CN114967330A

CN114967330A - Colored resin composition

Info

Publication number: CN114967330A
Application number: CN202210138522.2A
Authority: CN
Inventors: 滨木裕史
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2021-02-24
Filing date: 2022-02-15
Publication date: 2022-08-30
Also published as: JP2022129248A; TW202303277A; KR20220121204A

Abstract

The invention provides a colored resin composition capable of forming a color filter with excellent heat resistance. A colored resin composition comprising a colorant and a resin, wherein the colorant comprises a compound represented by the formula (I). In the formula (I), R ¹ ～R ¹¹ Independently of one another, a hydrogen atom, -R ^a1 、‑OR ^a1 Halogen atom, hydroxy group, carboxy group, -CO-O-R ^a1 、‑O‑CO‑R ^a1 、‑CO‑R ^a1 Or nitro, R ⁷ And R ⁸ May be bonded to each other to form a ring. E represents C-H, C-R ^a1 Or N. R ^a1 Can representA substituted hydrocarbon group having 1 to 20 carbon atoms.

Description

Colored resin composition

Technical Field

The present invention relates to a colored resin composition.

Background

Color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are made of colored resin compositions. As a colored resin composition used for forming the color filter, various colorants are used, and for example, an example is known in which a compound represented by the following formula (x) is used in a colored composition (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2020 and 79396

Disclosure of Invention

Problems to be solved by the invention

However, the above perylene compounds may not have sufficiently satisfactory heat resistance when prepared into a colored resin composition. Accordingly, an object of the present invention is to provide a colored resin composition capable of forming a color filter having excellent heat resistance.

Means for solving the problems

The gist of the present invention is as follows.

[1] A colored resin composition containing a colorant and a resin, wherein the colorant comprises a compound represented by the formula (I).

[ in the formula (I),

R ¹ ～R ¹¹ independently of one another, represents a hydrogen atom, -R ^a1 、-OR ^a1 Halogen atom, hydroxy group, carboxy group, -CO-O-R ^a1 、-O-CO-R ^a1 、-CO-R ^a1 Or nitro, R ⁷ And R ⁸ May be bonded to each other to form a ring.

E represents C-H, C-R ^a1 Or N.

R ^a1 Represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.]

[2] The colored resin composition according to [1], which further comprises a polymerizable compound and a polymerization initiator.

[3] A color filter comprising the colored resin composition according to [1] or [2 ].

[4] A display device comprising the color filter of [3 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a colored resin composition capable of forming a color filter having excellent heat resistance can be provided.

Detailed Description

The colored resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as a colorant (a)) and a resin (hereinafter, sometimes referred to as a resin (B)), and the colorant contains a compound represented by formula (I).

The colored resin composition of the present invention may further contain a polymerizable compound (hereinafter, sometimes referred to as a polymerizable compound (C)) and a polymerization initiator (hereinafter, sometimes 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 solvent (E)).

The colored resin composition of the present invention may further contain a polymerization initiation aid (hereinafter, sometimes referred to as polymerization initiation aid (D1)).

The colored resin composition of the present invention may further contain a leveling agent (hereinafter, sometimes referred to as a leveling agent (F)).

In the present specification, unless otherwise specified, the compounds exemplified as the respective components may be used alone or in combination of plural kinds.

< colorant (A) >)

The colorant (a) contains a compound represented by formula (I) (hereinafter, sometimes referred to as compound (I)). The colored resin composition containing the compound (I) as a colorant is excellent in heat resistance, preferably also excellent in light resistance.

Compound (I)

[ in the formula (I),

E represents C-H, C-R ^a1 Or N.

R ^a1 Represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.]

As R ^a1 Examples of the hydrocarbon group having 1 to 20 carbon atoms include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or alicyclic.

As R ^a1 Examples of the saturated or unsaturated chain hydrocarbon group include: linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl; isopropyl, (1-ethyl) propyl, isobutyl, sec-butyl, tert-butyl, (1-ethyl) butyl, (2-ethyl) butyl, (1-propyl) butyl, isopentyl, neopentyl, tert-pentyl, (2-methyl) pentyl, (1-ethyl) pentyl, (3-ethyl) pentyl, (1-propyl) pentyl, (1-butyl) pentyl, isohexyl, (2-methyl) hexyl, (5-methyl) hexyl, (2-ethyl) hexyl, (1-butyl) hexyl, (1-pentyl) hexyl, (2-methyl) heptyl, (2-ethyl) heptyl, (3-ethyl) heptyl, (1-hexyl) heptyl, (2-methyl) octyl, (2-ethyl) octyl, (1-heptyl) octyl, and, Branched alkyl groups such as (2-ethyl) nonyl and (1-octyl) nonyl; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), (1-methyl) vinyl, 2-butenyl, 3-butenyl, 1, 3-butadienyl, (1- (2-propenyl)) vinyl, (1, 2-dimethyl) propenyl, 2-pentenyl and the like; and so on. The number of carbon atoms of the saturated chain hydrocarbon group is preferably 1 to 18, more preferably 2 to 15, and further preferably 3 to 12. The number of carbon atoms of the unsaturated chain hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and further preferably 3 to 12.

As R ^a1 Examples of the saturated or unsaturated alicyclic hydrocarbon group include: cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; cycloalkenyl groups such as cyclohexenyl (e.g., cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, cyclooctenyl, and the like; norbornyl and adamantineAlkyl, bicyclo [2.2.2]Octyl; and so on. The number of carbon atoms of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 15, more preferably 3 to 12.

As R ^a1 Examples of the aromatic hydrocarbon group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group, an anthryl group, a pyrenyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12.

Then R ^a1 The hydrocarbon group represented may have an upper limit of 20 carbon atoms, and may be a combination of 2 or more of the above-mentioned chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Such a group may be, for example, a group obtained by combining an aromatic hydrocarbon group with at least one selected from the group consisting of a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and in the hydrocarbon group based on the combination, the chain hydrocarbon group may be combined as a divalent group (for example, alkanediyl). Examples of hydrocarbon groups based on the above combinations include: aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenylethyl; arylalkenyl groups such as phenylvinyl (styryl); arylalkynyl groups such as phenylethynyl; o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2, 3-dimethylphenyl group, 2, 4-dimethylphenyl group, 2, 5-dimethylphenyl group, 2, 6-dimethylphenyl group, 3, 4-dimethylphenyl group, 3, 5-dimethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 2, 3-diisopropylphenyl group, 2, 4-diisopropylphenyl group, 2, 5-diisopropylphenyl group, 2, 6-diisopropylphenyl group, 2,4, 6-triisopropylphenyl group, 4-butylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, 2, 6-di (tert-butyl) phenyl group, 3, 5-di (tert-butyl) phenyl group, alkylaryl groups such as 3, 6-di (tert-butyl) phenyl, 4-tert-butyl-2, 6-dimethylphenyl, 4-pentylphenyl, 4-octylphenyl, 4- (2,4, 4-trimethyl-2-pentyl) phenyl, 2-dodecylphenyl, 3-dodecylphenyl, 4-dodecylphenyl and the like; alkenylaryl such as 4-vinylphenyl; 2, 3-dihydro-4-indenyl, 1,2,3,5,6, 7-hexahydro-4-s-indacenyl, 8-methyl-1, 2,3,5,6, 7-hexahydro-4-s-indacenyl, 5,6,7, 8-tetrahydro-1-naphthyl, 5,6,7, 8-tetrahydro-2-naphthyl, 3-methyl-5, 6,7, 8-tetrahydro-2-naphthylAn aryl group to which an alkanediyl group is bonded, such as a 3,5,5,8, 8-pentamethyl-5, 6,7, 8-tetrahydro-2-naphthyl group; an aryl group having 1 or more aryl groups bonded thereto, such as a biphenyl group and a terphenyl group; cyclohexylmethylphenyl, benzylphenyl, (dimethyl (phenyl) methyl) phenyl; and so on. The hydrocarbon group may be, for example, a hydrocarbon group based on a combination of a chain hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include: 1-methylcyclopropyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1, 2-dimethylcyclohexyl group, 1, 3-dimethylcyclohexyl group, 1, 4-dimethylcyclohexyl group, 2, 3-dimethylcyclohexyl group, 2, 4-dimethylcyclohexyl group, 2, 5-dimethylcyclohexyl group, 2, 6-dimethylcyclohexyl group, 3, 4-dimethylcyclohexyl group, 3, 5-dimethylcyclohexyl group, 2-dimethylcyclohexyl group, 3-dimethylcyclohexyl group, 4-dimethylcyclohexyl group, 2,4, 6-trimethylcyclohexyl group, 2,6, 6-tetramethylcyclohexyl group, 3,5, 5-tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 3, 5-pentylcyclohexyl group, 2, 5-dimethylcyclohexyl group, 3, 4-dimethylcyclohexyl group, 3, 6-dimethylcyclohexyl group, 3, 6-dimethylcyclohexyl group, 2, 6-dimethylcyclohexyl group, 2, 6-dimethylcyclohexyl group, 2, 6-dimethylcyclohexyl group, 2,6, 2,6, 2,5, 6, 4-pentylcyclohexyl group, or a, Alicyclic hydrocarbon groups having 1 or more alkyl groups or alicyclic hydrocarbon groups bonded thereto, such as 4-octylcyclohexyl and 4-cyclohexylcyclohexyl; and an alkyl group to which 1 or more alicyclic hydrocarbon groups are bonded, such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, a cyclohexylethyl group, and an adamantylmethyl group. The number of carbon atoms of the group consisting of 2 or more chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups is preferably 6 to 18, more preferably 6 to 15.

As R ^a1 Examples of the substituent which may be contained in the hydrocarbon group having 1 to 20 carbon atoms include: a halogen atom; a nitrile group; a nitro group; an amino group; a hydroxyl group; alkoxy groups having 1 to 20 carbon atoms such as methoxy and ethoxy; an aryloxy group having 6 to 20 carbon atoms such as a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group, etc.; a thiol group; alkylthio groups having 1 to 20 carbon atoms such as methylthio and ethylthio; allylthio; an arylthio group having 6 to 20 carbon atoms such as a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group and the like; a sulfonyloxy group; an alkylsulfonyloxy group having 1 to 20 carbon atoms such as a methylsulfonyloxy group and an ethylsulfonyloxy group; arylsulfonyloxy group having 6 to 20 carbon atoms such as phenylsulfonyloxy group, 1-naphthylsulfonyloxy group, 2-naphthylsulfonyloxy group and the like(ii) a A silyl group; a boryl group; alkylamino groups having 1 to 20 carbon atoms such as monomethylamino, dimethylamino, trimethylamino, monoethylamino, diethylamino, and triethylamino; arylamino groups having 6 to 20 carbon atoms such as monophenylamino groups, diphenylamino groups, triphenylamino groups and the like; an aralkylamino group having 7 to 20 carbon atoms such as a benzylamino group; a carboxyl group; a carbamoyl group; an alkylcarbonyl group having 2 to 20 carbon atoms such as an acetyl group or a propionyl group; an arylcarbonyl group having 7 to 20 carbon atoms such as a benzoyl group, a 1-naphthylcarbonyl group, a 2-naphthylcarbonyl group and the like; alkoxycarbonyl groups having 2 to 20 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; an aryloxycarbonyl group having 7 to 20 carbon atoms such as a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, or a 2-naphthyloxycarbonyl group; and so on.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. From the viewpoint of synthesis, a chlorine atom and a bromine atom are preferable.

As R ^a1 Examples thereof include groups represented by the following formulae (D-1) to (D-47) and (G-1) to (G-22). It represents a connecting bond.

As R ¹ ～R ¹¹ Is represented by-OR ^a1 Examples thereof include compounds having the above-mentioned R ^a1 Examples of the oxy group include an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. as-OR ^a1 Specific examples thereof include methoxy, ethoxy, propoxy, butoxy, pentyloxy, phenoxy, naphthyloxy and the like.

With respect to as R ¹ ～R ¹¹ Examples of the halogen atom of (b) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of synthesis, a chlorine atom and a bromine atom are preferred.

As R ¹ ～R ¹¹ Represented by-CO-O-R ^a1 Examples thereof include compounds having the above-mentioned R ^a1 Examples of the oxycarbonyl group of (a) include an alkoxycarbonyl group having 2 to 21 carbon atoms and an aryloxycarbonyl group having 7 to 21 carbon atoms. as-CO-O-R ^a1 With R of ^a1 The hydrocarbon-based organic compound is preferably a saturated chain hydrocarbon group, a saturated alicyclic hydrocarbon group, a group obtained by combining an alicyclic hydrocarbon group and a chain hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining an aromatic hydrocarbon group and a chain hydrocarbon group, more preferably a saturated chain hydrocarbon group having 1 to 20 carbon atoms, a saturated alicyclic hydrocarbon group having 3 to 15 carbon atoms, a group obtained by combining an alicyclic hydrocarbon group and a chain hydrocarbon group having 4 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group obtained by combining an aromatic hydrocarbon group and a chain hydrocarbon group having 7 to 20 carbon atoms, further preferably a saturated chain hydrocarbon group having 3 to 18 carbon atoms, a group obtained by combining an alicyclic hydrocarbon group and a chain hydrocarbon group having 4 to 10 carbon atoms, or a group obtained by combining an aromatic hydrocarbon group and a chain hydrocarbon group having 7 to 15 carbon atoms. as-CO-O-R ^a1 Specific examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, (1-ethyl) pentyloxycarbonyl, hexyloxycarbonyl, (2-ethyl) hexyloxycarbonyl, heptyloxycarbonyl, (1-butyl) heptyloxycarbonyl, octyloxycarbonyl, (1-heptyl) octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, tridecyloxycarbonyl, tetradecyloxycarbonyl, pentadecyloxycarbonyl, hexadecyloxycarbonyl, heptadecyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, cyclohexyloxycarbonyl, cyclohexylmethoxycarbonyl, eicosyloxycarbonyl and the like.

As R ¹ ～R ¹¹ Represented by-O-CO-R ^a1 Examples thereof include compounds having the above-mentioned R ^a1 Examples of the carbonyloxy group include an alkylcarbonyloxy group having 2 to 21 carbon atoms and an arylcarbonyloxy group having 7 to 21 carbon atoms. as-O-CO-R ^a1 Specific examples thereof include methylcarbonyloxy, ethylcarbonyloxy and propylcarbonyloxyA phenyl group, a butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, a (2-ethyl) hexylcarbonyloxy group, a phenylcarbonyloxy group, a cyclohexylcarbonyloxy group, etc.

As R ¹ ～R ¹¹ Represented by-CO-R ^a1 Examples thereof include compounds having the above-mentioned R ^a1 Examples of the carbonyl group of (a) include an alkylcarbonyl group having 2 to 21 carbon atoms and an arylcarbonyl group having 7 to 21 carbon atoms. As a group-CO-R ^a1 Specific examples thereof include acetyl, propionyl, butyryl, pentanoyl, hexanoyl, cyclohexanoyl, and benzoyl.

As R ⁷ And R ⁸ Examples of the ring bonded to each other include those represented by the following formulae (H-1) to (H-4).

[ formulae (H-1) to (H-4),

R ¹² ～R ²⁴ independently of one another, represents a hydrogen atom, -R ^a2 、-OR ^a2 Halogen atom, hydroxy group, carboxy group, -CO-O-R ^a2 、-O-CO-R ^a2 、-CO-R ^a2 Or nitro, R ^a2 Represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.

R represents ⁷ Having a connecting bond represented by R ⁸ The connecting key is provided.]

With respect to R ^a2 The hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent(s) is represented by R ^a1 The same applies to the groups described above for the substituted hydrocarbon group having 1 to 20 carbon atoms, and the preferred embodiments are also the same.

As to R ¹² ～R ²⁴ Examples of the halogen atom of (b) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of synthesis, a chlorine atom and a bromine atom are preferable.

With respect to as R ¹² ～R ²⁴ OR of ^a2 、-CO-O-R ^a2 、-O-CO-R ^a2 and-CO-R ^a2 Are exemplified asR ¹ ～R ¹¹ Is represented by-OR ^a1 、-CO-O-R ^a1 、-O-CO-R ^a1 and-CO-R ^a1 The groups described.

In E, C-H means a carbon atom to which a hydrogen atom is bonded, C-R ^a1 Means that is bonded with R ^a1 N means a nitrogen atom.

As R ¹ And R ² The alkyl group is preferably a saturated chain hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a group in which an aromatic hydrocarbon group which may have a substituent and a chain hydrocarbon group are combined, independently of each other. The saturated chain hydrocarbon group is preferably a saturated branched hydrocarbon group from the viewpoint of improving the solubility of the compound (I) in the solvent. The saturated chain hydrocarbon group (preferably a saturated branched hydrocarbon group) preferably has 1 to 15 carbon atoms, more preferably 3 to 15 carbon atoms. As the above aromatic hydrocarbon group, a phenyl group is preferable. The group obtained by combining the aromatic hydrocarbon group and the chain hydrocarbon group is preferably a phenyl group to which a chain hydrocarbon group having 1 to 12 carbon atoms (preferably 1 to 10 carbon atoms) is bonded, more preferably a phenyl group to which a chain hydrocarbon group having 2 to 3 carbon atoms and 1 to 4 carbon atoms is bonded, and still more preferably a phenyl group to which a chain hydrocarbon group having 1 to 4 carbon atoms is bonded at 2 ortho-positions. Wherein, as R ¹ And R ² More preferably, the groups represented by the formulae (D-4) to (D-14) or (G-5) to (G-22) are independent of each other, and still more preferably, the groups represented by any one of the formulae (D-4) to (D-14), formula (G-5), formula (G-7), formula (G-8), formula (G-11) to (G-13), formula (G-15), formula (G-16), formula (G-19), formula (G-21) or formula (G-22) are independent of each other, particularly preferably a group represented by any one of the formulae (D-4) to (D-14), formula (G-7), formula (G-11), formula (G-13), formula (G-15) or formula (G-16) independently of one another.

In addition, as R ¹ And R ² Preferably, the same groups.

As R ³ ～R ⁶ Preferably, each independently of the other, a hydrogen atom, a halogen atom, or a hydroxyl group, and more preferably a hydrogen atom.

As R ⁷ And R ⁸ Preferably independently of one another, a hydrogen atom, a halogen atom or a hydroxyl group, or are bonded to one anotherThe two are combined to form a ring,

more preferably R ⁷ And R ⁸ Is a hydrogen atom, or R ⁷ And R ⁸ Are bonded to each other to form any of the groups represented by the formulae (H-1) to (H-3),

further preferred is R ⁷ And R ⁸ Is a hydrogen atom, or R ⁷ And R ⁸ Are bonded to each other to form the above formula (H-1) or formula (H-2).

As R ¹² ～R ²⁴ Preferably independently of one another, a hydrogen atom, -R ^a2 A halogen atom or a hydroxyl group, more preferably a hydrogen atom.

As R ⁹ ～R ¹¹ Preferably independently of one another, a hydrogen atom, -R ^a1 A halogen atom or a hydroxyl group, more preferably a hydrogen atom.

As E, C-H or N is preferred.

Specific examples of the compound (I) include the compounds (I-1) to (I-30) shown in the following Table 1.

[ Table 1]

In table 1, H represents a hydrogen atom, and N represents a nitrogen atom.

D-6, D-13 and G-7 each represents a group represented by the above formula (D-6), formula (D-13) or formula (G-7).

C-H means a carbon atom to which a hydrogen atom is bonded.

H-1-1, H-2-1, H-3-1, H-4-1 mean R ⁷ And R ⁸ And (b) are bonded to each other to form groups represented by the following formulae (H-1-1), (H-2-1), (H-3-1) and (H-4-1). In the formula, R represents ⁷ Having a connecting bond represented by R ⁸ The connecting key is provided.

The compound (I) is preferably the compounds (I-17) to (I-24), more preferably the compounds (I-17) to (I-22).

Compound (I) can be produced, for example, according to route 1 or route 2.

Route 1 includes the following steps: reacting a compound represented by the following formula (pt-1) with X ₂ A step (i) for obtaining a compound represented by the formula (pt-2) by a reaction; and a step (ii) in which a compound represented by the formula (pt-2) is reacted with a compound represented by the formula (MA-1) to obtain a compound (I).

The route 2 includes the following steps: a step (iii) in which a compound represented by the following formula (pt-2) is reacted with a compound represented by the formula (MA-2) to obtain a compound represented by the formula (pt-3); and a step (iv) for converting the compound represented by the formula (pt-3) to obtain a compound (I).

In the above formulae (pt-1) to (pt-3), R ¹ ～R ¹¹ And E represents the same meaning as described above. In the formulae (MA-1) and (MA-2), R ^B1 Independently of each other, a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group, 2R ^B1 2, 2-dimethylpropyl-1, 3-diyl group, 2, 3-dimethylbutyl-2, 3-diyl group, 2-methylpentyl-2, 4-diyl group, 1, 2-phenylene group and the like which are obtained by forming a ring.

X used in Process (i) of route 1 ₂ X in (A) represents a halogen atom, preferably a chlorine atom or a bromine atom. The compound represented by the formula (pt-2) can be prepared by reacting a compound represented by the formula (pt-1) with X ₂ In a solvent.

Examples of the compound represented by the formula (pt-1) include N, N' -bis (2, 6-diisopropylphenyl) -3,4,9, 10-perylenetetracarboxylic acid diimide and the like.

Examples of the solvent include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; 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, and 1, 2-dichlorobenzene; amide solvents such as N, N-dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and carboxylic acid solvents such as acetic acid, propionic acid and butyric acid, more preferably dichloromethane and chloroform.

X is added to 1 mole of the compound represented by the formula (pt-1) ₂ The amount of (b) to be used is usually 1 to 5 mol, more preferably 1 to 2.5 mol, and still more preferably 1 to 1.25 mol.

The solvent is usually used in an amount of 1 to 1000 parts by mass based on 1 part by mass of the compound represented by the formula (pt-1).

The reaction temperature is usually from-100 ℃ to 300 ℃.

The compound (I) in the step (ii) can be produced by: a compound represented by the formula (pt-2) (which may be referred to as a compound (pt-2)) is reacted with a compound represented by the formula (MA-1) in a solvent in the presence of a catalyst, a phosphine ligand and a base.

Examples of the catalyst include tris (dibenzylideneacetone) dipalladium (0), bis (dibenzylideneacetone) palladium (0), palladium (II) acetate, palladium (II) chloride, sodium tetrachloropalladium (II), palladium (II) chloride (pi-cinnamyl) (dimer), allylpalladium (II) chloride dimer, bis (benzonitrile) palladium (II) dichloride, and bis (acetonitrile) palladium (II) dichloride, and palladium (II) acetate and bis (dibenzylideneacetone) palladium (0) are more preferable.

Examples of the phosphine ligand include tributylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, tri (3-methoxyphenyl) phosphine, tris [3, 5-bis (trifluoromethyl) phenyl ] phosphine, ethyldiphenylphosphine, tris (2, 6-dimethoxyphenyl) phosphine, tris (4-fluorophenyl) phosphine, diphenylpropylphosphine, di-tert-butylphenyl phosphine, tris (2-furyl) phosphine, tris (2-thienyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, methyldiphenylphosphine, 1- [2- (di-tert-butylphosphino) phenyl ] -3, 5-diphenyl-1H-pyrazole, (4-dimethylaminophenyl) di-tert-butylphosphine, tris (o) phosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-fluorophenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (4-methoxyphenyl) di-tert-butylphenyl) phosphine, tris (p-methoxyphenyl) phosphine, and (p-methoxyphenyl) phosphine, 2- (di-tert-butylphosphino) biphenyl, di-tert-butyl (1, 1-diphenyl-1-propen-2-yl) phosphine, isopropyldiphenylphosphine, 2- (dicyclohexylphosphino) -2 ' - (dimethylamino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2- (diphenylphosphino) biphenyl, 2-dicyclohexylphosphino-2 ' -methylbiphenyl, 2-dicyclohexylphosphino-2 ', 6 ' -diisopropyloxybiphenyl, 2-dicyclohexylphosphino-2 ', 6 ' -dimethoxybiphenyl, dicyclohexyl (1-methyl-2, 2-diphenylcyclopropyl) phosphine, di-tert-butyl (2 ', 4 ', 6 ' -triisopropyl-3, 6-dimethoxy- [1,1 ' -biphenyl ] -2-yl) phosphine, 2-dicyclohexylphosphino-2 ', 4 ', 6 ' -triisopropylbiphenyl, 2-diphenylphosphino-2 ' - (N, N-dimethylamino) biphenyl, 2-di-tert-butylphosphino-2 ', 4 ', 6 ' -triisopropylbiphenyl, a monodentate phosphine ligand such as dicyclohexyl (2 ', 4 ', 6 ' -triisopropyl-3, 6-dimethoxy- [1,1 ' -biphenyl ] -2-yl) phosphine, dicyclohexyl (1, 1-diphenyl-1-propen-2-yl) phosphine, bis (diphenylphosphino) methane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 2 ' -diphenylphosphino-2 ' - (isopropylbiphenyl, 2-diphenylphosphino-2 ' - (N, N-dimethylamino) biphenyl, 2-di-tert-butylphosphino-2 ', 4 ', 6 ' -triisopropylbiphenyl, dicyclohexyl- [1,1 ' -diphenyl-1-propen-2-yl ] phosphine, 1, 3-bis (diphenylphosphino) propane, 2-bis (diphenylphosphino) propane, and the like, Bidentate phosphine ligands such as 1, 4-bis (diphenylphosphino) butane, 2 ' -bis (diphenylphosphino) -1,1 ' -binaphthyl, 4, 5-bis (dicyclohexylphosphino) -9, 9-dimethylxanthene, 1,2,3,4, 5-pentaphenyl-1 ' - (di-tert-butylphosphino) ferrocene, 1 ', 2 ' -bis [ bis (3, 5-dimethylphenyl) phosphino ] -1,1 ' -biphenyl, 4, 5-bis (diphenylphosphino) -9, 9-dimethylhexane, 1, 3-bis (diphenylphosphino) propane, 1 ' -bis (di-tert-butylphosphino) ferrocene, bis [2- (diphenylphosphino) phenyl ] ether, 1 ' -bis (diisopropylphosphino) ferrocene, 1 ' -bis (diphenylphosphino) ferrocene, preferred are monodentate phosphine ligands, more preferred are triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, and most preferred is triphenylphosphine.

Examples of the base include inorganic bases and organic bases.

Examples of the inorganic base include hydroxides, carbonates, bicarbonates, phosphates, carboxylates, alkoxides of alkali metals or alkaline earth metals. The form of the base used here may be an anhydride or a hydrate.

The inorganic base preferably includes hydroxides, carbonates, hydrogencarbonates, phosphates, and carboxylates of alkali metals or alkaline earth metals, and more preferably carbonates and phosphates of alkali metals or alkaline earth metals. The salt of an alkali metal or an alkaline earth metal is preferably a carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate or barium carbonate, or a phosphate such as lithium phosphate, sodium phosphate or potassium phosphate, and more preferably sodium carbonate, potassium carbonate or potassium phosphate.

Examples of the organic base include triethylamine, 4- (N, N-dimethylamino) pyridine, piperidine, 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 more preferably 1, 8-diazabicyclo [5.4.0] -7-undecene.

The base is preferably a hydroxide, carbonate, hydrogencarbonate, phosphate, or carboxylate of an alkali metal or an alkaline earth metal, or an organic base, and more preferably a carbonate, phosphate, or organic base of an alkali metal or an alkaline earth metal.

Examples of the solvent include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; 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, and 1, 2-dichlorobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and carboxylic acid solvents such as acetic acid, propionic acid and butyric acid, and preferably N, N-dimethylformamide, N-dimethylacetamide and toluene.

The amount of the catalyst to be used is usually 0.01 mol or more and 1 mol or less, more preferably 0.01 mol or more and 0.5 mol or less, and still more preferably 0.01 mol or more and 0.25 mol or less based on 1 mol of the compound (pt-2).

The amount of the phosphine ligand to be used is usually 0.01 mol or more and 3 mol or less, more preferably 0.02 mol or more and 1 mol or less, and still more preferably 0.02 mol or more and 0.5 mol or less based on 1 mol of the compound (pt-2).

The amount of the base to be used is usually 1 mol to 50 mol, more preferably 1 mol to 25 mol, and still more preferably 1 mol to 15 mol, based on 1 mol of the compound (pt-2).

The amount of the compound represented by the formula (MA-1) to be used is usually 1 mol or more and 10 mol or less, more preferably 1 mol or more and 5 mol or less, and still more preferably 1 mol or more and 2 mol or less based on 1 mol of the compound (pt-2).

The solvent is usually used in an amount of 1 to 1000 parts by mass based on 1 part by mass of the compound (pt-2).

The reaction temperature is usually from-100 ℃ to 300 ℃.

The compound represented by the formula (pt-3) (which may be referred to as the compound (pt-3)) in the step (iii) of route 2 can be produced by reacting the compound represented by the formula (MA-2) with the compound represented by the formula (pt-2) in a solvent in the presence of a catalyst, a phosphine ligand and a base. The compound (pt-2) can be produced, for example, by the step (i) described above.

Examples of the phosphine ligand include tributylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, tri (3-methoxyphenyl) phosphine, tris [3, 5-bis (trifluoromethyl) phenyl ] phosphine, ethyldiphenylphosphine, tris (2, 6-dimethoxyphenyl) phosphine, tris (4-fluorophenyl) phosphine, diphenylpropylphosphine, di-tert-butylphenyl phosphine, tris (2-furyl) phosphine, tris (2-thienyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, methyldiphenylphosphine, 1- [2- (di-tert-butylphosphino) phenyl ] -3, 5-diphenyl-1H-pyrazole, (4-dimethylaminophenyl) di-tert-butylphosphine, tris (o) phosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-fluorophenyl) phosphine, tris (3, 5-methoxyphenyl) phosphine, tris (4-tert-butylphenyl) phosphine, tris (4-methoxyphenyl) di-butyl phosphine, and a, 2- (di-tert-butylphosphino) biphenyl, di-tert-butyl (1, 1-diphenyl-1-propen-2-yl) phosphine, isopropyldiphenylphosphine, 2- (dicyclohexylphosphino) -2 ' - (dimethylamino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2- (diphenylphosphino) biphenyl, 2-dicyclohexylphosphino-2 ' -methylbiphenyl, 2-dicyclohexylphosphino-2 ', 6 ' -diisopropyloxybiphenyl, 2-dicyclohexylphosphino-2 ', 6 ' -dimethoxybiphenyl, dicyclohexyl (1-methyl-2, 2-diphenylcyclopropyl) phosphine, di-tert-butyl (2 ', 4 ', 6 ' -triisopropyl-3, 6-dimethoxy- [1,1 ' -biphenyl ] -2-yl) phosphine, 2-dicyclohexylphosphino-2 ', 4 ', 6 ' -triisopropylbiphenyl, 2-diphenylphosphino-2 ' - (N, N-dimethylamino) biphenyl, 2-di-tert-butylphosphino-2 ', 4 ', 6 ' -triisopropylbiphenyl, a monodentate phosphine ligand such as dicyclohexyl (2 ', 4 ', 6 ' -triisopropyl-3, 6-dimethoxy- [1,1 ' -biphenyl ] -2-yl) phosphine, dicyclohexyl (1, 1-diphenyl-1-propen-2-yl) phosphine, bis (diphenylphosphino) methane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 2 ' -diphenylphosphino-2 ' - (isopropylbiphenyl, 2-diphenylphosphino-2 ' - (N, N-dimethylamino) biphenyl, 2-di-tert-butylphosphino-2 ', 4 ', 6 ' -triisopropylbiphenyl, dicyclohexyl- [1,1 ' -diphenyl-1-propen-2-yl ] phosphine, 1, 3-bis (diphenylphosphino) propane, 2-bis (diphenylphosphino) propane, and the like, 1, 4-bis (diphenylphosphino) butane, 2 '-bis (diphenylphosphino) -1, 1' - ビ naphthyl, 4, 5-bis (dicyclohexylphosphino) -9, 9-dimethylxanthene, 1,2,3,4, 5-pentaphenyl-1 '- (di-tert-butylphosphino) ferrocene, 1', 2 '-bis [ bis (3, 5-dimethylphenyl) phosphino ] -1, 1' -biphenyl, 4, 5-bis (diphenylphosphino) -9, 9-dimethylhexane, 1, 3-bis (diphenylphosphino) propane, 1 '-bis (di-tert-butylphosphino) ferrocene, bis [2- (diphenylphosphino) phenyl ] ether, 1' -bis (diisopropylphosphino) ferrocene, 1, bidentate phosphine ligands such as 1' -bis (diphenylphosphino) ferrocene are preferably monodentate phosphine ligands.

Examples of the base include hydroxides, carbonates, bicarbonates, phosphates, carboxylates, alkoxides, and the like of alkali metals or alkaline earth metals as inorganic bases. The form of the base used here may be an anhydride or a hydrate. Preferred examples thereof include hydroxides, carbonates, bicarbonates, phosphates and carboxylates of alkali metals or alkaline earth metals, and more preferred examples thereof are carbonates and phosphates of alkali metals or alkaline earth metals. The alkali metal or alkaline earth metal salt is preferably lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, barium carbonate, lithium phosphate, sodium phosphate, and potassium phosphate, and more preferably sodium carbonate, potassium carbonate, and potassium phosphate.

Examples of the solvent include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; 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, and 1, 2-dichlorobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and carboxylic acid solvents such as acetic acid, propionic acid and butyric acid, and toluene, xylene and tetrahydrofuran are preferred.

The amount of the compound represented by the formula (MA-2) to be used is usually 1 mol or more and 10 mol or less, more preferably 1 mol or more and 5 mol or less, and still more preferably 1 mol or more and 2 mol or less based on 1 mol of the compound (pt-2).

The reaction temperature is usually from-100 ℃ to 300 ℃.

The compound (I) in the step (iv) of route 2 can be produced by reacting a compound represented by the formula (pt-3) (sometimes referred to as a compound (pt-3)) in a solvent by irradiation with light.

Examples of the solvent include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; 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, and 1, 2-dichlorobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and carboxylic acid solvents such as acetic acid, propionic acid and butyric acid, preferably dichloromethane and chloroform.

The light source used for light irradiation is not limited, and examples thereof include sunlight, xenon lamps, fluorescent lamps, Light Emitting Diodes (LEDs), low-pressure mercury lamps, high-pressure mercury lamps, and metal hydride lamps.

The solvent is usually used in an amount of 1 to 1000 parts by mass based on 1 part by mass of the compound (pt-3).

The reaction temperature is usually from-100 ℃ to 300 ℃.

The compound (I) in the step (iv) can also be produced by reacting the compound (pt-3) with the compound (MA-3) in a solvent.

Examples of the compound (MA-3) include metal chlorides, preferably iron (III) chloride, zinc chloride, and aluminum chloride.

The amount of the compound (MA-3) to be used is usually 0.01 to 10 mol, more preferably 0.1 to 5 mol, based on 1 mol of the compound (pt-3).

Examples of the solvent include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; 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, and 1, 2-dichlorobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and carboxylic acid solvents such as acetic acid, propionic acid and butyric acid, and nitro solvents such as nitromethane and nitrobenzene, with dichloromethane, chloroform and nitromethane being preferred.

The reaction temperature is usually from-100 ℃ to 300 ℃.

Color (A1)

The colored resin composition of the present invention may contain, as the colorant (A), a dye (hereinafter, sometimes referred to as a dye (A1-1)) and/or a pigment (hereinafter, sometimes referred to as a pigment (A1-2)) other than the compound (I). Hereinafter, the dye (A1-1) and the pigment (A1-2) may be collectively referred to as a colorant (A1). These may be used alone or in combination of two or more.

The dye (a1-1) may be any dye without particular limitation as long as it does not contain the compound (I), and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of The dye include compounds classified as dyes in The color index (published by The Society of Dyers and Colourists), and known dyes described in The dyeing guide (chromo). Further, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, and the like can be given. Among these, organic solvent-soluble dyes are preferred.

Specific examples of the dye (A1-1) include:

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 orange2, 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: 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; c.I. solvent dye,

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, 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: 1. 91, 92, 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: 1. 58, 63, 65, 80, 104, 105, 106, 109; and the like C.I. acid dye,

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, 256, 236, 229, 237, 242, 244, 245, 247, 238, 248, 250, 257, 275, 260, 251, 293, 268, 274, 251, 268;

c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; c.I. direct dye,

C.i. disperse yellow 51, 54, 76;

c.i. disperse violet 26, 27;

c.i. disperse blue 1, 14, 56, 6; 0, etc. of C.I. disperse dye,

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. alkaline green 1; and the like C.I. basic dyes,

C.i. reaction yellow 2, 76, 116;

c.i. reaction orange 16;

c.i. reaction red 36; 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; c.I. mordant dyes,

C.i. vat green 1; and c.i. vat dyes, etc. color index (c.i.) numbered dyes.

As The pigment (a1-2), as long as The compound (I) is not contained, known pigments can be used without particular limitation, and examples thereof include pigments classified as pigments (pigments) in The Society of Dyers and Colourists publication.

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 the like;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

red pigments such as c.i. pigment red 9, 97, 105, 122, 144, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and the like;

c.i. pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 60, and the like blue pigments;

c.i. pigment violet 1, 19, 23, 32, 36, 38 and the like violet pigment;

green pigments such as c.i. pigment green 7, 36, 58, 59, 62, 63;

c.i. brown pigments such as pigment brown 23, 25;

c.i. pigment black 1, 7 and the like.

As the colorant (a1), dyes and pigments of yellow, red or green are preferable.

The colorant (a1) may be subjected to, if necessary, rosin treatment, surface treatment using a derivative or the like to which an acidic group or a basic group is introduced, grafting treatment onto the surface of the colorant (a1) by a polymer compound or the like, microparticulation treatment by a sulfuric acid microparticulation method or the like, cleaning treatment for removing impurities by an organic solvent, water or the like, removal treatment of ionic impurities by an ion exchange method or the like, or the like. The particle diameter of the colorant (a1) is preferably substantially uniform.

When the colorant (a) further contains the colorant (a1), the content of the compound (I) is, for example, 1 mass% or more, preferably 2 mass% or more, more preferably 10 mass% or more, further preferably 25 mass% or more, and particularly preferably 50 mass% or more, relative to the total amount of the colorant (a). When the colorant (a) further contains the colorant (a1), the content of the compound (I) is, for example, less than 100% by mass relative to the total amount of the colorant (a).

In the case where the colored resin composition contains the solvent (E), a liquid containing a colorant (sometimes referred to as a colored composition) containing the colorant (a) and the solvent (E) may be prepared in advance, and then the colored resin composition may be prepared using the liquid containing the colorant. In the case where the colorant (a) is insoluble in the solvent (E), for example, in the case where the colorant (a) contains the pigment (a1-2), the colorant-containing liquid can be prepared by dispersing and mixing the colorant (a) in the solvent (E). The colorant-containing liquid may contain a part or all of the solvent (E) contained in the colored resin composition.

The content of the solid content in the liquid containing the colorant is preferably 0.01 to 99.99 mass%, more preferably 0.1 to 99.9 mass%, even more preferably 0.1 to 99 mass%, even more preferably 0.5 to 90 mass%, and particularly preferably 1 to 50 mass%, relative to the total amount of the liquid containing the colorant.

The colorant (a) may be dispersed by containing a dispersant, so that the colorant (a) is uniformly dispersed in the solution. When two or more colorants (a) are used in combination, each may be dispersed alone or in combination of two or more colorants (a).

Examples of the dispersant include surfactants, and the dispersant may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specifically, surfactants such as polyester, polyamine, and acrylic surfactants can be mentioned. These dispersants may be used alone or in combination of two or more. Examples of the dispersant include KP (manufactured by shin-Etsu chemical industry Co., Ltd.), FLOREN (manufactured by Kyowa chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by FiNETECHNO Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and the like. As the dispersant, the resin (B) described later can be used.

When a dispersant is used, the amount of the dispersant (solid component) used is usually 1 part by mass or more and 10000 parts by mass or less, preferably 5 parts by mass or more and 5000 parts by mass or less, more preferably 10 parts by mass or more and 1000 parts by mass or less, and still more preferably 15 parts by mass or more and 800 parts by mass or less, per 100 parts by mass of the colorant (a). When the amount of the dispersant used is within the above range, a more uniformly dispersed liquid containing a colorant tends to be obtained.

The content of the colorant (a) is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and still more preferably 1 to 30% by mass, based on the total amount of solid components in the colored resin composition. When the content of the colorant (a) is within the above range, the color density is sufficient when a color filter is produced, and a necessary amount of the resin (B) can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed, which is preferable.

Here, the "total amount of solid components" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the colored resin composition. The total amount of the solid components and the contents of the respective components relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.

< resin (B) >

The resin (B) is not particularly limited, but is preferably a resin used for forming a photoresist, unlike a thermoplastic resin. Among these, as the resin (B), an alkali-soluble resin is more preferable, and an alkali-soluble resin having a carboxylic acid is further preferable. A colored resin composition using an alkali-soluble resin as the resin (B) can be suitably used for photoresist applications.

Examples of the resin (B) include the following resins [ K1] to [ K6 ].

Resin [ K1 ]: a copolymer having a structural unit derived from at least one (a) (hereinafter, sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit derived from a monomer (b) (hereinafter, sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;

resin [ K2 ]: a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (wherein (a) and (b) are different) (hereinafter, may be referred to as "(c)");

resin [ K3 ]: a copolymer having a structural unit from (a) and a structural unit from (c);

resin [ K4 ]: a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c);

resin [ K5 ]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c);

resin [ K6 ]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride, and a structural unit derived from (c).

Examples of the monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexenedicarboxylic acid;

carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

carboxylic acid anhydrides such as anhydrides of the above unsaturated dicarboxylic acids other than fumaric acid and mesaconic acid;

unsaturated mono [ (meth) acryloyloxyalkyl ] esters of dibasic or higher polycarboxylic acids such as mono [2- (meth) acryloyloxyethyl ] succinate and mono [2- (meth) acryloyloxyethyl ] phthalate;

unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid; and so on.

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

In the present specification, "(meth) acrylic acid" means at least 1 selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acryloyl group" and "(meth) acrylate" and the like have the same meanings.

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

Examples of the monomer (b) include a monomer having an oxirane group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 3)"), and the like.

Examples of the monomer (b1) include a monomer having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, sometimes referred to as "monomer (b 1-1)") and a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter, sometimes referred to as "monomer (b 1-2)").

As the monomer (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specific examples of the monomer (b1-1) include glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, 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 (glycidyloxymethyl) styrene, 2, 5-bis (glycidyloxymethyl) styrene, 2, 6-bis (glycidyloxymethyl) styrene, p-vinylbenzyl glycidyl ether, p-vinylbenzyl ether, 2, 4-bis (glycidyloxymethyl) styrene, 2, 5-bis (glycidyloxymethyl) styrene, 2, 6-bis (glycidyloxymethyl) styrene, p-vinylbenzyl-vinyl-, 2,3, 4-tris (glycidyloxymethyl) 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.

Examples of the monomer (b1-2) include vinylcyclohexene monoxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000 (manufactured by Daicel Co., Ltd.), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, 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.), the compound represented by the formula (BI) and the compound represented by the formula (BII).

[ formula (BI) and formula (BII) wherein R ^a And R ^b Independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atomsThe hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a And X ^b Independently of one another, represent a single bond, or-R ^c -、＊-R ^c -O-、＊-R ^c -S-or-R ^c -NH-。

R ^c Represents an alkanediyl group having 1 to 6 carbon atoms.

Represents a bond with O. ]

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

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

As R ^a And R ^b Preferred examples thereof include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, and a hexane-1, 6-diyl group.

As X ^a And X ^b Preferred examples thereof include a single bond, methylene, ethylene and perylene-CH ₂ -O- (-O-represents a bond with O) group, or-CH ₂ CH ₂ an-O-group, more preferably a single bond, or a-CH group ₂ CH ₂ an-O-group (representing a bond to O).

Examples of the compound represented by formula (BI) include compounds represented by any one of formulae (BI-1) to (BI-15). Among them, preferred are compounds represented by the formulae (BI-1), (BI-3), (BI-5), (BI-7), (BI-9) and (BI-11) to (BI-15), and more preferred are compounds represented by the formulae (BI-1), (BI-7), (BI-9) and (BI-15).

Examples of the compound represented by formula (BII) include compounds represented by any one of formulae (BII-1) to (BII-15), among which compounds represented by formulae (BII-1), (BII-3), (BII-5), (BII-7), (BII-9), and (BII-11) to (BII-15) are preferable, and compounds represented by formulae (BII-1), (BII-7), (BII-9), and (BII-15) are more preferable.

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination. When these compounds 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: 95-95: 5, more preferably 10: 90-90: 10, more preferably 20: 80-80: 20.

as the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of the monomer (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethylobutane, and 3-ethyl-3- (meth) acryloyloxyethylooxetane.

As the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuranyl group and a (meth) acryloyloxy group is more preferable. Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V #150, manufactured by Osaka chemical industries, Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of the monomer (c) include:

methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and mixtures thereof) T-butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 (meth) acrylate ^2,6 ]Decan-8-yl ester (which is conventionally referred to as dicyclopentyl "(meth) acrylate. also, tricyclodecanyl (meth) acrylate) and tricyclo (meth) acrylate [5.2.1.0 ] ^2,6 ]Decan-9-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decen-8-yl ester (commonly known in the art by the name "dicyclopentenyl (meth) acrylate"), "tricyclo [5.2.1.0 (meth) acrylate") ^2,6 ](meth) acrylates such as decen-9-yl ester, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [2.2.1] hept-2-ene, 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, bicyclic unsaturated compounds such as 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [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;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

vinyl group-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-containing amides such as (meth) acrylamide; esters such as vinyl acetate; dienes such as 1, 3-butadiene, isoprene and 2, 3-dimethyl-1, 3-butadiene; and so on.

Among these, styrene, vinyltoluene, and tricyclo [5.2.1.0 (meth) acrylate are preferable from the viewpoint of copolymerization reactivity and heat resistance ^2,6 ]Decan-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decan-9-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decen-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decen-9-yl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1]Hept-2-ene, benzyl (meth) acrylate, and the like.

In the resin [ K1], the ratio of the structural units from each of all the structural units constituting the resin [ K1] is preferably:

structural unit from (a): 2 to 60 mol%

Structural units from (b): 40 to 98 mol percent,

more preferably:

structural unit from (a): 10 to 50 mol%

Structural units from (b): 50 to 90 mol%.

When the ratio of the structural unit of the resin [ K1] is within the above range, the colored resin composition tends to have excellent storage stability, developability in forming a colored pattern, and solvent resistance of the resulting color filter.

The resin [ K1] can be produced, for example, by a method described in "Experimental method for Polymer Synthesis" (published by Otsuka institute of Engineers, 1 st edition, chemical Co., Ltd., 1972, 3 months and 1 days), and a cited reference described in the above document.

Specifically, the following methods are mentioned: the predetermined amounts of (a) and (b), the polymerization initiator, the solvent and the like are charged into a reaction vessel, and oxygen is replaced with nitrogen gas, for example, to thereby form a deoxygenated atmosphere, and heating and heat-holding are performed while stirring. The polymerization initiator and the solvent used herein are not particularly limited, and those generally used in the art can be used. For example, the polymerization initiator may include an azo compound (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), etc.) and an organic peroxide (e.g., benzoyl peroxide), and the solvent may be a solvent which dissolves the monomers, and the solvent (E) of the colored resin composition of the present invention and is described later may be used.

The copolymer obtained may be used as it is, as a solution after the reaction, or as a solution after concentration or dilution, or as a substance taken out as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent contained in the colored resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be used as it is for the production of the colored resin composition of the present invention, and therefore, the production process of the colored resin composition of the present invention can be simplified.

In the resin [ K2], the ratio of the structural units from each of all the structural units constituting the resin [ K2] is preferably:

structural unit from (a): 2 to 45 mol%

Structural units from (b): 2 to 95 mol%

Structural units from (c): 1 to 65 mol% of a surfactant,

more preferably:

structural unit from (a): 5 to 40 mol%

Structural units from (b): 5 to 80 mol%

Structural units from (c): 5 to 60 mol%.

When the ratio of the structural unit of the resin [ K2] is within the above range, the colored resin composition tends to have excellent storage stability, developability in forming a colored pattern, and solvent resistance, heat resistance, and mechanical strength of the resulting color filter.

The resin [ K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [ K1 ].

In the resin [ K3], the ratio of structural units from each among all structural units constituting the resin [ K3] is preferably:

structural unit from (a): 2 to 60 mol%

Structural units from (c): 40 to 98 mol percent,

more preferably:

structural unit from (a): 10 to 50 mol%

Structural units from (c): 50 to 90 mol%.

The resin [ K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [ K1 ].

The resin [ K4] can be produced by: obtaining a copolymer of (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms of (b) to a carboxylic acid and/or a carboxylic acid anhydride of (a).

First, a copolymer of (a) and (c) was produced in the same manner as in the method described for producing resin [ K1 ]. In this case, the ratio of the structural units derived from each is preferably the same as that mentioned in the resin [ K3 ].

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

After the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and the reaction of (b), a catalyst for the reaction of a carboxylic acid or a carboxylic anhydride with a cyclic ether (e.g., tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (e.g., hydroquinone) are charged into the flask and reacted at 60 to 130 ℃ for 1 to 10 hours to produce a resin [ K4 ].

The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting the content within this range, the storage stability of the colored resin composition, the developability in forming a pattern, and the balance among solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good. The (b) used in the resin [ K4] is preferably (b1), more preferably (b1-1), from the viewpoint that the cyclic ether has high reactivity and unreacted (b) is not likely to remain.

The amount of the reaction catalyst is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the charging method, the reaction temperature and the reaction time can be appropriately adjusted in consideration of the production facilities, the amount of heat generated by polymerization, and the like. The charging method and the reaction temperature can be appropriately adjusted in consideration of the production facility, the amount of heat generated by polymerization, and the like, as in the case of the polymerization conditions.

As for the resin [ K5], a copolymer of (b) and (c) was obtained as the first stage in the same manner as in the above-described method for producing the resin [ K1 ]. The copolymer obtained may be used as it is, as described above, as a solution after the reaction, as a concentrated or diluted solution, or as a solid (powder) taken out by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) to the total number of moles of all the structural units constituting the copolymer is preferably:

structural units from (b): 5 to 95 mol%

Structural units from (c): 5 to 95 mol% of a surfactant,

more preferably:

a building block from (b); 10 to 90 mol%

A building block from (c); 10 to 90 mol%.

Further, the resin [ K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in (a) with the cyclic ether derived from (b) contained in the copolymer of (b) and (c) under the same conditions as the process for producing the resin [ K4 ].

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol based on 100 mol of (b). From the viewpoint that the cyclic ether has high reactivity and unreacted (b) is less likely to remain, (b1) is preferable, and (b1-1) is more preferable as (b) used in the resin [ K5 ].

The resin [ K6] is a resin obtained by further reacting a carboxylic anhydride with the resin [ K5 ]. The carboxylic anhydride is reacted with a hydroxyl group (which is generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride).

Examples of the carboxylic anhydride 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, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. The amount of the carboxylic anhydride used is preferably 0.5 to 1 mole per 1 mole of the amount of (a).

Specific examples of the resin (B) include: 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]Resins such as decyl ester/(meth) acrylic acid copolymers [ K1]](ii) a Glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, acrylic acid 3, 4-epoxy tricyclo [5.2.1.0 ] ^2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]Resins such as decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer [ K2](ii) a Benzyl (meth) acrylate/(meth) acrylic acid co-polymerResins such as copolymers and styrene/(meth) acrylic acid copolymers [ K3]](ii) a Resins obtained by adding benzyl (meth) acrylate/(meth) acrylic acid copolymer and glycidyl (meth) acrylate, resins obtained by adding tricyclodecyl (meth) acrylate/styrene/(meth) acrylic acid copolymer and glycidyl (meth) acrylate, and resins obtained by adding tricyclodecyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer and glycidyl (meth) acrylate [ K4]](ii) a Resins such as resins obtained by reacting a tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate) copolymer with (meth) acrylic acid, and resins obtained by reacting a tricyclodecyl (meth) acrylate/styrene/(glycidyl (meth) acrylate) copolymer with (meth) acrylic acid [ K5%](ii) a Resins such as resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate) with (meth) acrylic acid and further reacting the resin with tetrahydrophthalic anhydride [ K6]]And so on.

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

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 30,000. When the weight average molecular weight is within the above range, the following tendency is present: the unexposed portion has high solubility in a developer, and the obtained pattern has high residual film ratio and high hardness.

The dispersity [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B) is preferably 1 to 6, more preferably 1.001 to 4, and still more preferably 1.01 to 4.

The acid value (in terms of solid content) of the resin (B) is preferably 10mg-KOH/g or more and 300mg-KOH/g or less, more preferably 20mg-KOH/g or more and 250mg-KOH/g or less, still more preferably 25mg-KOH/g or more and 200mg-KOH/g or less, yet more preferably 30mg-KOH/g or more and 150mg-KOH/g or less, and particularly preferably 60mg-KOH/g or more and 135mg-KOH/g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin, and can be determined by titration using an aqueous potassium hydroxide solution, for example.

The content of the resin (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass, based on 100% by mass of the solid content of the colored resin composition. When the content of the resin (B) is within the above range, the solubility of the unexposed portion in the developer tends to be high.

< polymerizable Compound (C) >)

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and a (meth) acrylate compound is preferable.

Examples of the polymerizable compound having 1 ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone, and the above-mentioned monomer (a), monomer (b), and monomer (c).

Examples of the polymerizable compound having 2 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 (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate.

The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) The acrylic acid ester and the like are preferably dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

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

The content of the polymerizable compound (C) may be, for example, 1 mass% or more and 99 mass% or less, preferably 5 mass% or more and 90 mass% or less, more preferably 10 mass% or more and 80 mass% or less, and further preferably 20 mass% or more and 70 mass% or less, based on the total amount of solid components in the colored resin composition.

< polymerization initiator (D) >)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like under the action of light or heat to initiate polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- (4-phenylthiophenyl) -3-cyclohexylpropane-1-one-2-imine, and mixtures thereof, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxolanylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine -6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine and the like. Further, as the O-acyloxime compound, commercially available products such as Irgacure (registered trademark), OXE01, OXE02 (manufactured by BASF Co., Ltd.), N-1919 (manufactured by ADEKA Co., Ltd.) and the like can be used. Among them, as the O-acyloxime compound, at least one selected from the group consisting of N-benzoyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine, and N-benzoyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine is more preferable.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-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-morpholino) phenyl ] butan-1-one. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (manufactured by BASF) can be used as the alkylphenone compound.

Examples of the alkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone and benzildimethylketal.

Examples of the biimidazole compound include 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbiimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenylbiimidazole (see, for example, japanese patent application laid-open No. 6-75372, japanese patent application laid-open No. 6-75373, etc.), 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (alkoxyphenyl) biimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (dialkoxyphenyl) biimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (trialkoxyphenyl) biimidazole (for example, see, for example, Japanese patent application laid-open No. 48-38403, Japanese patent application laid-open No. 62-174204, etc.) and biimidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with an alkoxycarbonyl group (e.g., see, for example, Japanese patent application laid-open No. 7-10913, etc.).

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

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can be used.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, and the like.

These are preferably used in combination with the polymerization initiation aid (D1) (particularly, an amine compound) described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a bisimidazole compound, and more preferably a polymerization initiator containing an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) contained in the colored resin composition. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

< polymerization initiation assistant (D1) >)

The polymerization initiation assistant (D1) is a compound for promoting the polymerization of the polymerizable compound (C) which initiates the polymerization by the polymerization initiator (D), or a sensitizer. When the polymerization initiator aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 ' -bis (dimethylamino) benzophenone (known as michler's ketone), 4 ' -bis (diethylamino) benzophenone, and 4,4 ' -bis (ethylmethylamino) benzophenone, and preferably include 4,4 ' -bis (diethylamino) benzophenone. As the amine compound, a commercially available compound such as EAB-F (manufactured by UK chemical Co., Ltd.) can be used.

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

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.

When these polymerization initiating aids (D1) are used, the content thereof is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) contained in the colored resin composition.

< solvent (E) >, and

the solvent (E) is not particularly limited, and a solvent generally used in this field can be used.

Examples of the solvent (E) include 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 (a solvent containing-COO-and-O-in the molecule), a ketone solvent (a solvent containing-CO-and not containing-COO-in the molecule), an alcohol solvent (a solvent containing OH and not containing-O-, -CO-, and-COO-, in the molecule), an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide. Two or more of these solvents may be used in combination.

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

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

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and mixtures thereof, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.

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

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like.

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

The solvent (E) is preferably a solvent containing at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and cyclohexanone.

The content of the solvent (E) is usually 99.99% by mass or less, preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 95% by mass or less, further preferably 70% by mass or more and 95% by mass or less, and further preferably 75% by mass or more and 90% by mass or less, based on the total amount of the colored resin composition. In other words, the total amount of solid components in the colored resin composition is usually 0.01 mass% or more, preferably 1 mass% or more and 60 mass% or less, more preferably 5 mass% or more and 50 mass% or less, still more preferably 5 mass% or more and 30 mass% or less, and still more preferably 10 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 good, and the color density does not become insufficient at the time of forming a color filter, so that the display characteristics tend to become good.

< leveling agent (F) >

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

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, there may be mentioned TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, and TORAY SILICONE SH8400 (trade name, manufactured by Torildo Corning Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical industries, Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Mitigo high-tech materials Japan contract Co., Ltd.), and the like.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, FLOURAD (registered trademark) FC430, FLOURAD (registered trademark) FC431 (manufactured by sumitomo 3M corporation); MEGAFAC (registered trademark) F142D, MEGAFAC (registered trademark) F171, MEGAFAC (registered trademark) F172, MEGAFAC (registered trademark) F173, MEGAFAC (registered trademark) F177, MEGAFAC (registered trademark) F183, MEGAFAC (registered trademark) F554, MEGAFAC (registered trademark) R30, MEGAFAC (registered trademark) RS-718-K (manufactured by DIC corporation); EFTOP (registered trademark) EF301, EFTOP (registered trademark) EF303, EFTOP (registered trademark) EF351, EFTOP (registered trademark) EF352 (manufactured by mitsubishi integrated materials electronics corporation); SURFLON (registered trademark) S381, SURFLON (registered trademark) S382, SURFLON (registered trademark) SC101, and SURFLON (registered trademark) SC105(AGC (strain)); and E5844 (manufactured by Daiki Fine chemistry research institute).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there may be mentioned MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (available from DIC Co., Ltd.).

When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.0005 mass% or more and 1 mass% or less, more preferably 0.001 mass% or more and 0.5 mass% or less, and further preferably 0.005 mass% or more and 0.1 mass% or less, based on the total amount of the colored resin composition. Note that this content does not include the content of the foregoing dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

< other ingredients >

The colored resin composition may contain additives known in the art, such as a filler, another polymer compound, an adhesion promoter, a quencher, an antioxidant, a light stabilizer, and a chain transfer agent, as required.

< method for producing colored resin composition >

The colored resin composition is prepared by mixing the colorant (a), the resin (B), and, if necessary, the polymerizable compound (C), the polymerization initiator (D), the polymerization initiation aid (D1), the solvent (E), the leveling agent (F), and other components. The mixing can be carried out by known or customary apparatus and conditions.

The colorant (a) may be used in a state of being mixed with a part or all of the solvent (E) in advance and dispersed by a bead mill or the like until the average particle diameter becomes about 0.2 μm or less, and is preferably used in a dispersed state. In this case, a part or all of the above-mentioned dispersant and resin (B) may be blended as necessary. The colorant (a) may be used in a state of being dissolved in a part or all of the solvent (E) in advance. The liquid containing the colorant obtained in this manner is mixed with the remaining components so as to have a predetermined concentration, whereby the target colored resin composition can be prepared.

< method for manufacturing color filter >

A color filter (which may be a color conversion layer) may be formed from the colored resin composition of the present invention. Examples of a method for forming a colored pattern include a photolithography method, an ink jet method, a printing method, and the like. Among them, photolithography is preferable. The photolithography method is as follows: the colored resin composition is applied to a substrate, dried to form a colored resin composition layer, and the colored resin composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film which is a cured product of the colored resin composition layer can be formed without using a photomask and/or without developing at the time of exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.

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

As the substrate, there can be used: glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass having a silica-coated surface; or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate; silicon; a substrate having a thin film of aluminum, silver/copper/palladium alloy, or the like formed thereon. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by photolithography can be performed by a known or commonly used apparatus and conditions. For example, it can be produced in the following manner.

First, a colored resin composition is applied onto a substrate, and is dried by removing volatile components such as a solvent by heat drying (prebaking) and/or drying under reduced pressure, thereby obtaining a smooth colored resin composition layer.

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

The temperature at the time of heat drying is preferably 30 ℃ to 120 ℃ inclusive, and more preferably 50 ℃ to 110 ℃ inclusive. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When the drying is carried out under reduced pressure, it is preferably carried out under a pressure of 50Pa to 150Pa, and at a temperature of 20 ℃ to 25 ℃.

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 target color filter.

Next, the colored resin composition layer is exposed to light through a photomask for forming a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use may be used. In addition, in order to uniformly irradiate parallel light rays on the entire exposure surface or to accurately position the photomask and the substrate on which the colored resin composition layer is formed, it is preferable to use an exposure device such as a mask aligner or a stepper. In the case of forming a colored coating film, exposure may be performed without using a photomask.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250nm to 450 nm. For example, light below 350nm may be cut off using a filter that cuts off this wavelength range; band pass filters (band pass filters) for extracting these wavelength regions may be used for light near 436nm, near 408nm, and near 365 nm. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like can be given.

The exposed colored resin composition layer is developed by contacting it with a developing solution, thereby forming a colored pattern on the substrate. By the development, the unexposed portion of the colored resin composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. Further, the developer may contain a surfactant.

The developing method may be any of a spin-coating immersion method, a dipping method, a spraying method, and the like. In addition, the substrate may be tilted at an arbitrary angle during development.

The developed substrate is preferably washed with water.

The obtained colored pattern or colored coating film is preferably subjected to post-baking. The post-baking temperature is preferably 150 ℃ to 250 ℃, more preferably 160 ℃ to 240 ℃. The post-baking time is preferably 1 minute to 120 minutes, more preferably 10 minutes to 60 minutes.

< display device >

The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) or a solid-state imaging element, particularly a color filter used in an organic EL device.

Examples

The present invention will be described more specifically below with reference to examples, but the present invention is not limited to the examples described below, and may be carried out by appropriately changing the examples within a range that can be adapted to the gist described above and below, and these examples are included in the technical scope of the present invention. In the following description, "part" means "part by mass" and "%" means "% by mass" unless otherwise specified.

In the following examples, the structure of the compound was confirmed by MASS spectrometry (LC, model 1200 by Agilent, MASS, and model LC/MSD6130 by Agilent).

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.

The device comprises the following steps: HLC-8120GPC (manufactured by Tosoh corporation)

Column: TSK-GELG2000HXL

Column temperature: 40 deg.C

Solvent: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

Solid content concentration of analysis sample: 0.001 to 0.01% by mass

Injection amount: 50 μ L

A detector: RI (Ri)

Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

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

[ Synthesis example 1]

< preparation of Compound I-19 >

Compound (I-19) was synthesized according to the description of Chemical Communications 2005, 4045-4046.

< identification of Compound I-19 >

(Mass Spectrometry) ionization mode ESI +: m/z ═ M + H] ⁺ 875

Accurate quality: 874

[ Synthesis example 2]

< preparation of Compound I-17 >

Compound (I-17) was synthesized as described in European Journal of Organic Chemistry, 2014, 5178-5195.

< identification of Compound I-17 >

(Mass Spectrometry) ionization mode ESI +: m/z ═ M + H] ⁺ 801

Accurate quality: 800

[ Synthesis example 3]

< preparation of Compound I-22 >

Compound (I-22) was synthesized as described in Organic Letters, 2010, Vol.12, 228-.

< identification of Compound I-22 >

(Mass Spectrometry) ionization mode ESI +: m/z ═ M + H] ⁺ 877

Accurate quality: 876

[ Synthesis example 4]

< preparation of Compound I-18 >

Compound (I-18) was synthesized as described in Organic Letters, 2010, Vol.12, 228-231.

< identification of Compound I-18 >

(Mass Spectrometry) ionization mode ESI +: m/z ═ M + H] ⁺ 802

Accurate quality: 801

Lumogen (registered trademark) F Orange240 (a compound represented by the following formula (x)) was obtained from tokyo chemical industry co.

[ Synthesis example 5]

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the nitrogen atmosphere was replaced, and 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ℃ with stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over 5 hours ^2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]A mixture of decane-9-yl ester (containing 1: 1 in terms of molar ratio) 289 parts, propylene glycol monomethyl ether acetate 125 parts. On the other hand, a solution prepared by dissolving 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. The dropping is finishedThereafter, the mixture was held at 80 ℃ for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution having a solid content of 35.1% and a viscosity of 125 mPas as measured by a B-type viscometer (23 ℃). The weight-average molecular weight Mw of the resulting copolymer was 9.2X 10 ³ The dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. The resin B1 has the following structural units.

< example 1 >

(1) Preparation of colored resin composition

The respective components were mixed at the following ratio to obtain a colored resin composition 1.

(A) Colorant: 2.6 parts of a Compound represented by the formula (I-1)

(B) Resin: 54 parts of resin B1 solution

(E) Solvent: 420 parts of propylene glycol monomethyl ether acetate

(2) Preparation of colored curable resin composition

Next, the respective components were mixed at the following ratio to obtain a colored curable resin composition 1.

1478 parts of colored resin composition

(C) A polymerizable compound: dipentaerythritol hexaacrylate

(KAYARAD (registered trademark) DPHA; manufactured by JAPONIC CHEMICAL DRUG, Ltd.) 40 parts

(D) Polymerization initiator: n-benzoyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF corporation) 2 parts

(F) Leveling agent: 0.15 part of polyether-modified Silicone oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.)

(3) Production of colored coating film (color Filter)

A colored curable resin composition was applied onto a 5cm square glass substrate (Eagle XG; manufactured by Corning Corp.) by spin coating so that the film thickness after baking became 2 μm,then prebaked at 100 ℃ for 3 minutes to form a colored composition layer. After leaving to cool, the colored composition layer formed on the substrate was exposed to 80mJ/cm in an air atmosphere using an exposure machine (TME-150 RSK; manufactured by Topcon Co., Ltd.) ² The exposure amount (365nm basis) of (A) was irradiated with light. After the light irradiation, the coating film was post-baked in an oven at 230 ℃ for 30 minutes to obtain a colored coating film.

The thickness of the obtained colored coating film was measured by DEKTAK3 (manufactured by NIPPON VACUUM TECHNOLOGY CO., LTD.) and found to be 2 μm.

The evaluation of the color of the colored coating film was carried out in the following manner: the spectral distribution was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus, Inc.), and the xy chromaticity coordinates (x, Y) and stimulus value Y in the XYZ color system of CIE were measured using the characteristic function of the C light source.

(4) Heat resistance test

The obtained colored coating film was heated at 230 ℃ for 120 minutes in an oven under an atmospheric atmosphere. From xy chromaticity coordinates (x, Y) before and after the test and a measured value of Y, a value obtained by JIS Z8730: 2009(7. method for calculating color difference) the method described in ^* ab. For the color difference Δ E ^* ab, smaller represents smaller color change, and Δ E ^* When ab is 5 or less, it is considered that the colored coating film has no practical problem as a color filter. Further, when the heat resistance of the colored coating film is good, it is considered that the heat resistance of a colored pattern made of the same colored curable resin composition is also good. The results are shown in Table 2.

(5) Light resistance test

An ultraviolet-ray-intercepting filter (COLORED OPTICAL GLASS L38; manufactured by Hoya, Inc.; intercepting light of 380nm or less) was placed on the obtained COLORED coating film, and xenon light was irradiated for 48 hours by a light resistance tester (SUNTEST CPS +; manufactured by Toyo Seiki Seiko, Inc.). From xy chromaticity coordinates (x, Y) before and after the test and a measured value of Y, a value obtained by JIS Z8730: 2009(7. method for calculating color difference) the method described in ^* ab. Note that, regarding the color difference Δ E ^* ab, smaller represents smaller color change, and Δ E ^* ab is 5 or less, the colored coating film is considered to be used as a color filterHas no practical problem. Further, when the light resistance of the colored coating film is good, it is considered that the light resistance of a colored pattern formed from the same colored curable resin composition is also good. The results are shown in Table 2.

< examples 2 to 4 and comparative example 1 >

Instead of 2.6 parts of Compound (I-19), use was made of

2.6 parts of Compound (I-17) (example 2),

2.6 parts of Compound (I-22) (example 3),

2.6 parts of Compound (I-18) (example 4), or

A colored curable resin composition was obtained in the same manner as in example 1, except that 2.6 parts of Lumogen (registered trademark) F Orange240 (comparative example 1) was used as a colorant. Further, a colored coating film was produced in the same manner as in example 1, and the heat resistance test and the light resistance test were performed. The results are shown in Table 2.

[ Table 2]

Claims

1. A colored resin composition comprising a colorant and a resin, wherein the colorant comprises a compound represented by the formula (I),

in the formula (I), the compound is shown in the specification,

R ¹ ～R ¹¹ independently of one another, represents a hydrogen atom, -R ^a1 、-OR ^a1 Halogen atom, hydroxy group, carboxy group, -CO-O-R ^a1 、-O-CO-R ^a1 、-CO-R ^a1 Or nitro, R ⁷ And R ⁸ May be bonded to each other to form a ring,

e represents C-H, C-R ^a1 Or the number of the N-substituted aryl groups,

R ^a1 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

2. The colored resin composition according to claim 1, further comprising a polymerizable compound and a polymerization initiator.

3. A color filter formed from the colored resin composition according to claim 1 or 2.

4. A display device comprising the color filter of claim 3.