereof, and display element>

The colored curable resin composition of the present invention is useful as a material for color filters. A color filter formed from the colored curable resin composition of the present invention also falls within the scope of the invention of the present application. Color filters can also create tinted patterns.

As a method for producing a colored pattern from the colored curable resin composition of the present invention Methods include: photolithography method, inkjet method, printing method, etc. Preferably, photolithography method can be mentioned. The photolithography method is a method of applying a colored curable resin composition on a substrate, drying it to form a colored composition layer, and exposing and developing the colored composition layer through a light mask. In the photolithography method, by not using a photomask during exposure and/or not performing development, a colored coating film that is a cured product of the colored composition layer can be formed. The colored pattern or colored coating film formed from the colored curable resin composition of the present invention is the color filter of the present invention. The color filter of the present invention is typically used as a coloring pixel.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass with a silica-coated surface can be used; or polycarbonate, polymethyl methacrylate, poly(methylmethacrylate), etc. Resin plates such as ethylene terephthalate; silicon; aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. may also be formed on the substrates.

The formation of each colored pixel by the photolithography method can be carried out under known or conventional equipment or conditions, for example, it can be produced as follows. First, the colored curable resin composition is applied to a substrate, and is heated and dried (prebaked) and/or dried under reduced pressure to remove volatile components such as solvents and dry them, thereby obtaining a smooth colored composition. layer. Examples of coating methods include spin coating, slit coating, slit and spin coating, and the like.

The temperature during heat drying is preferably 30°C to 120°C, more preferably 50°C to 110°C. In addition, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When drying under reduced pressure, it is preferably between 50Pa and 150Pa. under pressure and in a temperature range of 20°C to 25°C. The film thickness of the coloring composition layer is not particularly limited and may be appropriately selected according to the film thickness of the target color filter.

Then, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on this photomask is not particularly limited, and a pattern corresponding to the intended use can be used. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 nm to 450 nm. For example, you can also use a filter that cuts off the wavelength range of less than 350 nm, or you can use a band pass filter that cuts out the light in those wavelength ranges around 436 nm, 408 nm, and 365 nm. filter) for selective removal. Specifically, the light source may include: mercury lamp, light emitting diode, metal halide lamp, halogen lamp, etc.

During exposure, in order to irradiate the entire exposure surface with parallel light evenly or to accurately align the mask and the substrate on which the colored composition layer is formed, it is best to use a mask aligner and a stepper. Exposure equipment such as stepper.

The exposed colored composition layer is brought into contact with a developer and developed, thereby forming a colored pattern on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer and removed.

The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 mass% to 10 mass%, more preferably 0.03 mass% to 5 mass%. Furthermore, the developer may contain a surfactant.

The development method may be any one of liquid coating method, dipping method, spray method, etc. Furthermore, the substrate can be tilted at any angle during development. After development, it is better to Wash with water.

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

The film thickness of the resulting coloring pattern will affect adjacent pixels, so it is preferably as thin as possible. Especially when the film is thick, when producing a liquid crystal panel, the light from the light source may leak through pixels of two or more colors. When the panel is viewed from an oblique direction, the vividness of the colors may be lost. Yu. Generally speaking, the film thickness of the colored pattern after post-baking is preferably 3 μm or less, more preferably 2.8 μm or less. The lower limit of the film thickness of the colored pattern is not particularly limited, but is usually 0.2 μm or more, and may be 0.5 μm or more. The colored curable resin composition of the present invention shows excellent developability when producing a colored pattern, and therefore is excellent as a color filter material.

The colored coating film formed from the colored curable resin composition of the present invention has excellent light resistance and preferably also excellent heat resistance. The light resistance (ΔEab*) of the colored coating film formed from the colored curable resin composition of the present invention may be, for example, less than 5.0, preferably 4.9 or less, and more preferably 4.8 or less. According to the present invention, in a colored coating film formed from a colored curable resin composition containing a specific colorant, compared with a colored coating film formed from a colored curable resin composition containing the same colorant and not according to the present invention, , the light resistance (ΔEab*) of the colored coating film can be reduced, for example, by 0.5 or more, preferably by 1.0 or more, and more preferably by 2.0 or more. The light resistance (ΔEab*) can be measured according to the method described in the Example column described below.

The color filter of the present invention is excellent in light resistance, preferably heat resistance and developability, and therefore is used as a color filter used in display elements, such as liquid crystal display elements, organic EL elements, electronic paper, etc., and solid-state imaging elements. Light and useful.

[Example]

Hereinafter, the curable resin composition of the present invention will be described with reference to specific examples. However, the present invention is not limited to the following examples unless the gist thereof is exceeded. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". In addition, unless otherwise specified, the reaction was carried out under a nitrogen atmosphere.

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

The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by gel permeation chromatography (GPC) using the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Tube string temperature: 40℃

Solvent: tetrahydrofuran (THF)

Flow rate: 1.0mL/min

Solid content concentration of the liquid to be tested: 0.001 mass%~0.01 mass%

Injection volume: 50μL

Detector: refractive index (RI)

Calibration standard material: TSK standard polystyrene

F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

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

The acid value of the resin in terms of solid content is a value obtained by titrating a solution containing the resin using an aqueous potassium hydroxide solution to determine the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin.

[Synthesis example 1]

The salt represented by formula (A-IV-27) is synthesized according to the method described in Japanese Patent Application Laid-Open No. 2015-38201.

[Synthesis example 2]

40.5 parts of the compound represented by formula (a2) and 60.5 parts of 2,6-xylidine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under light-shielding conditions, and mixed with 150 parts of N-methylpyridone in 200 parts of N-methylpyridone. °C and stirred for 8 hours. Cool the resulting mixture to room temperature Then, add it to a mixture of 1,200 parts of water and 75 parts of 35% hydrochloric acid, and stir at room temperature for 1 hour. As a result, crystals precipitate. The precipitated crystals were obtained by suction filtration, washed with 100 parts of methanol, and dried under reduced pressure at 60° C. overnight to obtain 49 parts of the compound represented by formula (a3). The yield is 85%.

Next, 28.8 parts of the compound represented by formula (a3), 21.6 parts of 1-bromopropane, and 24.2 parts of potassium carbonate were added to 144 parts of N-methylpyridone, and the mixture was stirred at 90° C. for 4 hours. The obtained reaction mixture was cooled to room temperature, concentrated, added to 560 parts of water, and stirred at 10°C to 15°C for 1 hour. As a result, crystals precipitated. The resulting crystals were collected by suction filtration, dried, washed with 1000 parts of ion-exchange water, and dried under reduced pressure at 60° C. overnight to obtain a compound represented by formula (1-32) (hereinafter referred to as compound (A-2)) 30.0 copies. The yield is 91%.

Identification of compound (A-2)

(Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 659.3

Exact Mass: 658.3

[Synthesis example 3]

According to the method described in Example 2 of Japanese Patent Application Laid-Open No. 2017-226814, 1.0 part of the compound represented by formula (1-97) (hereinafter, described as compound (A-4)) was obtained.

Identification of compounds represented by formula (1-199)

(Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 747.5

Exact Mass: 746.3

[Synthesis Example 4]

According to the method described in Example 1 of Japanese Patent Application Laid-Open No. 2016-27075, 52 parts of the compound represented by formula (1-44) (hereinafter, described as compound (A-5)) were obtained.

Identification of compounds represented by formula (1-34)

(Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 599.2

Exact Mass: 598.2

[Synthesis example 5-1]

(Synthesis of resin (B1-1a))

In a separable flask, the propylene glycol monomethyl ether acetate solution of bisphenol A type epoxy acrylate was 66.6 parts and 1,2,4,5-cyclohexanetetracarboxylic dianhydride 17.4 parts in terms of solid content. Mix 32.7 parts of propylene glycol monomethyl ether acetate with 32.7 parts of propylene glycol monomethyl ether acetate, and slowly raise the temperature to react at 100°C to 105°C for 14 hours. Thereafter, propylene glycol monomethyl ether acetate was added 7.2 parts were diluted to obtain a copolymer (resin (B1-1a) solution; solid content 56.9%) having a structure represented by the following formula (B1-1). The acid value of the obtained copolymer was 113.7 mg-KOH/g in terms of solid content, and the weight average molecular weight Mw was 6,400.

[In formula (B1-1), k represents an integer from 0 to 10, and m represents an integer from 1 to 50]

[Synthesis example 5-2]

(Synthesis of resin (B1-1b))

In a separable flask, the propylene glycol monomethyl ether acetate solution of bisphenol A type epoxy acrylate was 66.6 parts and 1,2,4,5-cyclohexanetetracarboxylic dianhydride 20.2 parts in terms of solid content. Mix 32.7 parts of propylene glycol monomethyl ether acetate with 32.7 parts of propylene glycol monomethyl ether acetate, and slowly raise the temperature to react at 100°C to 105°C for 14 hours. Thereafter, 9.6 parts of propylene glycol monomethyl ether acetate was added and diluted to obtain a copolymer having a structure represented by formula (B1-1) (resin (B1-1b) solution; solid content 58.5%). The acid value of the obtained copolymer was 126.0 mg-KOH/g in terms of solid content, and the weight average molecular weight Mw was 10,200.

[Synthesis example 6]

An appropriate amount of nitrogen was circulated in a flask equipped with a reflux cooler, a dropping funnel and a stirrer to replace it with a nitrogen environment. 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were put in and heated to 85°C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxy tricyclo acrylate [5.2.1.0 ^2,6 ] decane-8-yl ester and 3,4-epoxy tricyclo acrylate [5.2.1.0 ^{2 , 6} ] 25 parts of a mixture of decane-9-yl esters (the molar ratio is 1:1), 137 parts of N-cyclohexylmaleimide, and 50 parts of 2-hydroxyethyl methacrylate. , a mixed solution of 338 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution in which 5 parts of 2,2-azobisisobutyronitrile was dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition, the mixture was kept at 85°C for 4 hours, and then cooled to room temperature. The viscosity measured with a B-type viscometer (23°C) was 23mPa. s. A copolymer (resin (B-2)) solution with a solid content of 25.6%. The weight average molecular weight Mw of the produced copolymer was 8.0×10 ³ , the dispersion degree was 2.1, and the acid value in terms of solid content was 110 mg-KOH/g. Resin (B2-1) has the following structural units.

[Synthesis Example 7]

An appropriate amount of nitrogen was circulated in a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere. 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxy tricyclo acrylate [5.2.1.0 ^2,6 ] decane-8-yl ester and 3,4-epoxy tricyclo acrylate [5.2.1.0 ^{2 , 6} ] A mixed solution of 289 parts of a mixture of decane-9-yl esters (the molar ratio is 1:1) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution in which 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved 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 solid content of 35.1% and a viscosity of 125 mPa measured with a B-type viscometer (23°C). s copolymer (resin (B-3)) solution. The weight average molecular weight MW of the produced copolymer was 9.2×10 ³ , the dispersion degree was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. Resin (B2-2) has the following structural units.

[Preparation of dispersion 1]

51.2 parts of the salt represented by the formula (A-IV-27) obtained in Synthesis Example 1 and 21.4 parts of the dispersant (BYKLPN-6919 manufactured by BYK; propylene glycol monomethyl ether acetate 60% solution) parts, resin (B2-2) (solid content conversion) 20.5 parts, and 334 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion (A-1).

[Preparation of dispersion 2]

Mix 46.5 parts of C.I. Pigment Red 269, 23.2 parts of dispersant (converted to solid content), 13.9 parts of resin (B2-2) (converted to solid content), 57.7 parts of propylene glycol monomethyl ether, and 246 parts of propylene glycol monomethyl ether acetate. , and add 600 parts of 0.4 μm zirconia beads, and shake for 1 hour using a paint mixer (manufactured by LAU Corporation). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion (A-3).

[Example 1 to Example 5, Comparative Example 1 to Comparative Example 4]

[Preparation of colored curable resin composition]

Each component shown in Table 3 was mixed to obtain each colored curable resin composition.

． Colorant (A): Dispersion (A-1): Dispersion (A-1) obtained in [Preparation of Dispersion 1], Dispersion (A-3): Dispersion (A-3) obtained in [Preparation of Dispersion 2] Dispersion (A-3), coloring agent (A-2): compound (A-2) obtained in [Synthesis Example 2], coloring agent (A-4): compound (A) obtained in [Synthesis Example 3] -4), coloring agent (A-5): compound (A-5) obtained in [Synthesis Example 4],. Resin (B): (B1-1a): Resin (B1-1a) obtained in [Synthesis Example 5-1] (solid content conversion), (B1-1b): Resin (B1-1b) obtained in [Synthesis Example 5-2] (solid content conversion), (B2-1): Resin (B2-1) obtained in [6] (solid content conversion) ),. Polymeric compound (C)

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

． Polymerization initiator (D): (D-1): N-benzyloxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine (Irgacure ) (registered trademark) OXE-01; manufactured by BASF; oxime compound)

． Solvent (E):

(E-1): Ethyl lactate

(E-2): Propylene glycol monomethyl ether acetate

(E-3): diacetone alcohol

． Leveling agent (F):

(F-1): Polyether modified silicone oil (solid content conversion)

(Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

The obtained colored curable resin composition was evaluated by the following method. The results are shown in Table 3.

<Formation of color filter (colored coating film)>

The colored curable resin composition is coated on a 2-inch square glass substrate (Eagle 2000: manufactured by Corning Corporation) by spin coating, and then pre-baked at 100°C for 3 minutes to form the color. composition layer. After cooling, an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to irradiate the colored composition layer with light at an exposure dose of 60 mJ/cm ² (based on 365 nm) in an atmospheric environment. After light irradiation, post-baking is performed in an oven at 230° C. for 20 minutes to obtain a colored coating film. After leaving to cool, the film thickness of the obtained colored coating film was measured using a film thickness measuring device (DEKTAK 3; manufactured by Nippon Vacuum Technology Co., Ltd.). The result was 3.0 μm.

<Evaluation of light resistance>

For the thin film on the obtained glass substrate, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the International Commission on Illumination (Commission) was measured using the color matching function of the C light source. The xy chromaticity coordinates (x, y) and Y in the XYZ color system of the Internationale de I'Eclairage (CIE). The pattern was illuminated using a xenon lamp for 48 hours. After irradiation, the xy chromaticity coordinates and Y are measured again, and based on the measured values, the color difference Δ before and after irradiation is calculated using the method described in Japanese Industrial Standards (JIS) Z 8730: 2009 (7. Calculation method of color difference). Eab*. The results are shown in Table 3.

[table 3]

Unit: parts by mass

In the pattern formed using the colored curable resin composition of Examples 1 to 2, ΔEab* showed a smaller value than that of Comparative Example 1, and high light resistance was confirmed.

In the pattern formed using the colored curable resin composition of Example 3, ΔEab* showed a smaller value than that of Comparative Example 2, and high light resistance was confirmed.

In the pattern formed using the colored curable resin composition of Example 4, ΔEab* showed a smaller value than that of Comparative Example 3, and high light resistance was confirmed.

In the pattern formed using the colored curable resin composition of Example 5, ΔEab* showed a smaller value than that of Comparative Example 4, and high light resistance was confirmed.

Compared with Comparative Examples 1 to 4, Example 1 following the invention of this application ~The ΔEab* of Example 5 was all small, and high light resistance was confirmed. It is understood that the colored curable resin composition according to the invention of the present application can form an excellent colored coating film.

[Industrial availability]

According to the colored curable resin composition of the present invention, a colored coating film with excellent light resistance can be formed, and is extremely useful industrially.

Claims (6)

A colored curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the resin (B) contains the following formula (B1) The acid value of the resin represented by the formula (B1) in terms of solid content is 80 mg-KOH/g or more and 140 mg-KOH/g or less:

[In the formula, Z represents the residue of a tetracarboxylic acid with an alicyclic skeleton; G represents a hydrogen atom or -CO-X-(CO ₂ H)x, and X represents the residue of a (x+1)-valent polycarboxylic acid , x represents an integer from 1 to 3; R ¹ represents a hydrogen atom or a methyl group, and multiple R ^1s may be the same or different from each other; R ² represents an alkyl group or a halogen atom with a carbon number of 1 to 5 , when there are multiple R ^2s , the multiple R ^2s may be the same as each other, or they may be different; k represents an integer from 0 to 10, n represents an integer from 0 to 4, and m represents 1 or more. and an integer below 50]. The colored curable resin composition according to claim 1, wherein in the formula (B1), Z is the residue of a tetracarboxylic acid having an alicyclic skeleton having 4 to 10 carbon atoms. base. The colored curable resin composition according to Claim 1 or 2, wherein in the formula (B1), Z is a residue of a tetracarboxylic acid having a saturated alicyclic skeleton having 4 to 6 carbon atoms. A color filter formed from the colored curable resin composition according to any one of claims 1 to 3. A display element including the color filter as described in claim 4. A solid-state imaging element including the color filter according to claim 4.