TW202305504A - Colored resin composition, color filter and display device - Google Patents

Abstract

The invention relates to a colored resin composition, a color filter and a display device. The present invention addresses the problem of providing a colored resin composition capable of forming a color filter exhibiting good contrast. The solution of the present invention is a colored resin composition containing a colorant and a resin, the colorant including a compound represented by formula (I). In formula (I), R1-R3 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1-20 carbon atoms. R2 and R3 may form, together with the nitrogen atom to which each is bonded, a ring that may have a substituent. R4 to R8 independently represent a hydrogen atom,-R9,-O-R9,-CO-O-R9,-O-CO-R9, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, or a nitro group. R9 represents a C1-20 hydrocarbon group which may have a substituent, and when a plurality of R9 are present, the R9 may be the same as or different from each other.

Description

Colored resin composition, color filter, and display device

The invention relates to a colored resin composition, a color filter, and a display device.

Used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, or solid-state imaging devices such as CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor) sensors The color filter is made of colored resin composition. A perylenetetracarboxylic acid diimide compound is known as a coloring agent contained in such a colored resin composition (Patent Document 1). [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2020-079397

[Problem to be solved by the invention]

However, the conventionally known color filter formed from a colored resin composition using a perylenetetracarboxylic diimide compound as a colorant sometimes cannot sufficiently satisfy contrast. Therefore, the subject of this invention is providing the colored resin composition which can form the color filter which shows favorable contrast. [Technical means to solve the problem]

[式(I)中， R ¹～R ³彼此獨立地表示氫原子或可具有取代基之碳數1～20之烴基； R ²與R ³可與各自鍵結之氮原子一起形成可具有取代基之環； R ⁴～R ⁸彼此獨立地表示氫原子、-R ⁹、-O-R ⁹、-CO-O-R ⁹、-O-CO-R ⁹、鹵素原子、羥基、羧基、磺基、或硝基； R ⁹表示可具有取代基之碳數1～20之烴基，於R ⁹存在複數個之情形時，其等可相同，亦可不同]。 [2]如[1]之著色樹脂組合物，其進而含有聚合性化合物、及聚合起始劑。 [3]一種彩色濾光片，其係由如[1]或[2]之著色樹脂組合物形成。 [4]一種顯示裝置，其包含如[3]之彩色濾光片。 [發明之效果] The gist of the present invention is as follows. [1] A colored resin composition comprising a colorant and a resin, and the colorant comprises a compound represented by formula (I),

[In formula (I), R ¹ to R ³ independently represent a hydrogen atom or a hydrocarbon group with a carbon number of 1 to 20 that may have a substituent; R ² and R ³ may form a substituent R ⁴ ~ R ⁸ independently represent a hydrogen atom, -R ⁹ , -OR ⁹ , -CO-OR ⁹ , -O-CO-R ⁹ , halogen atom, hydroxyl, carboxyl, sulfo, or nitric acid R ⁹ represents a hydrocarbon group with 1 to 20 carbon atoms that may have a substituent, and when there are multiple R ⁹ s, they may be the same or different]. [2] The colored resin composition according to [1], further comprising a polymerizable compound and a polymerization initiator. [3] A color filter formed of the colored resin composition according to [1] or [2]. [4] A display device comprising the color filter of [3]. [Effect of Invention]

According to the present invention, there can be provided a colored resin composition capable of forming a color filter exhibiting good contrast.

The colored resin composition of the present invention contains a colorant (hereinafter, may be referred to as a colorant (A)) and a resin (hereinafter, may be referred to as a resin (B)). The colored resin composition of the present invention may further contain a polymerizable compound (hereinafter, may be referred to as a polymerizable compound (C)) and a polymerization initiator (hereinafter, may be referred to as a polymerization initiator (D)). The colored resin composition of the present invention may further contain a solvent (hereinafter, may be referred to as a solvent (E)). The colored resin composition of the present invention may further contain a polymerization initiation aid (hereinafter, may be referred to as a polymerization initiation aid (D1)). The colored resin composition of the present invention may further contain a leveling agent (hereinafter, may be referred to as a leveling agent (F)). In addition, in this specification, unless otherwise specified, the compound illustrated as each component can be used individually or in combination of several types.

＜Colorant (A)＞ The coloring agent (A) contains the compound (it may refer to a compound (I) hereafter) represented by formula (I). The colored resin composition of the present invention can form a color filter exhibiting good contrast by including the compound (I) in the colorant (A), preferably a color filter excellent in heat resistance and light resistance piece.

[式(I)中， R ¹～R ³彼此獨立地表示氫原子、或可具有取代基之碳數1～20之烴基； R ²與R ³可與各自鍵結之氮原子一起形成可具有取代基之環； R ⁴～R ⁸彼此獨立地表示氫原子、-R ⁹、-O-R ⁹、-CO-O-R ⁹、-O-CO-R ⁹、鹵素原子、羥基、羧基、磺基、或硝基； R ⁹表示可具有取代基之碳數1～20之烴基，於R ⁹存在複數個之情形時，其等可相同，亦可不同]。 ＜＜Compound (I)＞＞

[In formula (I), R ¹ to R ³ independently represent a hydrogen atom, or a hydrocarbon group with a carbon number of 1 to 20 that may have a substituent; R ² and R ³ may form together with their respective bonded nitrogen atoms and may have A ring of substituents; R ⁴ to R ⁸ independently represent a hydrogen atom, -R ⁹ , -OR ⁹ , -CO-OR ⁹ , -O-CO-R ⁹ , a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, or Nitro; R ⁹ represents a hydrocarbon group with 1 to 20 carbon atoms which may have a substituent, and when there are multiple R ⁹ , they may be the same or different].

The hydrocarbon group having 1 to 20 carbons represented by R ¹ to R ³ and R ⁹ may, for example, be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be chain or alicyclic.

Examples of saturated or unsaturated chain hydrocarbon groups represented by R ¹ to R ³ and R ⁹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl , Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Two Linear alkyl of dedecyl; isopropyl, (1-ethyl) propyl, isobutyl, second butyl, third butyl, (3-methyl) butyl, (1-methyl) Base) butyl, (1-ethyl) butyl, (2-methyl) butyl, (2-ethyl) butyl, (1-propyl) butyl, isopentyl, neopentyl, th Tripentyl, (2-methyl)pentyl, (3-methyl)pentyl, (1-ethyl)pentyl, (2-ethyl)pentyl, (3-ethyl)pentyl, ( 1-propyl)pentyl, (1-butyl)pentyl, (2-propyl)pentyl, isohexyl, (2-methyl)hexyl, (5-methyl)hexyl, (1-ethyl) )hexyl, (2-ethyl)hexyl, (1-propyl)hexyl, (2-propyl)hexyl, (1-butyl)hexyl, (2-butyl)hexyl, (1-pentyl)hexyl , (2-methyl)heptyl, (2-ethyl)heptyl, (3-ethyl)heptyl, (2-propyl)heptyl, (1-butyl)heptyl, (2-butyl Base) heptyl, (1-pentyl) heptyl, (2-pentyl) heptyl, (1-hexyl) heptyl, (2-methyl) octyl, (2-ethyl) octyl, ( 2-propyl)octyl, (2-butyl)octyl, (1-pentyl)octyl, (2-pentyl)octyl, (1-hexyl)octyl, (2-hexyl)octyl , (1-heptyl) octyl, (2-ethyl) nonyl, (2-propyl) nonyl, (2-butyl) nonyl, (2-pentyl) nonyl, (1-hexyl ) nonyl, (2-hexyl) nonyl, (1-heptyl) nonyl, (1-octyl) nonyl, (2-propyl) decyl, (2-butyl) decyl, (2 -Pentyl) decyl, (2-hexyl) decyl, (1-heptyl) decyl, (2-butyl) undecyl and other branched alkyl groups; vinyl, 1-propenyl, 2 -propenyl (allyl), (1-methyl) vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1-(2 -propenyl))ethenyl, (1,2-dimethyl)propenyl, alkenyl such as 2-pentenyl, etc. The carbon number of the saturated chain hydrocarbon group is preferably 1-18, more preferably 1-16, still more preferably 1-15. In addition, the number of carbon atoms in the unsaturated chain hydrocarbon group is preferably 2-18, more preferably 2-16, and still more preferably 2-15.

Examples of saturated or unsaturated alicyclic hydrocarbon groups represented by R ¹ to R ³ and R ⁹ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Alkyl; cyclohexenyl (such as cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, cyclooctenyl and other cycloalkenyl groups; .2] Octyl et al. The number of carbon atoms in the saturated or unsaturated alicyclic hydrocarbon group is preferably 3-18, more preferably 3-16, still more preferably 3-15.

The aromatic hydrocarbon group represented by R ¹ to R ³ and R ⁹ may, for example, be phenyl, 1-naphthyl, 2-naphthyl, phenanthrenyl, anthracenyl or pyrenyl. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-20, more preferably 6-18, still more preferably 6-15.

The hydrocarbon groups represented by R ¹ to R ³ and R ⁹ may be a combination of two or more of the above-mentioned chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups as long as the upper limit of the carbon number is 20 or less. The foundation of success. Such a group may be, for example, a combination of an aromatic hydrocarbon group and at least one group selected from a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. In the hydrocarbon group obtained by this combination, a combination of A chain hydrocarbon group is used as a divalent group (for example, an alkanediyl group). Examples of hydrocarbon groups obtained by combination include: benzyl, phenethyl, 1-methyl-1-phenylethyl, 1-naphthylmethyl, 2-naphthylmethyl, diphenyl Methyl, 2,2-diphenylethyl, 3,3-diphenylpropyl, 4,4-diphenylbutyl and other aralkyl groups; phenylvinyl (phenylvinyl) and other aryl groups Alkenyl; aryl alkynyl such as phenylethynyl; o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3- Dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5- Dimethylphenyl, 2,4,6-trimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, 2,3- Diisopropylphenyl, 2,4-diisopropylphenyl, 2,5-diisopropylphenyl, 2,6-diisopropylphenyl, 3,5-diisopropylphenyl , 2,4,6-triisopropylphenyl, 4-butylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, 2,6-di (Tertiary butyl)phenyl, 3,5-di(tertiary butyl)phenyl, 3,6-bis(tertiary butyl)phenyl, 4-tertiary butyl-2,6-dimethyl phenyl, 4-pentylphenyl, 4-octylphenyl, 4-(2,4,4-trimethyl-2-pentyl)phenyl, 2-dodecylphenyl, 3- Dodecylphenyl, 4-dodecylphenyl and other alkylaryl groups; o-trimethyl, m-tolylmethyl, p-tolylmethyl, 2-ethylphenylmethyl, 3-ethyl phenylmethyl, 4-ethylphenylmethyl, 2,3-dimethylphenylmethyl, 2,4-dimethylphenylmethyl, 2,5-dimethylphenylmethyl , 2,6-dimethylphenylmethyl, 3,4-dimethylphenylmethyl, 3,5-dimethylphenylmethyl, 2,4,6-trimethylphenylmethyl , 4-vinylphenylmethyl, o-isopropylphenylmethyl, m-isopropylphenylmethyl, p-isopropylphenylmethyl, 2,3-diisopropylphenylmethyl, 2,4-Diisopropylphenylmethyl, 2,5-Diisopropylphenylmethyl, 2,6-Diisopropylphenylmethyl, 3,5-Diisopropylphenylmethyl 2,3-dihydro-4-indenyl, 1,2,3,5,6,7-hexahydro-4-second cyclopentadienyl, 8-methyl Base-1,2,3,5,6,7-hexahydro-4-second cyclopentadienyl, 5,6,7,8-tetrahydro-1-naphthyl, 5,6,7 ,8-tetrahydro-2-naphthyl, 3-methyl-5,6,7,8-tetrahydro-2-naphthyl, 3,5,5,8,8-pentamethyl-5,6, 7,8-tetrahydro-2-naphthyl and other aryl groups bonded with alkanediyl; biphenyl, terphenyl and other aryl groups bonded with more than one aryl group; cyclohexylmethylphenyl , benzylphenyl, (dimethyl(phenyl)methyl)phenyl, etc. In addition, the above-mentioned hydrocarbon group may be, for example, a hydrocarbon group obtained by combining a chain hydrocarbon group and an alicyclic hydrocarbon group. As examples, 1-methylcyclopropyl, 2-methylcyclopentyl, 3-methylcyclopentyl, Cyclopentyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethyl Cyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethyl Cyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4,4-dimethyl Cyclohexyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl, 4-pentylcyclohexyl, 4-octylcyclohexyl, 4-cyclohexylcyclohexyl and other alicyclic hydrocarbon groups bonded with more than one alkyl group; cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl , cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, adamantylmethyl and other alkyl groups bonded to one or more alicyclic hydrocarbon groups; 2-methylcyclopropyl methyl, 2-methylcyclobutylmethyl, 3-methylcyclobutylmethyl, 2-methylcyclopentylmethyl, 3-methylcyclopentylmethyl, 2-methylcyclohexylmethyl, 3 - Alkyl groups such as methylcyclohexylmethyl and 4-methylcyclohexylmethyl, in which an alicyclic hydrocarbon group to which at least one alkyl group is bonded, etc. The carbon number of the group formed by combining two or more chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups is preferably 4-20, more preferably 5-18, and still more preferably 6-16.

Examples of -OR ⁹ include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, third butoxy, pentyloxy Base, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, (2-ethyl)hexyloxy, eicosyloxy, 1-phenylethoxy, 1-methyl -1-phenylethoxy, phenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6- Dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, etc.

As -CO-OR ⁹ , for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, (2 -ethyl)hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, phenyloxycarbonyl, eicosyloxycarbonyl and the like.

As -O-CO-R ⁹ , for example: acetyloxy, propionyloxy, butyryloxy, 2,2-dimethylpropionyloxy, pentyloxy, hexyloxy , (2-Ethyl)hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, benzoyloxy, etc.

As substituents that the hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ³ and R ⁹ may have, for example, halogen atoms; those selected from -O-, -CO-, and divalent hydrocarbon groups A group consisting of at least one of the group consisting of (including at least one -O- or -CO-) combined with a monovalent hydrocarbon group; nitrile group; nitro group; amine group; amide group; sulfonamide group ; Hydroxy; Thiol; Methylthio, ethylthio and other alkylthio groups with 1 to 15 carbons; Allylthio; Benzylthio, 1-naphthylthio, 2-naphthylthio and other carbons Arylthio groups with a number of 6 to 20; sulfonyl groups; methylsulfonyl, ethylsulfonyl and other alkylsulfonyl groups with 1 to 15 carbons; phenylsulfonyl, 1-naphthylsulfonyl , 2-naphthylsulfonyl and other arylsulfonyl groups with 6 to 20 carbon atoms; silyl groups; boron groups; monomethylamino groups, dimethylamino groups, monoethylamino groups, diethylamino groups Alkylamine groups with 1 to 15 carbons; arylamines with 6 to 20 carbons such as monophenylamine and diphenylamine; aralkylamines with 7 to 20 carbons such as benzylamine N-methylaminosulfonyl, N,N-dimethylaminosulfonyl, N-ethylaminosulfonyl and other alkylaminosulfonyl groups with 1 to 15 carbon atoms; carboxyl ; carbamoyl; furyl, pyrrolyl, thienyl and other heterocyclic groups with 1 to 20 carbon atoms.

As a combination of at least one selected from the group consisting of -O-, -CO-, and divalent hydrocarbon groups (including at least one -O- or -CO-) and a monovalent hydrocarbon group For example, groups represented by the following formula (Sa) and formula (Sb) may be mentioned.

[式(Sa)、式(Sb)中， R ^S表示碳數1～20之烴基，該烴基中所包含之亞甲基可被取代為-O-及/或-CO-； *表示鍵結鍵]。

[In formula (Sa) and formula (Sb), R ^S represents a hydrocarbon group with 1 to 20 carbon atoms, and the methylene contained in the hydrocarbon group can be substituted with -O- and/or -CO-; * represents a bond key].

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^S include the same ones as those represented by R ¹ to R ³ and R ⁹ described above. When the methylene group contained in the hydrocarbon group represented by R ^S is substituted with -O- and/or -CO-, the number may be one or two or more. Furthermore, when the methylene group contained in the hydrocarbon group is substituted with -O- and/or -CO-, the carbon number before the substitution is taken as the carbon number of the hydrocarbon group.

As the group represented by the formula (Sa), specifically, alkoxy groups having 1 to 15 carbon atoms such as methoxy and ethoxy; phenoxy, 1-naphthyloxy, and 2-naphthoxy Aryloxy groups with 6 to 20 carbon atoms, etc. As the group represented by the formula (Sb), specifically, an alkylcarbonyl group having 2 to 15 carbons such as an acetyl group and a propionyl group; a benzoyl group, a 1-naphthylcarbonyl group, and a 2-naphthyl group Arylcarbonyl with 7 to 20 carbons such as carbonyl; alkoxycarbonyl with 2 to 15 carbons such as methoxycarbonyl and ethoxycarbonyl; phenoxycarbonyl, 1-naphthyloxycarbonyl, 2-naphthyloxycarbonyl Aryloxycarbonyl groups with 7 to 19 carbon atoms, etc.

When the hydrocarbon groups represented by R ¹ to R ³ and R ⁹ have substituents, the number of substituents may be 1, or 2 or more, and the 2 or more substituents are independent of each other, and may be the same, or Can be different.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

R ¹ is preferably a methyl group, an ethyl group or a hydrogen atom, more preferably an ethyl group or a hydrogen atom, still more preferably a hydrogen atom.

The hydrocarbon groups with 1 to 20 carbons represented by ^R2 and ^R3 are preferably saturated chain hydrocarbon groups, saturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups and chain hydrocarbon groups, chain hydrocarbon groups and alicyclic hydrocarbon groups. A group formed by a combination of hydrocarbon groups, more preferably a saturated chain hydrocarbon group, a saturated alicyclic hydrocarbon group, an aromatic hydrocarbon group and a chain hydrocarbon group, and further preferably a saturated chain hydrocarbon group, an aromatic hydrocarbon group and a chain A combination of hydrocarbon groups, more preferably a saturated chain hydrocarbon group, further preferably a saturated chain hydrocarbon group with 2 to 15 carbons, even more preferably a saturated chain hydrocarbon group with 4 to 12 carbons, and even more preferably A saturated chain hydrocarbon group with 4 to 10 carbon atoms. Also, the hydrocarbon groups represented by R ² and R ³ may have substituents, but preferably have no substituents.

As a hydrocarbon group with 1 to 20 carbon atoms that may have substituents represented by R ² and R ³ , specifically, the following formulas (D-1) to (D-69), formula (G-1 )～the group represented by the formula (G-31), more preferably the group represented by the formula (D-1)～the formula (D-69), the formula (G-1)～the formula (G-19), and more It is preferably the group represented by formula (D-1) to formula (D-69), and more preferably is formula (D-1) to formula (D-18), formula (D-40) to formula (D-52 ) is more preferably a group represented by formula (D-1) to formula (D-18), and even more preferably a group represented by formula (D-2) to formula (D-15). In the formula, * represents a bonding bond.

The ring formed by R ² and R ³ and the nitrogen atom to which they are bonded may be saturated or unsaturated, and may be monocyclic or polycyclic.

The number of ring members of the ring formed by R ² and R ³ and the nitrogen atom to which they are bonded is preferably 3 to 15, more preferably 4 to 12, further preferably 5 to 10, and even more preferably 5 to 7.

As the ring formed by ^R2 and ^R3 and the nitrogen atom to which they are bonded together, for example, a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperidine ring, etc.; preferably a pyrrolidine ring and a piperidine ring etc. rings having only 1 nitrogen atom as a heteroatom.

As the ring formed by R ² and R ³ together with the nitrogen atom to which they are bonded, specifically, rings represented by the following formulas (J-1) to (J-9) may be exemplified. In the formula, * represents a bonding bond.

The ring formed by R ² and R ³ together with the nitrogen atoms to which they are bonded is preferably a ring represented by the above formula (J-1) to formula (J-9), more preferably a ring represented by formula (J-1) to The ring represented by the formula (J-7) is more preferably the ring represented by the formula (J-1) to the formula (J-6), and more preferably the ring represented by the formula (J-3) to the formula (J-5) represents the ring.

Examples of possible substituents for the ring formed by R ² and R ³ and the nitrogen atom to which they are bonded include possible substitutions with the hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ³ and R ⁹ An example of the same base. When the ring formed by ^R2 and ^R3 and the nitrogen atom to which they are bonded together has a substituent, the number of the substituent may be one or more than two, and the two or more substituents are independent of each other and may be Same or different.

As R ² and R ³ , particularly preferably, one of them is a hydrogen atom, and the other is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

R ⁴ to R ⁸ are preferably a hydrogen atom or -R ⁹ , more preferably a hydrogen atom. R ⁹ is preferably a saturated chain hydrocarbon group which may have a substituent, more preferably a saturated chain hydrocarbon group having 1 to 10 carbon atoms.

As the compound (I), for example: among the compounds represented by the following formula (Ii), the combination of R ¹ , R ² and R ³ is any one of the following Tables 1 to 4; and In the compound represented by the following formula (Iii), the combination of the ring formed by R ² and R ³ and the nitrogen atom to which they are bonded together, and R ¹ is any one of the compounds in Table 5 below. Furthermore, in Tables 1 to 5, H means a hydrogen atom, Et means an ethyl group, IBu means an isobutyl group, D-1 to D-15, D-19 to D-34, D-40 to D -67, G-1～G-6, G-9～G-14, G-20～G-27 respectively mean the above formula (D-1) ~ formula (D-15), formula (D-19) ~ Formula (D-34), Formula (D-40) ~ Formula (D-67), Formula (G-1) ~ Formula (G-6), Formula (G-9) ~ Formula (G-14), The groups represented by the formulas (G-20) to (G-27), and J-1 to J-9 mean the rings represented by the above formulas (J-1) to (J-9).

[Table 1]

[Table 2]

[table 3]

[Table 4]

[式(Iii)中，R ²³表示R ²與R ³與各自鍵結之氮原子一起形成之環]。

[In formula (Iii), R ²³ represents a ring formed by R ² and R ³ and the nitrogen atom to which they are bonded together].

[table 5]

Compound (I) is preferably compound (Ii-1) to compound (Ii-15), more preferably compound (Ii-2) to compound (Ii-15).

Also, as compound (I), Preferably compound (Ii-1) to compound (Ii-334), More preferably compound (Ii-1) to compound (Ii-237), compound (Ii-317) to compound (Ii-334), Further preferred are compound (Ii-1) to compound (Ii-15), compound (Ii-32) to compound (Ii-71), compound (Ii-80) to compound (Ii-94), compound (Ii- 111)～compound (Ii-150), compound (Ii-159)～compound (Ii-173), compound (Ii-190)～compound (Ii-229), compound (Ii-318)～compound (Ii-322 ), compound (Ii-327)～compound (Ii-331), Further more preferred are compound (Ii-2) to compound (Ii-14), compound (Ii-32) to compound (Ii-44), compound (Ii-60) to compound (Ii-71), compound (Ii- 81)～compound (Ii-93), compound (Ii-111)～compound (Ii-123), compound (Ii-139)～compound (Ii-150), compound (Ii-160)～compound (Ii-172 ), compound (Ii-190)～compound (Ii-202), compound (Ii-319)～compound (Ii-321), compound (Ii-328)～compound (Ii-330).

Compound (I) can be produced, for example, by reacting a compound represented by the following formula (pt1) (hereinafter, sometimes referred to as compound (pt1)) with malononitrile in a solvent to produce the following formula The compound represented by (pt2) (hereinafter sometimes referred to as compound (pt2)) is subjected to a condensation reaction of compound (pt2) in a solvent using a catalyst to produce a compound represented by the following formula (pt3) (hereinafter , sometimes referred to as compound (pt3)), and compound (pt3) is treated with concentrated sulfuric acid to produce a compound represented by the following formula (pt4) (hereinafter sometimes referred to as compound (pt4)), and the following The compound represented by the formula (MA1) (hereinafter sometimes referred to as the compound (MA1)) reacts with the compound (pt4) in a solvent to produce a compound represented by the following formula (pt5) (hereinafter sometimes referred to as is compound (pt5)), and further, a compound represented by the following formula (MA2) (hereinafter, may be referred to as compound (MA2)) is reacted with compound (pt5) in a solvent to produce it.

[式中，R ¹～R ⁸與上述定義相同；R ^A表示氫原子或鹵素原子，R ^B表示鹵素原子或對甲苯磺醯基]。

[wherein, R ¹ to R ⁸ are as defined above; R ^A represents a hydrogen atom or a halogen atom, and R ^B represents a halogen atom or a p-toluenesulfonyl group].

As a compound (pt1), acenaphthoquinone etc. are mentioned, for example.

The halogen atom represented by R ^A may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. R ^A is preferably a hydrogen atom.

The amount of malononitrile used is usually not less than 0.1 mol and not more than 500 mol, preferably not less than 0.3 mol and not more than 400 mol, more preferably not less than 0.5 mol and not more than 300 mol, relative to 1 mol of compound (pt1). Mole or less, and more preferably 0.8 mole or more and 200 mole or less.

As the solvent in the reaction between the compound (pt1) and malononitrile, in order to suppress side reactions, it is preferable to use a solvent (especially an organic solvent) sufficiently deoxidized and/or dehydrated, more preferably dehydrated acetonitrile.

The usage-amount of the solvent in the reaction of compound (pt1) and malononitrile is 0.1-1000 mass parts normally with respect to 1 mass part of compound (pt1).

The reaction temperature when reacting compound (pt1) with malononitrile is usually -100°C or higher and 300°C or lower. In addition, the reaction time when reacting the compound (pt1) with malononitrile is usually 0.5 hours to 300 hours.

As a compound (pt2), 2-(2-oxo-2H-acenaphthyl-1-ylidene)-malononitrile etc. are mentioned, for example.

As a catalyst for producing compound (pt3), tris(dibenzylideneacetone)dipalladium(0), bis(dibenzylideneacetone)palladium(0), palladium(II) acetate, chlorine Palladium (II), sodium tetrachloropalladate (II), palladium (II) (π-cinnamyl) chloride (dimer), allyl palladium (II) chloride (dimer), bis( Palladium compounds such as benzonitrile)palladium(II) dichloride, bis(acetonitrile)palladium(II) dichloride; triethylamine, 4-(N,N-dimethylamino)pyridine, pyridine, piperidine Pyridine, N,N-diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]-5-nonene, 1 , 8-diazabicyclo[5.4.0]-7-undecene and other organic bases; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium 3-butoxide, potassium 3-butoxide; sodium acetate, potassium phosphate , lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate and other inorganic bases. Preferred are cesium carbonate, potassium carbonate, potassium phosphate, triethylamine, 4-(N,N-dimethylamino)pyridine, N,N-diisopropylethylamine, 1,4-diazo Heterobicyclo[2.2.2]octane.

The amount of the catalyst used should be the amount of the catalyst, for example, relative to 100 moles of the compound (pt2), 0.1 moles to 50 moles, preferably 0.5 moles to 40 moles, more preferably 1.0 mol or more and 30 mol or less.

Examples of the solvent in the condensation reaction of the compound (pt2) in the presence of a catalyst include water; nitrile solvents such as acetonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 1-pentanol Alcohol solvents such as alcohol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, phenol; ether solvents such as diethyl ether and tetrahydrofuran; ketones such as acetone and methyl isobutyl ketone Solvents; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride, chloroform, and 1,2-dichlorobenzene; Amide solvents such as amide and N-methylpyrrolidone; dimethyl sulfide and other sulfide solvents; acetic acid, propionic acid, butyric acid and other carboxylic acid solvents; imidazole, etc.; preferably water and nitrile solvents, more preferably For water, acetonitrile.

The usage-amount of the solvent in the condensation reaction of the compound (pt2) in presence of a catalyst is 0.1-1000 mass parts normally with respect to 1 mass part of compound (pt2).

The reaction temperature in the condensation reaction of the compound (pt2) in the presence of a catalyst is usually -100°C or more and 300°C or less. Moreover, the reaction time at the time of carrying out condensation reaction of the compound (pt2) in presence of a catalyst is 0.5 hour - 300 hours normally.

As a compound (pt3), 1-oxo-1H-butadiene-2,3-dicarbonitrile etc. are mentioned, for example.

The reaction temperature when treating the compound (pt3) with concentrated sulfuric acid is usually 0°C or higher and 300°C or lower. In addition, the reaction time when the compound (pt3) is treated with concentrated sulfuric acid is usually 0.5 hours to 300 hours.

The compound (pt4) may, for example, be 1-oxo-1H-butadiene-2,3-dicarboxyimide or the like.

The compound (MA1) may, for example, be an alkyl halide (specifically, ethyl iodide or the like), an alkyl p-toluenesulfonate or the like.

The amount of compound (MA1) to be used is usually not less than 0.4 mole and not more than 20 mole, preferably not less than 0.5 mole and not more than 15 mole, more preferably not less than 0.6 mole and not more than 1 mole of compound (pt4). Below 10 moles.

As a solvent in the reaction of compound (pt4) and compound (MA1), for example: water; nitrile solvents such as acetonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol , 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, phenol and other alcohol solvents; diethyl ether, tetrahydrofuran and other ether solvents; acetone, methyl isobutyl ketone and other ketone solvents ; Ester solvents such as ethyl acetate; Aliphatic hydrocarbon solvents such as hexane; Aromatic hydrocarbon solvents such as toluene; Halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichlorobenzene, etc.; Amide solvents such as amine and N-methylpyrrolidone; dimethyl sulfide and other sulfide solvents; carboxylic acid solvents such as acetic acid, propionic acid, butyric acid; imidazole, etc.; preferably water, nitrile solvent, more preferably water, acetonitrile.

The usage-amount of the solvent in the reaction of compound (pt4) and compound (MA1) is 0.1-1000 mass parts normally with respect to 1 mass part of compound (pt4).

In order to neutralize the hydrogen halide or p-toluenesulfonic acid generated by the reaction, the reaction of the compound (pt4) and the compound (MA1) can also be accompanied by a base. As the base, for example, sodium carbonate, potassium carbonate , sodium bicarbonate, potassium bicarbonate, triethylamine, etc.

When a base is used in the reaction between the compound (pt4) and the compound (MA1), the amount of the base used is usually 0.1 mole to 50 mole, preferably 0.5 mole to 1 mole of the compound (pt4). More than mole and less than 30 mole.

As the compound (pt5), for example, N-ethyl-1-oxo-1H-butadiene-2,3-dicarboxyimide and the like may be mentioned.

As a compound (MA2), 1-hexylamine, n-butylamine, benzylamine, diisobutylamine, piperidine etc. are mentioned, for example.

The amount of compound (MA2) to be used is usually not less than 0.05 mol and not more than 20 mol, preferably not less than 0.1 mol and not more than 15 mol, more preferably not less than 0.2 mol and not more than 1 mol of compound (pt5). Below 10 moles.

As a solvent in the reaction between compound (pt5) and compound (MA2), water; nitrile solvents such as acetonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol , 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, phenol and other alcohol solvents; diethyl ether, tetrahydrofuran and other ether solvents; acetone, methyl isobutyl ketone and other ketone solvents ; Ester solvents such as ethyl acetate; Aliphatic hydrocarbon solvents such as hexane; Aromatic hydrocarbon solvents such as toluene; Halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichlorobenzene, etc.; Amide solvents such as amines and N-methylpyrrolidone; ethylene oxide solvents such as dimethyl sulfide; carboxylic acid solvents such as acetic acid, propionic acid, butyric acid; imidazole, etc.

The usage-amount of the solvent in the reaction of compound (pt5) and compound (MA2) is 0.1-1000 mass parts normally with respect to 1 mass part of compound (pt5).

In the reaction between the compound (pt5) and the compound (MA2), in order to react efficiently, a base may also coexist. As the base, it may be an organic base or an inorganic base, preferably an organic base, more preferably Trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenyl Amine, N,N-dimethylaniline, N,N,N',N'-tetramethylethylenediamine, N-methylpyrrolidine, 4-dimethylaminopyridine and other tertiary amines.

When a base is used in the reaction between the compound (pt5) and the compound (MA2), the amount of the base used is usually 0.1 mole to 50 mole, preferably 0.5 mole to 1 mole of the compound (pt5). More than mole and less than 30 mole.

The reaction temperature at the time of reacting compound (pt5) and compound (MA2) is -100 degreeC or more and 300 degreeC or less normally. In addition, the reaction time when reacting compound (pt5) and compound (MA2) is usually 0.5 hours to 300 hours.

Furthermore, when ^R1 is a hydrogen atom, the compound (MA1) is not reacted with the compound (pt4), but the compound (pt4) is reacted with the compound (MA2) instead of the compound (pt5), thereby producing the compound (I).

The method for taking out the target compound after each of the above reactions is not particularly limited, and various known methods can be used for taking out. After taking out, the obtained residue can also be purified by column chromatography or recrystallization. The chemical structures of the obtained compounds can be analyzed by known analytical methods and conditions. Such an analysis method is not particularly limited, and examples thereof include X-ray crystal structure analysis, mass spectrometry (LC), NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) analysis, and elemental analysis. The X-ray crystal structure analysis method can be performed according to Chemistry of Materials, 2012, volume 24, p.4647-4652, for example.

The content of the compound (I) may be 100% by mass relative to the total amount of the colorant (A), and the lower limit may be, for example, 0.1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more , more preferably at least 20% by mass, further preferably at least 30% by mass, further preferably at least 50% by mass.

＜＜Colorant (A1)＞＞ The coloring agent (A) of the present invention may also contain dyes other than compound (I) (hereinafter sometimes referred to as dye (A1-1)) and/or pigments (hereinafter sometimes referred to as pigment (A1-2)) (Hereinafter, the dye (A1-1) and the pigment (A1-2) may be collectively referred to as a colorant (A1)). These may be used individually or in combination of 2 or more types.

染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基染料、甲亞胺染料、方酸鎓染料、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料、硝基染料、酞菁染料、苝染料、喹酞酮染料、異吲哚啉染料等。該等之中，較佳為有機溶劑可溶性染料。Known dyes can be used for the dye (A1-1) as long as the compound (I) is not included, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as dyes based on the color index (published by The Society of Dyers and Colourists) and known dyes described in Dyeing Notes (Yorsensha). Also, depending on the chemical structure, there may be mentioned: azo dyes, cyanine dyes, triphenylmethane dyes, 𠮿

Dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, formimine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro Dye, phthalocyanine dye, perylene dye, quinophthalone dye, isoindoline dye, etc. Among these, organic solvent-soluble dyes are preferred.

Specifically, dyes with the following color index (C.I.) numbers may, for example, be mentioned. C.I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189; C.I. Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172 , 175, 181, 207, 218, 222, 227, 230, 245, 247; C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94 , 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; etc. C.I. Solvent Dyes, C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 ,113,114,116,119,123,128,134,135,138,139,140,144,150,155,157,160,161,163,168,169,172,177,178,179,184 ,190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251; C.I. Acid 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 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; C.I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; C.I. 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, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80 , 104, 105, 106, 109 and other C.I. acid dyes, C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102 , 108, 109, 129, 132, 136, 138, 141; C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. 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 ,85,86,87,90,93,94,95,97,98,99,100,101,106,107,108,109,113,114,115,117,119,120,137,149,150 ,153,155,156,158,159,160,161,162,163,164,165,166,167,168,170,171,172,173,188,189,190,192,193,194,195 ,196,198,199,200,201,202,203,207,209,210,212,213,214,222,225,226,228,229,236,237,238,242,243,244,245 , 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; etc. C.I. Direct Dyes, C.I. Disperse Yellow 51, 54, 76; C.I. Disperse Violet 26, 27; C.I. Disperse blue 1, 14, 56, 6; 0 etc. C.I. Disperse dyes, C.I. Basic Red 1, 10; C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; C.I. Basic Violet 2; C.I. Basic Red 9; C.I. Basic Green 1; etc. C.I. Basic Dyes, C.I. Reactive Yellow 2, 76, 116; C.I. Reactive Orange 16; C.I. Reactive Red 36; etc. C.I. Reactive Dyes, C.I. 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 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84; C.I. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53; etc. C.I. Mordant Dyes, C.I. Vat Green 1; etc. C.I. Vat Dyes etc.

As the pigment (A1-2), known pigments can be used as long as the compound (I) is not contained, and for example, pigments classified as pigments according to the color index (published by The Society of Dyers and Colourists) are exemplified.

Specific examples of pigments classified as 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, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264 , 265, 266, 268, 269, 273 and other red pigments; C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 and other blue pigments; C.I. Pigment Violet 1, 19, 23, 32, 36, 38 and other purple pigments; C.I. Pigment Green 7, 36, 58, 59, 62, 63 and other green pigments; C.I. Pigment Brown 23, 25 and other brown pigments; C.I. Pigment Black 1, 7, 31, 32 and other black pigments; etc.

When the colorant (A) contains the colorant (A1), the content of the colorant (A1) in the colorant (A) is, for example, 0.1% by mass or more and 99.9% by mass relative to the total amount of the colorant (A). Mass % or less, Preferably it is 1 mass % or more and 50 mass % or less.

In the case where the colored resin composition contains the solvent (E), a colored composition (hereinafter, sometimes also referred to as a colorant-containing solution) containing the colorant (A) and the solvent (E) can be prepared in advance, and then, use The colored composition prepares a colored resin composition. In the case where the colorant (A) is insoluble in the solvent (E), for example, when the colorant (A) contains the pigment (A1-2), etc., the coloring composition can be mixed by dispersing the colorant (A) Prepared in solvent (E). The colored composition may also contain a part or all of the solvent (E) contained in the colored resin composition.

The content of the solid content in the coloring composition is less than 100% by mass relative to the total amount of the coloring composition, preferably 0.01% by mass to 99.99% by mass, more preferably 0.1% by mass to 99.9% by mass , and more preferably at least 0.1% by mass and at most 99% by mass, still more preferably at least 1% by mass and not more than 90% by mass, particularly preferably at least 1% by mass and not more than 80% by mass, further preferably at least 1% by mass And 70% by mass or less, particularly preferably 1% by mass to 60% by mass, most preferably 1% by mass to 50% by mass.

The content of the colorant (A) in the coloring composition is 100% by mass or less, preferably 0.001% by mass or more and 99.999% by mass or less, more preferably 0.01% by mass relative to the total amount of solids in the coloring composition % to 99 mass%, more preferably 0.1 mass% to 95 mass%, still more preferably 0.5 mass% to 90 mass%, particularly preferably 1.0 mass% to 80 mass%.

The coloring agent (A) may also be subjected to rosin treatment, surface treatment using a derivative having an acidic group or a basic group, etc., grafting treatment on the surface of the coloring agent (A) with a polymer compound, etc., by Micronization treatment by sulfuric acid micronization method, salt milling method, etc., cleaning treatment by organic solvent or water to remove impurities, treatment by ion exchange method, etc. to remove ionic impurities, etc. The particle size of the colorant (A) is preferably substantially uniform.

The coloring agent (A) can be brought into a state where the coloring agent (A) is uniformly dispersed in a solution by containing a dispersant and carrying out a dispersion treatment. When using in combination of 2 or more types as a coloring agent (A), you may perform a dispersion process individually, respectively, and may perform a dispersion process after mixing several types.

As a dispersant, a surfactant etc. are mentioned, for example, Any one of cationic, anionic, nonionic, and amphoteric surfactants may be used. Specifically, polyester-based, polyamine-based, and acrylic-based surfactants, etc. may, for example, be mentioned. These dispersants may be used alone or in combination of two or more. The dispersant is represented by a trade name, and examples thereof include: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF Corporation), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (BYK-Chemie (shares) manufacturing), etc.

When a dispersant is used, the amount of the dispersant (solid content) used is usually 1 part by mass to 10000 parts by mass, preferably 100 parts by mass relative to 100 parts by mass of the colorant (A) in the coloring composition. 5 parts by mass to 5000 parts by mass, more preferably 10 parts by mass to 3000 parts by mass, still more preferably 15 parts by mass to 1000 parts by mass. When the usage-amount of this dispersant exists in the said range, it exists in the tendency to obtain the coloring composition with a more uniform dispersion state.

In the case of preparing a coloring composition containing a colorant (A) and a solvent (E) in advance, and using the coloring composition to prepare a coloring resin composition, the coloring composition may previously contain the resin contained in the coloring resin composition ( A part or all of B), preferably a part. By containing resin (B) beforehand, the dispersion stability of a coloring composition can be improved further.

When the coloring composition contains the resin (B), the content of the resin (B) is, for example, 0.01 to 10,000 parts by mass relative to 100 parts by mass of the colorant (A) in the coloring composition, preferably 0.01 to 10,000 parts by mass. 0.01 to 8000 parts by mass, more preferably 0.01 to 5000 parts by mass, still more preferably 0.1 to 3000 parts by mass.

The content of the colorant (A) in the total solid content of the colored resin composition is preferably from 0.1% by mass to 50% by mass, more preferably from 0.5% by mass to 40% by mass, and even more preferably Preferably, it is 1.0 mass % or more and 30 mass % or less, More preferably, it is 1.5 mass % or more and 20 mass % or less. If the content of the colorant (A) is within the above range, the color density of the color filter is sufficient, and the required amount of resin (B) can be contained in the composition, so it can form a color filter with sufficient mechanical strength. pattern, so better. Here, the "total amount of solid content" in this specification means the amount remaining after subtracting the content of the solvent from the total amount of the colored resin composition. The total amount of solid content and the content of each component relative to it can be measured by known analysis methods such as liquid chromatography or gas chromatography, for example.

The content ratio of the colorant (A) in the colored resin composition to the following resin (B) (resin (B)/colorant (A)) is, for example, based on mass, preferably 2.0 or more, more preferably 3.0 or more , and more preferably 4.0 or more, preferably 20 or less, more preferably 15 or less, still more preferably 13 or less.

＜Resin (B)＞ Resin (B) is different from thermoplastic resin and is not particularly limited as long as it is used to form photoresist. It is an alkali-soluble resin, preferably an alkali-soluble resin having a carboxylic acid.

As the resin (B), the following resins [K1] to [K6] and the like may, for example, be mentioned. Resin [K1]; having at least one monomer (a) (hereinafter sometimes referred to as "(a)" or "monomer ( a)") structural unit, and monomer (b) derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)" or "monomer (b) ") copolymers of structural units; Resin [K2]; having a structural unit derived from (a), a structural unit derived from (b), and a monomer (c) derived from (a) copolymerizable (wherein, with (a) and (b) ) different) (hereinafter, sometimes referred to as "(c)" or "monomer (c)") of the structural unit of the copolymer; Resin [K3]; a copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]; a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c); Resin [K5]; a copolymer having a structural unit derived from (a) added to a structural unit derived from (b) and a structural unit derived from (c); Resin [K6]; a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b), and further adding a carboxylic anhydride, and a structural unit derived from (c).

As the monomer (a), for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid can be cited; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6- Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; Methyl-5-northene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2- ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene and 5-carboxy-6- Bicyclic unsaturated compounds containing carboxyl groups such as ethylbicyclo[2.2.1]hept-2-ene; Carboxylic acid anhydrides such as anhydrides of the above-mentioned unsaturated dicarboxylic acids other than fumaric acid and mesaconic acid; Unsaturated polycarboxylic acids with more than two valences such as mono[2-(meth)acryloxyethyl] succinate and mono[2-(meth)acryloxyethyl] phthalate Mono[(meth)acryloxyalkyl]esters; For example, α-(hydroxymethyl)acrylic acid contains unsaturated acrylic acid esters with hydroxyl and carboxyl groups in the same molecule. Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable in terms of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution. In addition, in this specification, "(meth)acrylic acid" means at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations such as "(meth)acryl" and "(meth)acrylate" also have the same meaning.

Monomer (b) is a cyclic ether structure with 2 to 4 carbons (for example, one selected from the group consisting of oxirane ring, oxetane ring and tetrahydrofuran ring (oxolane ring) at least 1) a polymerizable compound with an ethylenically unsaturated bond. The monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

As the monomer (b), for example, a monomer having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)" or "monomer (b1)"), a monomer having A monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b2)" or "monomer (b2)"), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, , sometimes referred to as "(b3)" or "monomer (b3)"), etc.

As the monomer (b1), for example, a monomer having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as "(b1-1)" or "monomer (b1-1) )"), a monomer having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon (hereinafter, sometimes referred to as "(b1-2)" or "monomer (b1-2)").

The monomer (b1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. As the monomer (b1-1), specifically, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, etc. Esters, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α -Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyl Glyceryloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene Glyceryloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5 - Tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene and the like.

As the monomer (b1-2), for example: vinyl cyclohexene monooxide, 1,2-epoxy-4-vinyl cyclohexane (such as Celloxide (registered trademark) 2000; Daicel (stock) manufactured), 3,4-epoxycyclohexylmethyl (meth)acrylate (such as Cyclomer (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate ( For example, Cyclomer (registered trademark) M100; manufactured by Daicel Co., Ltd.), a compound represented by formula (BI), a compound represented by formula (BII), and the like.

[In formula (BI) and formula (BII), R ^a and R ^b independently represent a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group can be replaced by a hydroxyl group; X ^a and X ^b independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-; R ^c represents an alkane with 1 to 6 carbons Two bases; * represents a bond with O].

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

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

As R ^a and R ^b , preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1 ,5-diyl, hexane-1,6-diyl, etc.

Preferred examples of X ^a and X ^b include single bond, methylene group, ethylene group, *-CH ₂ -O- (* represents a bond with O) group, *-CH ₂ CH ₂ -O - group, more preferably a single bond, *-CH ₂ CH ₂ -O- group (* represents a bond with O).

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

As a compound represented by formula (BII), a compound represented by any one of formula (BII-1) to formula (BII-15) can be exemplified, and among them, formula (BII-1), Compounds represented by formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) and formula (BII-11) ~ formula (BII-15), more preferably Examples include compounds represented by formula (BII-1), formula (BII-7), formula (BII-9) and formula (BII-15).

The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone, respectively, or the compound represented by formula (BI) and the compound represented by formula (BII) may be used in combination. When these are used in combination, the content ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) is preferably 5:95 to 95:5, more preferably 10, on a molar basis. : 90 to 90: 10, more preferably 20: 80 to 80: 20.

The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is more preferably a monomer having an oxetanyl group and a (meth)acryloxy group. Examples of the monomer (b2) include: 3-methyl-3-(meth)acryloxymethyloxetane, 3-ethyl-3-(meth)acryloxy Methyloxetane, 3-methyl-3-(meth)acryloxyethyloxetane, 3-ethyl-3-(meth)acryloxyethyloxetane Cyclobutane etc.

The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is more preferably a monomer having a tetrahydrofuryl group and a (meth)acryloxy group. As a monomer (b3), tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc. are mentioned, for example.

As the monomer (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second-butyl (meth)acrylate, (meth)acrylate ) tertiary butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) ) cyclopentyl acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (In this technical field, the commonly used names are "dicyclopentyl (meth)acrylate" and "tricyclodecanyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decane Alk-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (in this technical field, as a common name, called "(meth)acrylate base) dicyclopentenyl acrylate"), tricyclo[5.2.1.0 ^2,6 ]decen-9-yl (meth)acrylate, dicyclopentyl ethyl (meth)acrylate, (meth)acrylic acid Isothionate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and (meth) (meth)acrylates such as benzyl acrylate; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as ethyl ester, diethyl fumarate and diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]heptane -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-ethane Oxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1 ]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept- 2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy- 5-Ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene Bicyclic unsaturated compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-butadiamide -3-maleimide benzoate, N-butadiamide-4-maleimide butyrate, N-butadiamide-6-cis Butenediimide hexanoate, N-butadiimide-3-maleimide propionate and N-(9-acridyl)maleimide, etc. Carbonyl imide derivatives; Vinyl-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; (methyl ) acrylonitrile and other vinyl-containing nitriles; vinyl chloride and vinylidene chloride and other halogenated hydrocarbons; (meth)acrylamide and other vinyl-containing amides; vinyl acetate and other esters; 1,3-butadiene, Dienes such as isoprene and 2,3-dimethyl-1,3-butadiene, etc. Among these, styrene, vinyl toluene, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate are preferable in terms of copolymerization reactivity and heat resistance. , tricyclo[5.2.1.0 ^2,6 ]decane-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate, tricyclo[ 5.2.1.0 ^2,6 ]decen-9-yl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide Alkenedimide, bicyclo[2.2.1]hept-2-ene, benzyl (meth)acrylate, etc.

In the resin [K1], the ratio of the structural units derived from each in the total structural units constituting the resin [K1], preferably Structural unit derived from (a): 2-60 mol% Structural unit derived from (b): 40-98 mol%, better to Structural unit derived from (a): 10-50 mol% Structural unit derived from (b): 50-90 mol%.

When the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the colored resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained optical filter tend to be excellent. Resin [K1], for example, can refer to the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing Office (Stock) Chemical Doujin 1st Edition, 1st Brush, March 1, 1972) and the method described in the document Recorded citations are produced.

Specifically, the following method can be exemplified: a specific amount of (a) and (b), a polymerization initiator, a solvent, etc. are added to a reaction vessel, and oxygen is replaced by, for example, nitrogen to thereby create a deoxygenated atmosphere, Stir while heating and keeping warm. In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, Those who are usual in this field can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or Organic peroxides (benzoyl peroxide, etc.); as the solvent, any monomer may be dissolved, and the solvent (E) of the colored resin composition of the present invention may, for example, be the following solvents.

Furthermore, the obtained copolymer may be used as a solution after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like. Especially in this polymerization, by using the solvent contained in the colored resin composition of the present invention as a solvent, the solution after the reaction can be directly used to prepare the colored resin composition of the present invention, so the colored resin composition of the present invention can be made The manufacturing steps of the resin composition are simplified.

In the resin [K2], the ratio of the structural units derived from each in the total structural units constituting the resin [K2], preferably Structural unit derived from (a): 2-45 mol% Structural unit derived from (b): 2-95 mol% Structural unit derived from (c): 1-65 mol%, better to Structural unit derived from (a): 5-40 mol% Structural unit derived from (b): 5-80 mol% Structural unit derived from (c): 5-60 mol%. If the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance and Tendency to be excellent in mechanical strength.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

In the resin [K3], the ratio of the structural units derived from each in the total structural units constituting the resin [K3], preferably Structural unit derived from (a): 2-60 mol% Structural unit derived from (c): 40-98 mol%, better to Structural unit derived from (a): 10-50 mol% Structural unit derived from (c): 50-90 mol% Resin [K3] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

Resin [K4] can be obtained by obtaining a copolymer of (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms in (b) to the carboxylic acid and/or Carboxylic anhydrides are produced. First, the copolymer of (a) and (c) was produced in the same manner as the method described as the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same ratio as exemplified in resin [K3].

Next, a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the above-mentioned copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms contained in (b). After producing the copolymer of (a) and (c), the atmosphere in the flask was replaced from nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic acid anhydride and cyclic ether (such as tris(dimethylamine) (methyl) phenol, etc.) and polymerization inhibitors (such as hydroquinone, etc.) are added to the flask, and reacted at, for example, 60-130° C. for 1-10 hours, whereby the resin [K4] can be produced. The usage-amount of (b) is preferably 5-80 mol, more preferably 10-75 mol with respect to 100 mol of (a). By setting it as this range, there exists a tendency for the balance of the storage stability of a colored resin composition, the developability at the time of pattern formation, and the solvent resistance of the obtained pattern, heat resistance, mechanical strength, and sensitivity to become favorable. In terms of the high reactivity of the cyclic ether and the fact that unreacted (b) is less likely to remain, the (b) used as the resin [K4] is preferably (b1), and more preferably (b1-1 ). As the usage-amount of the said reaction catalyst, it is preferable that it is 0.001-5 mass parts with respect to 100 mass parts of total amounts of (a), (b) and (c). As the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b) and (c). Reaction conditions such as addition method, reaction temperature and time can be appropriately adjusted in consideration of production equipment and heat generation due to polymerization. In addition, similarly to the polymerization conditions, the addition method and the reaction temperature can be appropriately adjusted in consideration of production facilities, heat generation by polymerization, and the like.

Resin [K5] The copolymer of (b) and (c) can be obtained as the first stage in the same manner as the production method of the above-mentioned resin [K1]. Similar to the above, the obtained copolymer may be used as a solution after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like. The ratio of the structural units derived from (b) and (c) to the total molar number of the total structural units constituting the above-mentioned copolymer is preferably respectively Structural units derived from (b): 5-95 mol% Structural unit derived from (c): 5-95 mol%, better to Structural unit derived from (b): 10-90 mol% Structural unit derived from (c): 10-90 mol%.

Furthermore, under the same conditions as the production method of resin [K4], the cyclic ring derived from (b) contained in the carboxylic acid or carboxylic anhydride contained in (a) and the copolymer of (b) and (c) contained Ether reaction, whereby the resin [K5] can be obtained. The usage-amount of (a) reacted with the said copolymer is preferably 5-80 mol with respect to 100 mol of (b). In terms of the high reactivity of the cyclic ether and the unreacted (b) is not easy to remain, the (b) used as the resin [K5] is preferably (b1), preferably further (b1-1 ).

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

Specific resins (B) include: 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxycyclohexyl acrylic acid [5.2.1.0 ^2.6 ]decyl ester/(meth)acrylic acid copolymer and other resins [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate /Styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl(meth)acrylate Resins such as copolymers, 3-methyl-3-(meth)acryloxymethyloxetane/(meth)acrylic acid/styrene copolymers [K2]; benzyl (meth)acrylate/ Resins such as (meth)acrylic acid copolymers, styrene/(meth)acrylic acid copolymers [K3]; add glycidyl (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymerization Resin made by adding glycidyl (meth)acrylate to tricyclodecanyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, shrinking (meth)acrylic acid Glyceride added to tricyclodecanyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer [K4]; make (meth)acrylic acid and (meth)acrylic acid ) Resin formed by the reaction of tricyclodecanyl acrylate/glycidyl (meth)acrylate copolymer, which shrinks (meth)acrylic acid and tricyclodecanyl (meth)acrylate/styrene/(meth)acrylic acid Resins such as resins formed by the reaction of copolymers of glycerides [K5]; Tetrahydrophthalic anhydride is further combined with (meth)acrylic acid and tricyclodecanyl (meth)acrylate/glycidyl (meth)acrylate Resins formed by the reaction of ester copolymers, resins formed by the reaction of resins [K6], etc.

The resin (B) is more preferably resin [K1] and resin [K2], particularly preferably resin [K1].

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (B) is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000, still more preferably from 3,000 to 30,000. When the weight average molecular weight exists in the said range, the solubility to the developing solution of an unexposed part becomes high, and there exists a tendency for the remaining film rate and hardness of the obtained pattern to become high also. The degree of dispersion of the resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably from 1 to 6, more preferably from 1.001 to 5, still more preferably from 1.01 to 4.

The acid value (solid content conversion value) of the resin (B) is preferably from 10 mg-KOH/g to 300 mg-KOH/g, more preferably from 20 mg-KOH/g to 250 mg-KOH/g or less, more preferably 25 mg-KOH/g or more and 200 mg-KOH/g or less, even more preferably 30 mg-KOH/g or more and 150 mg-KOH/g or less, especially preferably 60 mg-KOH/g More than g and less than 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 5 to 98 mass%, more preferably from 10 to 95 mass%, and still more preferably from 15 to 93 mass%, in 100 mass% of solid content of the colored resin composition. Also, when the colored resin composition contains the polymerizable compound (C) and the polymerization initiator (D), the content of the resin (B) is preferably 5-90 mass %, More preferably, it is 5-50 mass %, More preferably, it is 10-40 mass %, More preferably, it is 15-35 mass %. When content of resin (B) exists in the said range, there exists a tendency for the solubility to the developing solution of an unexposed part to be high.

＜Polymerizable compound (C)＞ The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D), for example, a polymerizable compound having an ethylenically unsaturated bond, etc. Preferred are (meth)acrylate compounds.

Examples of polymerizable compounds having one ethylenically unsaturated bond include: nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol Acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and the above-mentioned monomer (a), monomer (b) and monomer (c).

Examples of polymerizable compounds having two ethylenically unsaturated bonds include: 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di (Meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Acrylates, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate Acrylates, Tris(2-(meth)acryloxyethyl)isocyanurate, Ethylene glycol-modified pentaerythritol tetra(meth)acrylate, Ethylene glycol-modified dipentaerythritol hexa(meth)acrylic acid Ester, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate and caprolactone modified dipentaerythritol hexa(meth)acrylate Meth)acrylate and the like; dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably from 50 to 4,000, more preferably from 70 to 3,500, still more preferably from 100 to 3,000, still more preferably from 150 to 2,900, especially preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) may be, for example, 1% by mass to 99% by mass, preferably 5% by mass to 90% by mass, with respect to the total amount of solid content of the colored resin composition. Preferably, it is 10 mass % or more and 80 mass % or less, More preferably, it is 20 mass % or more and 70 mass % or less.

＜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 known polymerization initiators can be used.

The polymerization initiator (D) may, for example, be an O-acyl oxime compound, a benzophenone compound, a biimidazole compound, a trioxine compound or an acyl phosphine oxide compound.

As the O-acyl oxime compound, for example, N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyl Oxy-1-(4-phenylthiophenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3- Cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-Acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine, N-acetyloxy-1-[9-ethyl- 6-(2-Methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2- Methyl-4-(3,3-dimethyl-2,4-dioxabicyclopentylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-ylidene Amine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-ylidene Amine and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1- Keto-2-imine etc. In addition, as the O-acyl oxime compound, commercially available items such as Irgacure (registered trademark) OXE01 and OXE02 (manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used. Among them, as the O-acyl oxime compound, it is preferably selected from N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzene Formyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)- At least one of the group consisting of 3-cyclopentylpropane-1-one-2-imine, more preferably N-benzoyloxy-1-(4-phenylthiophenyl)octane -1-keto-2-imine.

As the benzophenone compound, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-( 4-morpholinophenyl)-2-benzylbutan-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4- (4-morpholinyl)phenyl]butan-1-one, etc. Commercial items such as Irgacure (registered trademark) 369, 907, and 379 (the above are manufactured by BASF Corporation) can also be used as the benzophenone compound. Examples of benzophenone compounds include: 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy Base) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl) propan-1-one, α,α-diethoxyacetophenone and benzoyl dimethyl ketal.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3 -dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open Publication No. 6-75372, Japanese Patent Laid-Open Publication No. 6-75373, etc.), 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4' ,5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl) ) biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.) and the 4,4',5,5'-position phenyl is substituted by alkoxycarbonyl A biimidazole compound (for example, refer to Japanese Patent Laid-Open No. 7-10913, etc.) and the like.

Examples of trioxane compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-trimethoxyphenyl, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-trimethoxylate, 2,4-bis(trichloromethyl)-6-helianthyl-1,3,5-trimethoxazole , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three methionyl, 2,4-bis(trichloromethyl)-6-[ 2-(5-Methylfuran-2-yl)ethenyl]-1,3,5-trisulfone, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-Trisal, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-trimethoxyphenyl and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-trimethoxyphenyl wait.

The acylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzoyldiphenylphosphine oxide or the like. Commercial items such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

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; , 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tertiary butylperoxycarbonyl) diphenyl Benzophenone compounds such as ketone and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2- Chloracridone, benzyl, methyl phenylglyoxylate and titanocene compounds, etc. These are preferably used in combination with the following polymerization initiation aids (D1) (especially amines).

The polymerization initiator (D) is preferably a polymerization initiator comprising at least one selected from the group consisting of benzophenone compounds, trioxane compounds, acyl phosphine oxide compounds, O-acyl oxime compounds and biimidazole compounds. agent, more preferably a polymerization initiator comprising an O-acyl oxime compound.

The content of the polymerization initiator (D) is preferably not less than 0.1 parts by mass and not more than 30 parts by mass relative to 100 parts by mass of the total amount of all resins (B) and polymerizable compounds (C) contained in the colored resin composition , More preferably at least 1 part by mass and at most 20 parts by mass. When content of a polymerization initiator (D) exists in the said range, since there exists a tendency for high sensitivity and shortening of exposure time, the productivity of a color filter improves.

＜Polymerization Initiation Auxiliary (D1)＞ The polymerization initiation aid (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator (D). In the case of containing the polymerization initiation aid (D1), it is usually used in combination with the polymerization initiator (D).

化合物及羧酸化合物等。Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, and 9-oxothiophene

compounds and carboxylic acid compounds.

As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate, Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (collectively known as Micheler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-bis(ethylamino)benzophenone methylamino) benzophenone, etc.; a preferred example is 4,4'-bis (diethylamino) benzophenone. In addition, commercial items such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used as the amine compound.

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

化合物，可例舉：2-異丙基9-氧硫𠮿

、4-異丙基9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

、2,4-二氯9-氧硫𠮿

及1-氯-4-丙氧基9-氧硫𠮿

等。as 9-oxosulfur

Compounds, for example: 2-isopropyl 9-oxosulfur

, 4-isopropyl 9-oxosulfur 𠮿

, 2,4-Diethyl 9-oxosulfur 𠮿

, 2,4-dichloro-9-oxosulfur 𠮿

and 1-chloro-4-propoxy-9-oxosulfur

wait.

As the carboxylic acid compound, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio Acetic acid, N-naphthylglycine and naphthyloxyacetic acid, etc.

When using such a polymerization initiation aid (D1), its content is preferably 100 parts by mass of the total amount of all resins (B) and polymerizable compounds (C) contained in the colored resin composition. 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass.

＜Solvent (E)＞ The solvent (E) is not particularly limited, and solvents generally used in this field can be used. The solvent (E) can be, for example, an ester solvent (a solvent containing -COO- and not containing -O- in the molecule), an ether solvent (a solvent containing -O- and not containing -COO- in the molecule), an ether ester solvent (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (containing OH in the molecule and not containing -O-, -CO - and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc. These solvents can also use 2 or more types together.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isopentyl acetate. ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetyl acetate, ethyl acetyl acetate, Cyclohexanol 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, Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol , tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, two Ethylene glycol dibutyl ether, anisole, phenetole and methyl anisole, etc.

Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropane Methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Propyl 2-methoxypropionate, 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 monoethyl ether acetate Ester, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and Dipropylene glycol methyl ether acetate, etc.

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

The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol or glycerin.

The aromatic hydrocarbon solvent may, for example, be benzene, toluene, xylene or mesitylene.

The amide solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

As the solvent (E), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N-methylpyrrolidone, ethyl lactate, and cyclohexanone are preferable.

When the solvent (E) is included, the content of the solvent (E) is usually at most 99.99% by mass, preferably at least 40% by mass and at most 99% by mass, more preferably at most 99% by mass, based on the total amount of the colored resin composition 50 mass % or more and 97 mass % or less, More preferably, it is 70 mass % or more and 95 mass % or less, More preferably, it is 75 mass % or more and 95 mass % or less. In other words, the total amount of the solid content of the colored resin composition is usually 0.01% by mass or more, preferably 1% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 50% by mass or less, and still more preferably 5 mass % or more and 30 mass % or less, More preferably, it is 5 mass % or more and 25 mass % or less. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes favorable, and the color density when forming a color filter is sufficient, so the display characteristics tend to become favorable.

＜Leveling agent (F)＞ The leveling agent (F) may, for example, be a silicone-based surfactant, a fluorine-based surfactant, or a silicone-based surfactant having a fluorine atom. These may have a polymeric group in a side chain.

As a polysiloxane-type surfactant, the thing which has a siloxane bond in a molecule|numerator, etc. are mentioned. Specifically, Toray Silicone DC3PA, the SH7PA, the DC11PA, the SH21PA, the SH28PA, the SH29PA, the SH30PA, the SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive High-Tech Materials Japan Co., Ltd.), etc.

As a fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, examples include: Fluorad (registered trademark) FC430, the FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, the F171, the F172, the F173, the F177, the F183, and the F554 , the R30, the RS-718-K (manufactured by DIC Co., Ltd.), Eftop (registered trademark) EF301, the EF303, the EF351, the EF352 (manufactured by Mitsubishi Materials Corporation), Surflon (registered trademark) S381, the S382, the SC101, the SC105 (manufactured by AGC Co., Ltd.), E5844 (manufactured by Daikin Institute of Fine Chemicals Co., Ltd.), and the like.

Examples of the polysiloxane-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, the BL20, the F475, the F477, and the F443 (manufactured by DIC Co., Ltd.) may, for example, be mentioned.

When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably from 0.0005% by mass to 1% by mass, more preferably 0.001% by mass, based on the total amount of the colored resin composition 0.5% by mass or more, and more preferably 0.005% by mass or more and 0.1% by mass or less. Furthermore, the content of the pigment dispersant is not included in the content. When the content rate of a leveling agent (F) exists in the said range, the flatness of a color filter can be made favorable.

＜Other ingredients＞ The colored resin composition may optionally contain fillers, other polymer compounds, adhesion promoters, quenching agents, antioxidants, light stabilizers, chain transfer agents, and other known additives in the technical field.

<Manufacturing method of colored resin composition> The colored resin composition can be obtained by mixing a colorant (A), a resin (B), an optional polymerizable compound (C), a polymerization initiator (D), a solvent (E), a leveling agent (F) and Other ingredients are mixed to prepare. Mixing can be performed by known or customary equipment and conditions. The colorant (A) may be mixed with a part or all of the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter becomes about 0.2 μm or less. It is preferably used in a dispersed state. At this time, part or all of the above-mentioned dispersant and resin (B) may also be prepared as needed. Moreover, the coloring agent (A) can also be used in the state which melt|dissolved in some or all of solvents (E) beforehand. The target colored resin composition can be prepared by mixing the remaining components in the colorant-containing solution obtained as described above so as to have a specific concentration.

＜Manufacturing method of color filter＞ A color conversion layer or a color filter can be formed using the colored resin composition. As a method for forming a colored pattern, photolithography, inkjet method, printing method and the like are preferable. Among them, photolithography is preferred. Photolithography is a method in which the above-mentioned colored resin composition is applied to a substrate, dried to form a colored resin composition layer, and the colored resin composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film that is a cured product of the above-mentioned colored resin composition layer can be formed by not using a photomask and/or not performing development during exposure. Moreover, it is also possible to form a colored coating film by applying the above-mentioned colored resin composition on a substrate, drying it to form a colored resin composition layer, and post-baking it. The colored pattern or colored coating film formed in the above manner is the color filter of the present invention.

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

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica, or polycarbonate, polymethylmethacrylate, polyterephthalate, etc. are used. Resin plates such as ethylene formate, silicon, and aluminum, silver, silver/copper/palladium alloy thin films formed on the above-mentioned substrates. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The formation of pixels of each color by photolithography can be carried out with known or commonly used equipment and conditions. For example, it can be produced as follows. First, the colored resin composition is coated on the substrate, and then heat-dried (pre-baked) and/or reduced-pressure drying is performed to remove volatile components such as solvents and dry the colored resin composition to obtain a smooth colored resin composition object layer. As a coating method, a spin coat method, a slit coat method, a slit and spin coat method, etc. are mentioned. The temperature at the time of heat drying is preferably 30°C or more and 120°C or less, more preferably 50°C or more and 110°C or less. Moreover, as heating time, it is preferable that it is 10 seconds or more and 60 minutes or less, and it is more preferable that it is 30 seconds or more and 30 minutes or less. When performing reduced-pressure drying, it is preferable to carry out in the temperature range of 20 degreeC or more and 25 degreeC or less under the pressure of 50 Pa or more and 150 Pa or less. The film thickness of the colored resin composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the intended color filter.

Then, the colored resin composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application is used. In addition, in order to uniformly irradiate the entire exposure surface with parallel light rays and accurately position the mask and the substrate on which the colored resin composition layer is formed, it is preferable to use a mask alignment exposure machine or a stepper exposure machine for exposure. device.

As a light source for exposure, a light source that generates light having a wavelength of not less than 250 nm and not more than 450 nm is preferable. For example, for light below 350 nm, use a filter that cuts off the wavelength region, or use a bandpass filter that extracts these wavelength regions for light near 436 nm, 408 nm, or 365 nm The device selectively extracts. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

The exposed colored resin composition layer is developed in contact with a developer, thereby forming a colored pattern on the substrate. By image development, the unexposed part of the colored resin composition layer is dissolved in a developing solution and removed. As a developing solution, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration in the aqueous solution of these basic compounds is preferably not less than 0.01% by mass and not more than 10% by mass, more preferably not less than 0.03% by mass and not more than 5% by mass. Furthermore, the developer may also contain a surfactant. The developing method may be any one of a liquid covering method, a dipping method, and a spraying method. Furthermore, the substrate can be tilted at any angle during image development. The developed substrate is preferably washed with water.

Furthermore, it is preferable to post-bak the obtained colored pattern. The post-baking temperature is preferably not less than 150°C and not more than 250°C, more preferably not less than 160°C and not more than 240°C. The post-baking time is preferably from 1 minute to 120 minutes, more preferably from 10 minutes to 60 minutes.

＜Display device＞ The above-mentioned color filter is effectively used as a color filter for display devices (such as liquid crystal display devices, organic EL (Electroluminescence, electroluminescence) devices, electronic paper, etc.) and solid-state imaging devices, especially organic EL devices. The color filter. [Example]

Hereinafter, the present invention will be described in more detail by citing examples. Of course, the present invention is not limited by the following examples, and it is reasonable to add changes and implement them appropriately within the scope of the above-mentioned and the following gist, etc. All are included in the technical scope of the present invention. In addition, hereinafter, "part" means "mass part", and "%" means "mass %", unless otherwise specified.

In the following examples, the structures of the compounds were confirmed by mass spectrometry (LC; Model 1200, MASS manufactured by Agilent; Model LC/MSD6130 manufactured by Agilent).

The polystyrene conversion weight average molecular weight (Mw) and the number average molecular weight (Mn) of resin were measured by GPC (Gel Permeation Chromatography, gel permeation chromatography) under the following conditions. Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: tetrahydrofuran Flow rate: 1.0 mL/min The solid content concentration of the analysis sample: 0.001 to 0.01% by mass Injection volume: 50 μL Detector: RI (Refractive Index, Refractive Index) Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.) The ratio (Mw/Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was made into degree of dispersion.

(Synthesis Example 1) 42 parts of acenaphthylquinone (manufactured by Tokyo Chemical Industry Co., Ltd.), 15 parts of malononitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 672 parts of dehydrated acetonitrile (manufactured by Kanto Chemical Co., Ltd.) were mixed and heated at 82° C. Stirring was continued for 6 hours. The obtained mixture was cooled to 0°C, resulting in an orange-red precipitate. The mixture containing the orange-red precipitate was filtered, and the filtered residue was washed with 200 parts of acetonitrile and 400 parts of water. The obtained residue was dried under reduced pressure at 60° C. to obtain 48 parts of the compound represented by formula (pt2) (90% yield).

<Identification of compound (pt2)> (mass spectrometry) ionization mode = ESI +: m/z = [M + H] ⁺ 231 accurate mass: 230

(Synthesis Example 2) 25 parts of the compound (pt2) obtained in Synthesis Example 1, 1.5 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.), 312 parts of acetonitrile (manufactured by Kanto Chemical Co., Ltd.), and 2 parts of water were mixed, and mixed at 80 Stir at °C for 5 hours. Cooling to 0°C resulted in a brown precipitate. The mixture containing the brown precipitate was filtered, and the filtered residue was washed with 400 parts of water and 50 parts of acetonitrile. The obtained residue was dried under reduced pressure at 60°C, and purified with a silica gel column (solvent: chloroform/ethyl acetate=10/1, vol/vol), and the yellowish-brown formula (pt3) was obtained 17 parts of the compound (yield 68%).

<Identification of compound (pt3)> (mass spectrometry) ionization mode = ESI +: m/z = [M + H] ⁺ 231 accurate mass: 230

(Synthesis Example 3) To 1.0 part of compound (pt3) obtained in Synthesis Example 2, 5.6 parts of 98% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) was added, followed by stirring at 50° C. for 10 hours. The reaction solution was added dropwise to ice water, and the obtained residue was filtered. The obtained solid was washed with water and then with methanol, and dried under reduced pressure at 60° C. to obtain 0.90 parts of the compound represented by formula (pt4) (83% yield).

<Identification of Compound (pt4)> (Mass Spectrometry) Ionization Mode = ESI-: m/z = [MH] ^- 248 Accurate Mass: 249

(Synthesis Example 4) 1.0 parts of the compound (pt4) obtained in Synthesis Example 3 was dissolved in 50 parts of N,N-dimethylformamide, 0.5 parts of 1-hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the Stirring was continued for 5 hours. The reaction liquid was added dropwise to a mixed solvent of hexane and chloroform, and the obtained residue was filtered. The obtained solid was purified using an alumina column (solvent: tetrahydrofuran/water=1/1, vol/vol), and dried under reduced pressure at 60° C. to obtain the compound represented by formula (Ii-6) ( Hereinafter, it may be referred to as compound (Ii-6)) 0.20 parts (yield 16%).

<Identification of compound (Ii-6)> (mass spectrometry) ionization mode = ESI +: m/z = [M + H] ⁺ 349 accurate mass: 348

(Synthesis Example 5) 1.0 parts of the compound (pt4) obtained in Synthesis Example 3, 3.1 parts of ethyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.4 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.) and 50 parts of acetonitrile were mixed, and mixed at 40 Stir at °C for 12 hours. The reaction solution was filtered with diatomaceous earth, the filtrate was concentrated, and the obtained solid was purified using an alumina column (solvent: decreasing from chloroform to acetonitrile), and dried under reduced pressure at 60°C to obtain the formula (pt5 ) represented 0.56 parts of the compound (yield 47%).

<Identification of compound (pt5)> (mass spectrometry) ionization mode = ESI +: m/z = [M + H] ⁺ 278 accurate mass: 277

(Synthesis Example 6) Replace 1.0 parts of compound (pt4) with 1.1 parts of compound (pt5) obtained in Synthesis Example 5, and replace 1.0 parts of 1-hexylamine with 0.9 parts of n-butylamine. Method The compound represented by formula (Ii-83) (hereinafter, sometimes referred to as compound (Ii-83)) was obtained in 0.20 parts (yield 18%).

<Identification of compound (Ii-83)> (mass spectrometry) ionization mode = ESI +: m/z = [M + H] ⁺ 349 accurate mass: 348

(Synthesis Example 7) Except that 1.0 parts of 1-hexylamine was replaced by 1.1 parts of benzylamine, the compound represented by formula (Ii-66) (hereinafter sometimes referred to as compound (Ii-66) was obtained in the same manner as in Synthesis Example 4. )) 0.2 parts (yield 21%).

<Identification of compound (Ii-66)> (mass spectrometry) ionization mode = ESI +: m/z = [M + H] ⁺ 355 accurate mass: 354

(Synthesis Example 7) In addition to replacing 1.0 parts of 1-hexylamine with 1.2 parts of diisobutylamine, the compound represented by formula (Ii-190) (hereinafter sometimes referred to as compound (Ii) was obtained in the same manner as in Synthesis Example 4. -190)) 0.1 part (yield 9%).

<Identification of compound (Ii-190)> (mass spectrometry) ionization mode = ESI +: m/z = [M + H] ⁺ 377 accurate mass: 376

(Synthesis Example 8) Except that 1.0 parts of 1-hexylamine was replaced by 1.1 parts of piperidine, the compound represented by formula (Ii-320) (hereinafter sometimes referred to as compound (Ii-320) was obtained in the same manner as in Synthesis Example 4. ) 0.3 parts (yield 28%).

<Identification of compound (Ii-320)> (mass spectrometry) ionization mode = ESI +: m/z = [M + H] ⁺ 333 accurate mass: 332

(Synthesis Example 9) A compound represented by the following formula (x) (hereinafter, sometimes referred to as compound (x)) was synthesized according to the description in Synthesis Example 2 of JP-A-2020-079397.

(Synthesis Example 28) An appropriate amount of nitrogen gas was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere, and 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-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^{2, 6} ] A mixed solution of 289 parts of a mixture of decane-9-yl acrylate (containing a molar ratio of 1:1) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution obtained by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition, it was kept at 80°C for 4 hours, and then cooled to room temperature to obtain a copolymer with a solid content of 35.1% and a viscosity of 125 mPa·s as measured by a B-type viscometer (23°C) ( Resin B1) Solution. The weight average molecular weight Mw of the produced copolymer was 9.2×10 ³ , the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. Resin B1 has the following structural units.

<Example 1> (1) Preparation of coloring composition The following components were mixed, and coloring composition 1 was obtained. (A) Colorant: compound (Ii-6) 2.6 parts (B) Resin: Resin B1 solution 54 parts (E) Solvent: propylene glycol monomethyl ether acetate 420 parts (2) Preparation of colored resin composition Next, the following components were mixed, and the colored resin composition 1 was obtained. Coloring composition 1 478 parts (C) Polymerizable compound: dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation) 2 parts (F) Leveling agent: polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts

(3) Production of colored coating film (color filter) The colored resin composition was coated on a 5 cm square glass substrate (Eagle XG; Corning company) and then prebaked at 100°C for 3 minutes to form a colored resin composition layer. After cooling, use an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) to expose the colored resin composition layer formed on the substrate at an exposure dose of 80 mJ/cm ² (based on 365 nm) in the atmosphere. light exposure. After light irradiation, post-baking was performed at 230° C. for 30 minutes in an oven to obtain a colored coating film. In addition, the film thickness of the colored coating film was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 6.

(4) Contrast evaluation For the obtained colored coating film, a contrast meter (CT-1: manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5A: manufactured by TOPCON Corporation, light source: F-10, polarizing film: manufactured by Tsubosaka Electric Co., Ltd.) was used Measure contrast. In addition, the blank value at the time of measurement was 30,000. If the contrast of the colored coating film is good, the colored pattern produced from the same colored resin composition can also be said to have good contrast. The results are shown in Table 6.

(5) Heat resistance test The obtained colored coating film was heated in an oven at 230° C. for 120 minutes in the atmosphere. According to the measured values of xy chromaticity coordinates (x, y) and Y before and after the test, the color difference ΔE*ab is calculated according to the method described in JIS Z 8730:2009 (7. Calculation method of color difference). Regarding the color difference ΔE*ab, the smaller the value, the smaller the color change, and as long as ΔE*ab is 10 or less, it can be said that the colored coating film has no problem in practical use as a color filter. Moreover, as long as the heat resistance of the colored coating film is good, it can be said that the heat resistance of the colored pattern produced from the same colored resin composition is also good. The results are shown in Table 7.

(6) Light fastness test A UV cut filter (COLORED OPTICAL GLASS L38; manufactured by HOYA Corporation; cut off light below 380 nm) was arranged on the obtained colored coating film, and was irradiated for 48 Hour xenon light. According to the measured values of xy chromaticity coordinates (x, y) and Y before and after the test, the color difference ΔE*ab is calculated according to the method described in JIS Z 8730:2009 (7. Calculation method of color difference). Regarding the color difference ΔE*ab, the smaller the value, the smaller the color change, and as long as ΔE*ab is 10 or less, it can be said that the colored coating film has no problem in practical use as a color filter. Moreover, as long as the light resistance of the colored coating film is good, it can be said that the light resistance of the colored pattern produced from the same colored resin composition is also good. The results are shown in Table 7.

＜Comparative example 1＞ Except having replaced the compound (Ii-6) of Example 1 with compound (x), the colored resin composition was prepared in the same manner as Example 1, the colored coating film was produced, and contrast evaluation was performed. The results are shown in Table 6.

[Table 6] Film thickness (μm) contrast Example 1 2.0 6800 Comparative example 1 2.0 333

[Table 7] Heat Resistance (∆E*ab) Lightfastness (∆E*ab) Example 1 4 8

In addition to using the compound represented by formula (Ii-83), formula (Ii-66), formula (Ii-190), or formula (Ii-320) instead of the compound represented by formula (Ii-6) to implement The colored coating film obtained from the colored resin composition prepared in the same manner as in Example 1 is the same as in Example 1, and the results of higher contrast, higher heat resistance and higher light resistance are obtained.

Claims (4)

A colored resin composition, which contains a colorant and a resin, and the colorant comprises a compound represented by formula (I),

[In formula (I), R ¹ to R ³ independently represent a hydrogen atom or a hydrocarbon group with a carbon number of 1 to 20 that may have a substituent; R ² and R ³ may form a substituent R ⁴ ~ R ⁸ independently represent a hydrogen atom, -R ⁹ , -OR ⁹ , -CO-OR ⁹ , -O-CO-R ⁹ , halogen atom, hydroxyl, carboxyl, sulfo, or nitric acid R ⁹ represents a hydrocarbon group with 1 to 20 carbon atoms that may have a substituent, and when there are multiple R ⁹ s, they may be the same or different]. The colored resin composition according to claim 1, further comprising a polymerizable compound and a polymerization initiator. A color filter formed of the colored resin composition according to claim 1 or 2. A display device comprising the color filter according to claim 3.