JP2022129248A - colored resin composition - Google Patents

Abstract

To provide a colored resin composition capable of forming a color filter excellent in heat resistance.SOLUTION: The colored resin composition contains a colorant and a resin, where the colorant comprises a compound represented by formula (I). [In formula (I), R1 to R11 each independently represent a hydrogen atom, -Ra1, -ORa1, a halogen atom, a hydroxy group, a carboxy group, -CO-O-Ra1, -O-CO-Ra1, -CO-Ra1, or a nitro group, provided that R7 and R8 may be linked to each other to form a ring; E represents C-H, C-Ra1, or N; and Ra1 represents an optionally substituted C1-20 hydrocarbon group.]SELECTED DRAWING: None

Description

The present invention relates to colored resin compositions.

Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are produced from colored resin compositions. Various coloring agents are used as the colored resin composition for forming the color filter. 1).

JP 2020-79396 A

However, the perylene compound described above may not have sufficient heat resistance when used as 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.

［式（Ｉ）中、
Ｒ¹～Ｒ¹¹は、互いに独立に、水素原子、－Ｒ^a1、－ＯＲ^a1、ハロゲン原子、ヒドロキシ基、カルボキシ基、－ＣＯ－Ｏ－Ｒ^a1、－Ｏ－ＣＯ－Ｒ^a1、－ＣＯ－Ｒ^a1又はニトロ基を表し、Ｒ⁷とＲ⁸とは互いに結合して環を形成してもよい。
Ｅは、Ｃ－Ｈ、Ｃ－Ｒ^a1又はＮを表す。
Ｒ^a1は、置換基を有していてもよい炭素数１～２０の炭化水素基を表す。］
［２］ さらに重合性化合物及び重合開始剤を含有する［１］に記載の着色樹脂組成物。
［３］ ［１］又は［２］に記載の着色樹脂組成物から形成されるカラーフィルタ。
［４］ ［３］に記載のカラーフィルタを含む表示装置。 The gist of the present invention is as follows.
[1] A colored resin composition containing a coloring agent and a resin, wherein the coloring agent contains a compound represented by formula (I).

[in the formula (I),
R ¹ to R ¹¹ each independently represent a hydrogen atom, -R ^a1 , -OR ^a1 , halogen atom, hydroxy group, carboxy group, -CO-O-R ^a1 , -O-CO-R ^a1 , -CO- represents R ^a1 or a nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring;
E represents CH, ^{CR a1} or N;
R ^a1 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms. ]
[2] The colored resin composition according to [1], further comprising a polymerizable compound and a polymerization initiator.
[3] A color filter formed from the colored resin composition according to [1] or [2].
[4] A display device including the color filter described in [3].

ADVANTAGE OF THE INVENTION According to this invention, the colored resin composition which can form a color filter excellent in heat resistance can be provided.

The colored resin composition of the present invention contains a coloring agent (hereinafter sometimes referred to as coloring agent (A)) and a resin (hereinafter sometimes referred to as resin (B)), wherein the coloring agent is represented by formula (I) Including the compounds represented.
The colored resin composition of the present invention further contains 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)). good.
The colored resin composition of the present invention may further contain a solvent (hereinafter sometimes 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 leveling agent (F)).
In this specification, the compounds exemplified as each component can be used singly or in combination, unless otherwise specified.

<Colorant (A)>
Colorant (A) includes a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)). A colored resin composition containing compound (I) as a coloring agent has excellent heat resistance, preferably excellent light resistance.

［式（Ｉ）中、
Ｒ¹～Ｒ¹¹は、互いに独立に、水素原子、－Ｒ^a1、－ＯＲ^a1、ハロゲン原子、ヒドロキシ基、カルボキシ基、－ＣＯ－Ｏ－Ｒ^a1、－Ｏ－ＣＯ－Ｒ^a1、－ＣＯ－Ｒ^a1又はニトロ基を表し、Ｒ⁷とＲ⁸とは互いに結合して環を形成してもよい。
Ｅは、Ｃ－Ｈ、Ｃ－Ｒ^a1又はＮを表す。
Ｒ^a1は、置換基を有していてもよい炭素数１～２０の炭化水素基を表す。］ <<Compound (I)>>

[in the formula (I),
R ¹ to R ¹¹ each independently represent a hydrogen atom, -R ^a1 , -OR ^a1 , halogen atom, hydroxy group, carboxy group, -CO-O-R ^a1 , -O-CO-R ^a1 , -CO- represents R ^a1 or a nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring;
E represents CH, ^{CR a1} or N;
R ^a1 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms. ]

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Aliphatic hydrocarbon groups may be saturated or unsaturated and may be linear or alicyclic.

Saturated or unsaturated chain hydrocarbon groups represented by R ^a1 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group. , dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group; isopropyl group, (1-ethyl) propyl group, isobutyl group, sec -butyl group, tert-butyl group, (1-ethyl)butyl group, (2-ethyl)butyl group, (1-propyl)butyl group, isopentyl group, neopentyl group, tert-pentyl group, (2-methyl)pentyl group, (1-ethyl)pentyl group, (3-ethyl)pentyl group, (1-propyl)pentyl group, (1-butyl)pentyl group, isohexyl group, (2-methyl)hexyl group, (5-methyl) hexyl group, (2-ethyl)hexyl group, (1-butyl)hexyl group, (1-pentyl)hexyl group, (2-methyl)heptyl group, (2-ethyl)heptyl group, (3-ethyl)heptyl group , (1-hexyl) heptyl group, (2-methyl) octyl group, (2-ethyl) octyl group, (1-heptyl) octyl group, (2-ethyl) nonyl group, (1-octyl) nonyl group, etc. branched chain alkyl group, etc.; vinyl group, 1-propenyl group, 2-propenyl group (allyl group), (1-methyl)ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, alkenyl groups such as (1-(2-propenyl))ethenyl group, (1,2-dimethyl)propenyl group, 2-pentenyl group; and the like. The number of carbon atoms in the saturated chain hydrocarbon group is preferably 1-18, more preferably 2-15, still more preferably 3-12. The unsaturated chain hydrocarbon group preferably has 2 to 18 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 12 carbon atoms.

Saturated or unsaturated alicyclic hydrocarbon groups represented by R ^a1 include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups; cyclohexenyl groups (e.g. cycloalkenyl groups such as cycloheptenyl group, cycloheptenyl group and cyclooctenyl group; norbornyl group, adamantyl group, bicyclo[2.2.2]octyl group and the like. The saturated or unsaturated alicyclic hydrocarbon group preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms.

Examples of the aromatic hydrocarbon group represented by R ^a1 include phenyl group, 1-naphthyl group, 2-naphthyl group, phenanthryl group, anthryl group and pyrenyl group. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-15, more preferably 6-12.

The hydrocarbon group represented by R ^a1 is a combination of two or more of the chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups listed above, as long as the upper limit of the number of carbon atoms is 20. may be a base. Such a group may be, for example, a combination of an aromatic hydrocarbon group and at least one group selected from a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group, In the hydrocarbon group resulting from the combination, a chain hydrocarbon group may be combined as a divalent group (eg, an alkanediyl group). Examples of hydrocarbon groups obtained by the above combinations include aralkyl groups such as benzyl group, phenethyl group, and 1-methyl-1-phenylethyl group; arylalkenyl groups such as phenylethenyl group (phenylvinyl group); and phenylethynyl group. arylalkynyl group; 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-butyl phenyl 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, 3,6-di(tert-butyl)phenyl group, 4-tert-butyl-2,6-dimethylphenyl group, 4-pentylphenyl group, 4-octylphenyl group, 4-(2,4,4 -trimethyl-2-pentyl)phenyl group, 2-dodecylphenyl group, 3-dodecylphenyl group, alkylaryl group such as 4-dodecylphenyl group; alkenylaryl group such as 4-vinylphenyl group; 2,3-dihydro- 4-indenyl group, 1,2,3,5,6,7-hexahydro-4-s-indacenyl group, 8-methyl-1,2,3,5,6,7-hexahydro-4-s-indacenyl group , 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro-2-naphthyl group, 3-methyl-5,6,7,8-tetrahydro-2-naphthyl group, Aryl groups bonded with alkanediyl groups such as 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl groups; one or more aryl groups such as biphenylyl groups and terphenylyl groups aryl group; cyclohexylmethylphenyl group, benzylphenyl group, (dimethyl(phenyl)methyl)phenyl group, and the like. Further, the above hydrocarbon group may be, for example, a hydrocarbon group obtained by combining a chain hydrocarbon group and an alicyclic hydrocarbon group, examples of which include a 1-methylcyclopropyl group, a 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, 2,2-dimethylcyclohexyl group, 3, 3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group, 4-cyclohexylcyclohexyl group, and other alicyclic hydrocarbon groups bonded with one or more alkyl groups or alicyclic hydrocarbon groups; cyclopropylmethyl group, cyclopropylethyl group , cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, 2-methylcyclohexylmethyl group, cyclohexylethyl group, adamantylmethyl group, etc. and the like. The number of carbon atoms in the group obtained by combining two or more chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups is preferably 6-18, more preferably 6-15.

Substituents which the hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 may have include, for example, a halogen atom; a nitrile group; a nitro group; an amino group; a hydroxy group; a methoxy group; alkoxy group having 1 to 20 carbon atoms; aryloxy group having 6 to 20 carbon atoms such as phenyloxy group, 1-naphthyloxy group and 2-naphthyloxy group; thiol group; -20 alkylthio groups; allylthio groups; arylthio groups having 6 to 20 carbon atoms such as phenylthio groups, 1-naphthylthio groups and 2-naphthylthio groups; sulfoxy groups; 20 alkylsulfoxy group; phenylsulfoxy group, 1-naphthylsulfoxy group, arylsulfoxy group having 6 to 20 carbon atoms such as 2-naphthylsulfoxy group; silyl group; boryl group; monomethylamino group, dimethylamino Alkylamino groups having 1 to 20 carbon atoms such as trimethylamino group, monoethylamino group, diethylamino group and triethylamino group; arylamino group; aralkylamino group having 7 to 20 carbon atoms such as benzylamino group; carboxy group; carbamoyl group; alkylcarbonyl group having 2 to 20 carbon atoms such as acetyl group and propionyl group; benzoyl group and 1-naphthylcarbonyl group , arylcarbonyl groups having 7 to 20 carbon atoms such as 2-naphthylcarbonyl group; alkoxycarbonyl groups having 2 to 20 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; phenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2 - an aryloxycarbonyl group having 7 to 20 carbon atoms such as a naphthyloxycarbonyl group;

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From a synthetic point of view, chlorine and bromine atoms are preferred.

Examples of R ^a1 include groups represented by the following formulas (D-1) to (D-47) and formulas (G-1) to (G-22). * represents a bond.

—OR ^a1 represented by R ¹ to R ¹¹ includes the oxy group having the above R ^a1 , and includes an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. . —OR ^a1 specifically includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a phenoxy group, a naphthyloxy group and the like.

Halogen atoms for R ¹ to R ¹¹ include fluorine, chlorine, bromine and iodine atoms. From a synthetic point of view, chlorine and bromine atoms are preferred.

--CO--O--R ^a1 represented by R ¹ to R ¹¹ includes oxycarbonyl groups having the above R ^a1 , alkoxycarbonyl groups having 2 to 21 carbon atoms, and aryl groups having 7 to 21 carbon atoms. An oxycarbonyl group and the like can be mentioned. —CO—O—R ^{a1 includes} a saturated chain hydrocarbon group, a saturated alicyclic hydrocarbon group, a combination of an alicyclic hydrocarbon group and a chain hydrocarbon group, and an aromatic hydrocarbon group. It is preferably a hydrogen group or a group in which an aromatic hydrocarbon group and a chain hydrocarbon group are combined, a saturated chain hydrocarbon group having 1 to 20 carbon atoms, a saturated alicyclic hydrocarbon group having 3 to 15 carbon atoms a hydrogen group, a group obtained by combining an alicyclic hydrocarbon group having 4 to 15 carbon atoms and a chain hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic hydrocarbon having 7 to 20 carbon atoms It is more preferable to be a group combining a group and a chain hydrocarbon group, a saturated chain hydrocarbon group having 3 to 18 carbon atoms, an alicyclic hydrocarbon group having 4 to 10 carbon atoms and a chain hydrocarbon group or a group obtained by combining an aromatic hydrocarbon group having 7 to 15 carbon atoms and a chain hydrocarbon group. —CO—O—R ^a1 specifically includes a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, (1 -ethyl)pentyloxycarbonyl group, hexyloxycarbonyl group, (2-ethyl)hexyloxycarbonyl group, heptyloxycarbonyl group, (1-butyl)heptyloxycarbonyl group, octyloxycarbonyl group, (1-heptyl)octyloxy carbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, undecyloxycarbonyl group, dodecyloxycarbonyl group, tridecyloxycarbonyl group, tetradecyloxycarbonyl group, pentadecyloxycarbonyl group, hexadecyloxycarbonyl group, heptadecyl oxycarbonyl group, octadecyloxycarbonyl group, phenyloxycarbonyl group, benzyloxycarbonyl group, cyclohexyloxycarbonyl group, cyclohexylmethoxycarbonyl group, icosyloxycarbonyl group and the like.

—O—CO—R ^a1 represented by R ¹ to R ¹¹ includes carbonyloxy groups having the above R ^a1 , alkylcarbonyloxy groups having 2 to 21 carbon atoms, and alkylcarbonyloxy groups having 7 to 21 carbon atoms. An arylcarbonyloxy group and the like can be mentioned. —O—CO—R ^a1 specifically includes a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, a butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, and (2-ethyl). A hexylcarbonyloxy group, a phenylcarbonyloxy group, a cyclohexylcarbonyloxy group and the like can be mentioned.

--CO--R ^a1 represented by R ¹ to R ¹¹ includes carbonyl groups having the above R ^a1 , such as alkylcarbonyl groups having 2 to 21 carbon atoms and arylcarbonyl groups having 7 to 21 carbon atoms. is mentioned. —CO—R ^a1 specifically includes an acetyl group, a propionyl group, a butyroyl group, a pentanoyl group, a hexanoyl group, a cyclohexanoyl group, a benzoyl group and the like.

Examples of the ring formed by combining R ⁷ and R ⁸ include groups represented by the following formulas (H-1) to (H-4).

［式（Ｈ－１）～式（Ｈ－４）中、
Ｒ¹²～Ｒ²⁴は、互いに独立に、水素原子、－Ｒ^a2、－ＯＲ^a2、ハロゲン原子、ヒドロキシ基、カルボキシ基、－ＣＯ－Ｏ－Ｒ^a2、－Ｏ－ＣＯ－Ｒ^a2、－ＣＯ－Ｒ^a2又はニトロ基を表し、Ｒ^a2は、置換基を有していてもよい炭素数１～２０の炭化水素基を表す。
＊はＲ⁷が有する結合手を表し、＊＊はＲ⁸が有する結合手を表す。］

[In the formulas (H-1) to (H-4),
R ¹² to R ²⁴ each independently represent a hydrogen atom, -R ^a2 , -OR ^a2 , halogen atom, hydroxy group, carboxy group, -CO-OR ^{a2 , -O-CO-R a2 ,} -CO- represents R ^a2 or a nitro group, where R ^a2 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent;
* represents a bond possessed by ^R7 , and ** represents a bond possessed by ^R8 . ]

The hydrocarbon group having 1 to 20 carbon atoms optionally having substituent(s) represented by R ^a2 is the hydrocarbon group having 1 to 20 carbon atoms optionally having substituent(s) represented by R ^a1 and the same groups as those described above, and preferred embodiments thereof are also the same.

Halogen atoms for R ¹² to R ²⁴ include fluorine, chlorine, bromine and iodine atoms. From a synthetic point of view, chlorine and bromine atoms are preferred.

--OR ^a2 , --CO--O--R ^a2 , --O--CO--R ^a2 , ^--CO --R ^a2 as R ¹² to R ²⁴ , ^{--OR a1} , -- The groups described as CO--O--R ^a1 , --O--CO--R ^a1 , and --CO--R ^a1 can be mentioned.

In E, CH means a carbon atom to which a hydrogen atom is bonded, C-R ^a1 means a carbon atom to which R ^a1 is bonded, and N means a nitrogen atom.

R ¹ and R ² are, independently of each other, an optionally substituted saturated chain hydrocarbon group, an optionally substituted aromatic hydrocarbon group, or a substituted It is preferably a group in which an aromatic hydrocarbon group and a chain hydrocarbon group are combined. From the viewpoint of improving the solubility of compound (I) in a solvent, the saturated chain hydrocarbon group is preferably a saturated branched chain hydrocarbon group. The saturated chain hydrocarbon group (preferably saturated branched chain hydrocarbon group) preferably has 1 to 15 carbon atoms, more preferably 3 to 15 carbon atoms. A phenyl group is preferable as the aromatic hydrocarbon group. The group in which the aromatic hydrocarbon group and the chain hydrocarbon group are combined is preferably a phenyl group to which a chain hydrocarbon group having 1 to 12 carbon atoms (preferably 1 to 10) is bonded. It is more preferably a phenyl group in which 2 to 3 chain hydrocarbon groups having a number of 1 to 4 are bonded, and a phenyl group in which a chain hydrocarbon group having 1 to 4 carbon atoms is bonded to two ortho positions. More preferred. Among them, R ¹ and R ² are, independently of each other, groups represented by the above formulas (D-4) to (D-14) or formulas (G-5) to (G-22). More preferably, independently of each other, formulas (D-4) to (D-14), formula (G-5), formula (G-7), formula (G-8), formula (G-11) ~ Formula (G-13), Formula (G-15), Formula (G-16), Formula (G-19), Formula (G-21), or Formula (G-22) It is more preferably a group, independently of each other, formula (D-4) to formula (D-14), formula (G-7), formula (G-11), formula (G-13), formula (G -15) or a group represented by formula (G-16).
Also, R ¹ and R ² are preferably the same group.

R ³ to R ⁶ are each independently preferably a hydrogen atom, a halogen atom or a hydroxy group, more preferably a hydrogen atom.

R ⁷ and R ⁸ are preferably each independently a hydrogen atom, a halogen atom, or a hydroxy group, or are preferably bonded to each other to form a ring,
R ⁷ and R ⁸ may be hydrogen atoms, or R ⁷ and R ⁸ may be combined to form any of the groups represented by formulas (H-1) to (H-3) above. more preferably
More preferably, R ⁷ and R ⁸ are hydrogen atoms, or R ⁷ and R ⁸ are bonded together to form formula (H-1) or formula (H-2) above.

R ¹² to R ²⁴ are each independently preferably a hydrogen atom, —R ^a2 , a halogen atom or a hydroxy group, more preferably a hydrogen atom.

R ⁹ to R ¹¹ are each independently preferably a hydrogen atom, —R ^a1 , a halogen atom or a hydroxy group, more preferably a hydrogen atom.

E is preferably CH or N.

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

In Table 1, H represents a hydrogen atom and N represents a nitrogen atom.
D-6, D-13 and G-7 mean groups represented by the above formulas (D-6), (D-13) and (G-7) respectively.
C—H means a carbon atom bonded to a hydrogen atom.
H-1-1, H-2-1, H-3-1, and H ^- 4-1 are represented by the following formulas (H-1-1), ⁽ H- 2-1), formula (H-3-1), and formula (H-4-1). In the formula below, * represents a bond possessed by R ⁷ and ** represents a bond possessed by R ⁸ .

Compound (I) is preferably compounds (I-17) to (I-24), more preferably compounds (I-17) to (I-22).

Compound (I) can be prepared according to Route 1 or Route 2, for example.
Route 1 comprises a step (i) of reacting a compound represented by the following formula (pt-1) with X ₂ to obtain a compound represented by the formula (pt-2), and and a step (ii) of reacting the compound represented by the formula (MA-1) with the compound represented by the formula (MA-1) to obtain the compound (I).
Route 2 is a step (iii) of reacting a compound represented by the following formula (pt-2) with a compound represented by the formula (MA-2) to obtain a compound represented by the formula (pt-3); It comprises step (iv) of converting the compound represented by formula (pt-3) to obtain compound (I).

In the above formulas (pt-1) to (pt-3), R ¹ to R ¹¹ and E have the same meanings as above. In formulas (MA-1) and (MA-2), R ^B1 each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a sec-butyl group. , a tert-butyl group, a 2,2-dimethylpropyl-1,3-diyl group ring-formed by two R ^B1 , a 2,3-dimethylbutyl-2,3-diyl group, a 2-methylpentyl-2,4 - represents a diyl group, a 1,2-phenylene group, or the like.

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

Examples of the compound represented by 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; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, Alcohol solvents such as 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; Hydrocarbon solvents; halogenated hydrocarbon solvents such as methylene chloride, chloroform and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethylsulfoxide; acetic acid, propionic acid , butyric acid, etc., and methylene chloride and chloroform are more preferred.

The amount of X ₂ to be used is generally 1 mol or more and 5 mol or less, more preferably 1 mol or more and 2.5 mol or less, per 1 mol of the compound represented by the formula (pt-1). It is preferably 1 mol or more and 1.25 mol or less.

The amount of the solvent to be used is generally 1-1000 parts by mass per 1 part by mass of the compound represented by formula (pt-1).

The reaction temperature is usually -100°C or higher and 300°C or lower.

Compound (I) in step (ii) is a compound represented by formula (pt-2) (sometimes referred to as compound (pt-2)) and a compound represented by formula (MA-1) in a solvent. It can be produced by reacting in the presence of a medium, 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) (π-cinnamyl) chloride (dimer), allyl palladium (II) chloride dimer, bis (benzonitrile) palladium (II) dichloride, bis (acetonitrile) palladium (II) dichloride, palladium acetate ( II), bis(dibenzylideneacetone)palladium(0) is more preferred.

The phosphine ligands include tributylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, Tris(3-methoxyphenyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, ethyldiphenylphosphine, tris(2,6-dimethoxyphenyl)phosphine, tris(4-fluorophenyl), diphenylpropyl Phosphine, di-tert-butylphenylphosphine, tri(2-furyl)phosphine, tri(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, 2-(di-tert-butylphosphino) Biphenyl, di-tert-butyl(1,1-diphenyl-1-propen-2-yl)phosphine, isopropyldiphenylphosphine, 2-(dicyclohexylphosphino)-2'-(dimethylamino)biphenyl, 2-(dicyclohexylphosphine) phino)biphenyl, 2-(diphenylphosphino)biphenyl, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 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, dicyclohexyl (2',4',6'-triisopropyl-3,6-dimethoxy-[1,1'-biphenyl ]-2-yl)phosphine, monodentate phosphine such as dicyclohexyl(1,1-diphenyl-1-propen-2-yl)phosphine fin ligand, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 2 ,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-dimethylxane, 1,3-bis(diphenylphosphino)propane, 1,1'-bis(di-tert-butylphosphino)ferrocene, bis[2-(diphenylphosphino)phenyl]ether, Bidentate phosphine ligands such as 1,1′-bis(diisopropylphosphino)ferrocene, 1,1′-bis(diphenylphosphino)ferrocene, preferably monodentate phosphine ligands, and more Preferred are triphenylphosphine, tri-tert-butylphosphine and tricyclohexylphosphine, most preferred is triphenylphosphine.

Examples of the base include inorganic bases and organic bases.
Inorganic bases include hydroxides, carbonates, hydrogencarbonates, phosphates, carboxylates, alkoxides, etc. of alkali metals or alkaline earth metals. Here, the form of the base used may be either an anhydrous substance or a hydrated substance.
Inorganic bases preferably include alkali metal or alkaline earth metal hydroxides, carbonates, hydrogen carbonates, phosphates and carboxylates, and alkali metal or alkaline earth metal carbonates and phosphoric acid. Salt is more preferred. Alkali metal or alkaline earth metal salts include carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate and barium carbonate, and phosphates such as lithium phosphate, sodium phosphate and potassium phosphate. is preferred, and sodium carbonate, potassium carbonate and potassium phosphate are more preferred.
Examples of organic bases include triethylamine, 4-(N,N-dimethylamino)pyridine, pyridine, piperidine, N,N-diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[ 4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene and the like, and 1,8-diazabicyclo[5.4.0]-7-undecene is more preferable.
As bases, alkali metal or alkaline earth metal hydroxides, carbonates, hydrogen carbonates, phosphates and carboxylates, and organic bases are preferred, alkali metal or alkaline earth metal carbonates, and Phosphates and organic bases are more preferred.

Examples of the solvent include water; nitrile solvents such as acetonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, Alcohol solvents such as 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; hydrocarbon solvents; halogenated hydrocarbon solvents such as methylene chloride, chloroform and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; dimethylsulfoxide and the like sulfoxide solvent; carboxylic acid solvents such as acetic acid, propionic acid and butyric acid, and the like, preferably N,N-dimethylformamide, N,N-dimethylacetamide and toluene.

The amount of the catalyst to be used is generally 0.01 mol or more and 1 mol or less, more preferably 0.01 mol or more and 0.5 mol or less, still more preferably 1 mol of compound (pt-2). It is 0.01 mol or more and 0.25 mol or less.
The amount of the phosphine ligand to be used is generally 0.01 mol or more and 3 mol or less, more preferably 0.02 mol or more and 1 mol or less, still more preferably, per 1 mol of compound (pt-2). is 0.02 mol or more and 0.5 mol or less.
The amount of the base to be used is generally 1 mol or more and 50 mol or less, more preferably 1 mol or more and 25 mol or less, still more preferably 1 mol or more and 15 mol or less, per 1 mol of compound (pt-2). is.

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

The amount of the solvent to be used is generally 1-1000 parts by mass per 1 part by mass of the compound (pt-2).

The reaction temperature is usually -100°C or higher and 300°C or lower.

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

Examples of the catalyst include tris(dibenzylideneacetone)dipalladium(0), bis(dibenzylideneacetone)palladium(0), palladium(II) acetate, palladium(II) chloride, sodium tetrachloropalladium(II), palladium (II) (π-cinnamyl) chloride (dimer), allyl palladium (II) chloride dimer, bis (benzonitrile) palladium (II) dichloride, bis (acetonitrile) palladium (II) dichloride, palladium acetate ( II), bis(dibenzylideneacetone)palladium(0) is more preferred.

The phosphine ligands include tributylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, Tris(3-methoxyphenyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, ethyldiphenylphosphine, tris(2,6-dimethoxyphenyl)phosphine, tris(4-fluorophenyl), diphenylpropyl Phosphine, di-tert-butylphenylphosphine, tri(2-furyl)phosphine, tri(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, 2-(di-tert-butylphosphino) Biphenyl, di-tert-butyl(1,1-diphenyl-1-propen-2-yl)phosphine, isopropyldiphenylphosphine, 2-(dicyclohexylphosphino)-2'-(dimethylamino)biphenyl, 2-(dicyclohexylphosphine) phino)biphenyl, 2-(diphenylphosphino)biphenyl, 2-dicyclohexylphosphino-2'-methylbiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 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, dicyclohexyl (2',4',6'-triisopropyl-3,6-dimethoxy-[1,1'-biphenyl ]-2-yl)phosphine, monodentate phosphine such as dicyclohexyl(1,1-diphenyl-1-propen-2-yl)phosphine fin ligand, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 2 ,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-dimethylxane, 1,3-bis(diphenylphosphino)propane, 1,1'-bis(di-tert-butylphosphino)ferrocene, bis[2-(diphenylphosphino)phenyl]ether, Bidentate phosphine ligands such as 1,1′-bis(diisopropylphosphino)ferrocene and 1,1′-bis(diphenylphosphino)ferrocene are included, preferably monodentate phosphine ligands.

Examples of the base include hydroxides, carbonates, hydrogen carbonates, phosphates, carboxylates, alkoxides, etc. of alkali metals or alkaline earth metals, which are inorganic bases. Here, the form of the base used may be either an anhydrous substance or a hydrated substance. Preferred are alkali metal or alkaline earth metal hydroxides, carbonates, hydrogen carbonates, phosphates and carboxylates, more preferably alkali metal or alkaline earth metal carbonates and phosphates. preferable. Preferred alkali metal or alkaline earth metal salts are lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, barium carbonate, lithium phosphate, sodium phosphate, and potassium phosphate. and potassium phosphate are more preferred.

Examples of the solvent include water; nitrile solvents such as acetonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, Alcohol solvents such as 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; hydrocarbon solvents; halogenated hydrocarbon solvents such as methylene chloride, chloroform and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; dimethylsulfoxide and the like Sulfoxide solvent; carboxylic acid solvents such as acetic acid, propionic acid and butyric acid, and the like, preferably toluene, xylene and tetrahydrofuran.

The amount of the catalyst to be used is generally 0.01 mol or more and 1 mol or less, more preferably 0.01 mol or more and 0.5 mol or less, still more preferably 1 mol of compound (pt-2). It is 0.01 mol or more and 0.25 mol or less.
The amount of the phosphine ligand to be used is generally 0.01 mol or more and 3 mol or less, more preferably 0.02 mol or more and 1 mol or less, still more preferably, per 1 mol of compound (pt-2). is 0.02 mol or more and 0.5 mol or less.
The amount of the base to be used is generally 1 mol or more and 50 mol or less, more preferably 1 mol or more and 25 mol or less, still more preferably 1 mol or more and 15 mol or less, per 1 mol of compound (pt-2). is.

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

The amount of the solvent to be used is generally 1-1000 parts by mass per 1 part by mass of the compound (pt-2).

The reaction temperature is usually -100°C or higher and 300°C or lower.

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

Examples of the solvent include water; nitrile solvents such as acetonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, Alcohol solvents such as 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; hydrocarbon solvents; halogenated hydrocarbon solvents such as methylene chloride, chloroform and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; dimethylsulfoxide and the like sulfoxide solvents; carboxylic acid solvents such as acetic acid, propionic acid and butyric acid, and the like, 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, metal hydride lamps, and the like.

The amount of the solvent to be used is generally 1-1000 parts by mass per 1 part by mass of the compound (pt-3).

The reaction temperature is usually -100°C or higher and 300°C or lower.

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

The compound (MA-3) includes metal chlorides, preferably iron (III) chloride, zinc chloride and aluminum chloride.

The amount of compound (MA-3) to be used is generally 0.01 mol or more and 10 mol or less, more preferably 0.1 mol or more and 5 mol or less, per 1 mol of compound (pt-3).

Examples of the solvent include water; nitrile solvents such as acetonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, Alcohol solvents such as 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; hydrocarbon solvents; halogenated hydrocarbon solvents such as methylene chloride, chloroform and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; dimethylsulfoxide and the like sulfoxide solvent; carboxylic acid solvents such as acetic acid, propionic acid and butyric acid, nitro solvents such as nitromethane and nitrobenzene, and the like, with dichloromethane, chloroform and nitromethane being preferred.

The amount of the solvent to be used is generally 1-1000 parts by mass per 1 part by mass of the compound (pt-3).

The reaction temperature is usually -100°C or higher and 300°C or lower.

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

Dye (A1-1) is not particularly limited as long as it does not include compound (I), and known dyes can be used. Examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Dyes include, for example, compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in Dye Note (Shikisensha). Also, according to 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, quinolines Dyes, nitro dyes, phthalocyanine dyes, and the like. Among these, organic solvent-soluble dyes are preferred.

Specifically, as the dye (A1-1),
C. I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;
C. I. Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;
C. I. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. solvent blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; I. solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. acid blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
C. I. acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109; 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, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; I. direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. C.I., such as Disperse Blue 1, 14, 56, 6; I. disperse dyes,
C. I. Basic Red 1, 10;
C. I. basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. basic violet 2;
C. I. basic red 9;
C. I. Basic Green 1; I. basic dye,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. C.I. Reactive Red 36; 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. Modern Tread 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. Modant 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. Modant 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. such as C.I. I. modant dye,
C. I. Bat Green 1; I. Color Index (C.I.) number dyes such as vat dyes are included.

The pigment (A1-2) is not particularly limited as long as it does not include the compound (I), and known pigments can be used. pigments.
Pigments classified as pigments include, for example, C.I. 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, yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231;
C. I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
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, red pigments such as 273;
C. I. Blue pigments such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60;
C. I. Violet color pigments such as Pigment Violet 1, 19, 23, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7, 36, 58, 59, 62, 63;
C. I. Brown pigments such as Pigment Brown 23 and 25;
C. I. black pigments such as Pigment Black 1 and 7;

As colorants (A1), yellow, red or green dyes and pigments are preferred.

The coloring agent (A1) may be subjected, if necessary, to rosin treatment, surface treatment using a derivative into which an acidic group or a basic group is introduced, or the like, graft treatment to the surface of the coloring agent (A1) with a polymer compound or the like, sulfuric acid Atomization treatment by an atomization method or the like, washing treatment with an organic solvent, water, or the like for removing impurities, removal treatment by an ion exchange method or the like for ionic impurities, or the like may be performed. The particle size 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% by mass or more, preferably 2% by mass, relative to the total amount of the colorant (A). or more, more preferably 10% by mass or more, still more preferably 25% by mass or more, and particularly preferably 50% by mass or more. Moreover, when the colorant (A) further contains the colorant (A1), the content of the compound (I) is, for example, less than 100% by mass with respect to the total amount of the colorant (A).

When the colored resin composition contains the solvent (E), a colorant-containing liquid (sometimes referred to as a colored composition) containing the colorant (A) and the solvent (E) is prepared in advance, and then the colorant is added. A colored resin composition may be prepared using the containing liquid. When the colorant (A) does not dissolve in the solvent (E), for example, when the colorant (A) contains the pigment (A1-2), the colorant-containing liquid contains the colorant (A) and the solvent (E ) can be prepared by dispersing and mixing. The colorant-containing liquid may contain part or all of the solvent (E) contained in the colored resin composition.

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

The coloring agent (A) may be dispersed uniformly in the solution by incorporating a dispersing agent into the coloring agent (A) and performing a dispersion treatment. When two or more types are used in combination as the colorant (A), each of them may be subjected to dispersion treatment alone, or a plurality of types may be mixed and subjected to dispersion treatment.

Examples of dispersing agents include surfactants, and cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples include surfactants such as polyester-based, polyamine-based and acrylic-based surfactants. These dispersants may be used alone or in combination of two or more. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), and EFKA (registered trademark). (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and the like. . A resin (B) described later may be used as a dispersant.

When a dispersant is used, the amount of the dispersant (solid content) 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, relative to 100 parts by mass of the colorant (A). 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. When the amount of the dispersant used is within the above range, there is a tendency to obtain a colorant-containing liquid in a more uniformly dispersed state.

The content of the coloring agent (A) is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.5% by mass or more and 40% by mass, based on the total solid content of the colored resin composition. or less, more preferably 1% by mass or more and 30% by mass or less. When the content of the coloring agent (A) is within the above range, the color density of the color filter is sufficient, and the necessary amount of the resin (B) can be contained in the composition. It is preferable because a pattern with sufficient strength can be formed.
Here, the "total amount of solid content" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
Although the resin (B) is not particularly limited, it is preferably a resin used for forming a photoresist unlike a thermoplastic resin. Among them, the resin (B) is more preferably an alkali-soluble resin, more preferably an alkali-soluble resin having a carboxylic acid. A colored resin composition in which an alkali-soluble resin is used as the resin (B) can be suitably used as a photoresist.

Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]: a structural unit derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)"); A copolymer having a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure and an ethylenically unsaturated bond of ~4;
Resin [K2]; a structural unit derived from (a), a structural unit derived from (b), and a monomer (c) copolymerizable with (a) (where (a) and (b) are different.) (hereinafter sometimes referred to as "(c)") and a copolymer having a structural unit derived from;
Resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c);
Resin [K4]; a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c);
Resin [K5]; a copolymer having a structural unit 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 monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and o-, m-, p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;
methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-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] Bicyclounsaturated compounds containing a carboxy group such as hept-2-ene;
Carboxylic acid anhydrides such as the anhydrides of the above unsaturated dicarboxylic acids except fumaric acid and mesaconic acid;
Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate kind;
unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid;
Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.
In this specification, "(meth)acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

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

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

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

As the monomer (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferred. 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, 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 (eg, Celloxide (registered trademark) 2000; manufactured by Daicel Corporation), and 3,4-epoxycyclohexylmethyl. (Meth)acrylate (eg, Cychromer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cychromer (registered trademark) M100; manufactured by Daicel Corporation) , a compound represented by the formula (BI), a compound represented by the formula (BII), and the like.

[In formula (BI) and formula (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. may be substituted with
X ^a and X ^b each independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond with O. ]

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

Alkyl groups in which a hydrogen atom is substituted with hydroxy include, for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1 -hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

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

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, A hexane-1,6-diyl group and the like can be mentioned.

X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, a *—CH ₂ —O— (* represents a bond with O) group, or a *—CH ₂ CH ₂ —O— group. more preferably a single bond or *--CH ₂ CH ₂ --O-- group (* represents a bond with O).

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

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

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

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 preferred. Examples of the monomer (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyl oxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyloxetane and the like.

As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., 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, tert-butyl (meth)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 ^2,6 ]decane-8-yl (meth)acrylate (in the technical field, it is commonly referred to as “dicyclopentanyl (meth)acrylate”. Also, “tricyclodecyl (meth)acrylate ”), tricyclo[5.2.1.0 ^2,6 ]decan-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth ) acrylate (commonly referred to as “dicyclopentenyl (meth)acrylate” in the technical field), tricyclo[5.2.1.0 ^2,6 ]decen-9-yl (meth)acrylate, di Cyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate (meth)acrylic acid esters such as acrylates;
Hydroxy group-containing (meth)acrylic acid esters 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-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2′-hydroxyethyl)bicyclo[2.2. 1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy -5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2 .2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyl oxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 - dicarbonylimide derivatives such as 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; vinyl chloride and vinylidene chloride, etc. 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; .
Among these, styrene, vinyl toluene, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, tricyclo[5.2.1 .0 ^2,6 ]decane-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^{2, 6} ]decen-9-yl(meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and benzyl(meth)acrylate are preferred.

In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1] is
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40 to 98 mol%
is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (b); 50 to 90 mol%
is more preferable.
When the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the colored resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter tend to be excellent. be.

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin, 1st edition, 1st edition, published on March 1, 1972) and the literature It can be manufactured with reference to the cited document described in .

Specifically, predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, by replacing oxygen with nitrogen, a deoxygenated atmosphere is created, and while stirring, A method of heating and keeping warm can be mentioned. The polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). As the solvent, any solvent can be used as long as it dissolves each monomer, and examples thereof include the solvents described later as the solvent (E) for the colored resin composition of the present invention.

The obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. You can use things. In particular, by using the solvent contained in the colored resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored resin composition of the present invention. The manufacturing process of the colored resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the total structural units constituting the resin [K2] is
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
is preferably
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
is more preferable.
When the ratio of the structural units of the resin [K2] is in the above range, the storage stability of the colored resin composition, the developability when forming a colored pattern, and the solvent resistance and heat resistance of the resulting color filter are improved. And tend to be excellent in mechanical strength.

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

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

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

Next, part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms of (b).
Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst (e.g., tris ( dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in a flask and reacted at, for example, 60 to 130° C. for 1 to 10 hours to produce resin [K4]. can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting this range, the storage stability of the colored resin composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity balance of the resulting pattern tend to be good. be. Since the cyclic ether has high reactivity and unreacted (b) hardly remains, (b1) is preferable as the (b) used in the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by weight per 100 parts by weight of the total amount of (a), (b) and (c).
Reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

For resin [K5], as the first step, a copolymer of (b) and (c) is obtained in the same manner as in the method for producing resin [K1] described above. In the same manner as described above, the obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be converted into a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer is, respectively,
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
is preferably
Structural unit derived from (b); 10 to 90 mol%
Structural unit derived from (c); 10 to 90 mol%
is more preferable.

Furthermore, under the same conditions as in the method for producing resin [K4], the cyclic ether derived from (b) in the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic anhydride of (a). Resin [K5] can be obtained by reacting substances.
The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol per 100 mol of (b). Since the cyclic ether has high reactivity and unreacted (b) does not easily remain, (b1) is preferable as (b) used in resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by reacting resin [K5] with a carboxylic acid anhydride. The hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride is reacted with the carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like. The amount of carboxylic acid anhydride to be used is preferably 0.5 to 1 mol per 1 mol of (a).

Specific resins (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] Resin [K1] such as decyl acrylate/(meth)acrylic acid copolymer; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth) Acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[ 5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyl Resins such as oxetane/(meth)acrylic acid/styrene copolymer [K2]; resins such as benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer [K3] ; Resin obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer Resins such as acrylate-added resins and resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer [K4]; tricyclodecyl (Meth)acrylate/glycidyl (meth)acrylate copolymer reacted with (meth)acrylic acid, tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate copolymer (meth)acrylic Resin [K5] such as acid-reacted resin; tricyclodecyl (meth) acrylate/glycidyl (meth) acrylate copolymer reacted with (meth)acrylic acid and further reacted with tetrahydrophthalic anhydride resin [K6] such as a resin obtained by

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

The polystyrene equivalent weight average molecular weight (Mw) of the resin (B) is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 50,000 or less, and still more preferably 3,000 or more. 30,000 or less. When the weight-average molecular weight is within the above range, the unexposed area tends to have high solubility in a developer, and the resulting pattern tends to have a high residual film rate and hardness.
The dispersity [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1 or more and 6 or less, more preferably 1.001 or more and 4 or less, and still more preferably 1.001 or more. 01 or more and 4 or less.

The acid value (solid content conversion value) of the resin (B) is preferably 10 mg-KOH/g or more and 300 mg-KOH/g or less, more preferably 20 mg-KOH/g or more and 250 mg-KOH/g or less, More preferably 25 mg-KOH/g or more and 200 mg-KOH/g or less, still more preferably 30 mg-KOH/g or more and 150 mg-KOH/g or less, particularly preferably 60 mg-KOH/g or more and 135 mg-KOH/g g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by titration with 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, still more preferably 15 to 30% by mass, based on 100% by mass of the solid content of the colored resin composition. is. When the content of the resin (B) is within the above range, the solubility of the unexposed area in the developer tends to be high.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D). is a (meth)acrylic acid ester compound.

Examples of polymerizable compounds having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. etc., as well as monomers (a), (b) and (c) described above.

Polymerizable compounds having two ethylenically unsaturated bonds include, for example, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, (meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate and the like.

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 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, Examples include caprolactone-modified pentaerythritol tetra(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate, preferably dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

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

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

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat, and known polymerization initiators 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 O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- 1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)- 3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl -2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3- cyclopentylpropan-1-one-2-imine and the like. As the O-acyl oxime compound, commercial products such as Irgacure (registered trademark) OXE01 and OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA Corporation) may be used. Among them, O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- At least one selected from the group consisting of 1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyl Oxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferred.

Alkylphenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1- and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercially available products such as Irgacure (registered trademark) 369, 907, 379 (manufactured by BASF) may be used as the alkylphenone compound.
Examples of alkylphenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, Also included are 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone and benzyl dimethyl ketal.

Biimidazole compounds include, for example, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2,3-dichlorophenyl)-4 ,4′,5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis(2-chlorophenyl)-4,4 ',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2' -bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.) and 4 , 4′,5,5′-positioned phenyl groups are substituted with carboalkoxy groups (see, for example, JP-A-7-10913).

Triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 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)ethenyl]-1,3,5-triazine, 2,4-bis( trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methyl phenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. .

Acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

Furthermore, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate and titanocene compounds.
These are preferably used in combination with a 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 alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, more preferably It is a polymerization initiator containing an O-acyl oxime compound.

The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 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. or less, more preferably 1 part by mass or more and 20 parts by mass or less. 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, thereby improving the productivity of the color filter.

<Polymerization initiation aid (D1)>
The polymerization initiation aid (D1) is a compound or a sensitizer used to accelerate the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D). When the polymerization initiation aid (D1) is included, 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 amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N,N-dimethylp-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-bis( ethylmethylamino)benzophenone and the like, preferably 4,4'-bis(diethylamino)benzophenone. As the amine compound, a commercially available product such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

Alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxy and anthracene and 2-ethyl-9,10-dibutoxyanthracene.

Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propoxythioxanthone.

Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

When these polymerization initiation aids (D1) are used, the content thereof is preferably 0.5 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) contained in the colored resin composition. It is 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.

<Solvent (E)>
The solvent (E) is not particularly limited, and solvents commonly used in the field can be used.
The solvent (E) is, for example, an ester solvent (a solvent containing -COO- in the molecule but not containing -O-), an ether solvent (a solvent containing -O- in the molecule but not containing -COO-), Ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not containing -COO-), alcohol solvents (containing OH in the molecule , —O—, —CO— and —COO—-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like. These solvents may be used in combination of two or more.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and 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, phenetol, methylanisole and the like.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. etc.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene and the like.

Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

The solvent (E) is preferably a solvent containing at least one selected from 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, relative to the total amount of the colored resin composition. % by mass or less, more preferably 70% by mass or more and 95% by mass or less, and even more preferably 75% by mass or more and 90% by mass or less. In other words, the total solid content of the colored resin composition is usually 0.01% by mass or more, preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less. , more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 25% by mass or less. When the content of the solvent (E) is within the above range, the flatness at the time of coating is improved, and when a color filter is formed, the color density is not insufficient, so the display characteristics tend to be improved. .

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC), etc. .

Examples of fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, Florard FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Florado F171, Flora F172, Flora F173, Flora F177, Flora F183, Flora F554 R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by AGC Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratory Co., Ltd.).

Examples of fluorine atom-containing silicone-based surfactants include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.

When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.0005% by mass or more and 1% by mass or less, more preferably 0.0005% by mass or more and 1% by mass or less, relative to the total amount of the colored resin composition. 001% by mass or more and 0.5% by mass or less, more preferably 0.005% by mass or more and 0.1% by mass or less. This content does not include the content of the dispersant described above. 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, if necessary, contains additives known in the art such as fillers, other polymer compounds, adhesion promoters, quenchers, antioxidants, light stabilizers, chain transfer agents, etc. It's okay.

<Method for producing colored resin composition>
The colored resin composition contains a colorant (A), a resin (B), and optionally a polymerizable compound (C), a polymerization initiator (D), a polymerization initiation aid (D1), and a solvent (E). , leveling agent (F) and other ingredients. Mixing can be performed by a known or commonly used device and conditions.
The colorant (A) may be mixed with part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle size is about 0.2 μm or less. It is preferable to use it in a state in which it is folded. At this time, if necessary, a part or all of the dispersant and resin (B) may be blended. Further, the coloring agent (A) may be dissolved in the solvent (E) in part or in its entirety before use. The desired colored resin composition can be prepared by mixing the colorant-containing liquid thus obtained with the remaining components so as to have a predetermined concentration.

<Manufacturing method of color filter>
A color filter, which may be a color conversion layer, can be formed from the colored resin composition of the present invention. A photolithography method, an inkjet method, a printing method, and the like can be used as a method for forming a colored pattern. Among them, the photolithographic method is preferred. The photolithographic method is a method in which the colored resin composition is applied to a substrate, dried to form a colored resin composition layer, exposed through a photomask, and developed. In the photolithographic method, a colored coating film, which is a cured product of the colored resin composition layer, can be formed by not using a photomask during exposure and/or not developing. The colored pattern or colored coating film thus formed is 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 and application. More preferably, it is 0.5 μm or more and 6 μm or less.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass whose surface is coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; A thin film of aluminum, silver, silver/copper/palladium alloy, etc., is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be carried out using a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored resin composition is applied onto a substrate, dried by heating (pre-baking) and/or dried under reduced pressure to remove volatile components such as solvents, and dried to obtain a smooth colored resin composition layer.
Examples of coating methods include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature for heat drying is preferably 30° C. or higher and 120° C. or lower, more preferably 50° C. or higher and 110° C. or lower. The heating time is preferably 10 seconds or more and 60 minutes or less, more preferably 30 seconds or more and 30 minutes or less.
When drying under reduced pressure, it is preferable to carry out under a pressure of 50 Pa or more and 150 Pa or less in a temperature range of 20° C. or more and 25° C. or less.
The thickness of the colored resin composition layer is not particularly limited, and may be appropriately selected according to the desired thickness of the color filter.

Next, the colored resin composition layer is exposed through a photomask to form a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use is used. In addition, since it is possible to uniformly irradiate the entire exposure surface with parallel light rays and to accurately align the photomask and the substrate on which the colored resin composition layer is formed, the exposure apparatus such as a mask aligner and a stepper can be used. is preferably used. When forming a colored coating film, exposure may be performed without using a photomask.

A light source used for exposure is preferably a light source that emits light having a wavelength of 250 nm or more and 450 nm or less. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You can Specifically, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like can be used.

A colored pattern is formed on the substrate by contacting the exposed colored resin composition layer with a developer for development. By development, the unexposed portion of the colored resin composition layer is dissolved in the developer and removed. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less. Furthermore, the developer may contain a surfactant.
The developing method may be any of a puddle method, a dipping method, a spray method, and the like. Furthermore, the substrate may be tilted at any angle during development.
The substrate after development is preferably washed with water.

Furthermore, it is preferable to post-bake the obtained colored pattern or colored coating film. The post-baking temperature is preferably 150° C. or higher and 250° C. or lower, more preferably 160° C. or higher and 240° C. or lower. The post-baking time is preferably 1 minute or more and 120 minutes or less, more preferably 10 minutes or more and 60 minutes or less.

<Display device>
The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices, especially as a color filter used in organic EL devices.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and can be modified appropriately within the scope that can conform to the gist of the above and later descriptions. It is of course possible to implement them, and all of them are included in the technical scope of the present invention. In the following description, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

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

The polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40°C
Solvent: Tetrahydrofuran Flow rate: 1.0 mL/min Solid content concentration of analysis sample: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw/Mn) of the polystyrene-equivalent weight-average molecular weight and the number-average molecular weight obtained 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 in Chemical Communications 2005, 4045-4046.

<Identification of Compound I-19>
(mass spectrometry) ionization mode = ESI+: m/z = [M+H] ⁺ 875
Exact Mass: 874

[Synthesis Example 2]
<Preparation of compound I-17>
Compound (I-17) was synthesized according to the description in European Journal of Organic Chemistry, 2014, 5178-5195.

<Identification of Compound I-17>
(mass spectrometry) ionization mode = ESI+: m/z = [M+H] ⁺ 801
Exact Mass: 800

[Synthesis Example 3]
<Preparation of compound I-22>
Compound (I-22) was synthesized according to the description in Organic Letters, 2010, Vol. 12, 228-231.

<Identification of compound I-22>
(mass spectrometry) ionization mode = ESI+: m/z = [M+H] ⁺ 877
Exact Mass: 876

[Synthesis Example 4]
<Preparation of compound I-18>
Compound (I-18) was synthesized according to the description in Organic Letters, 2010, Vol. 12, 228-231.

<Identification of Compound I-18>
(mass spectrometry) ionization mode = ESI+: m/z = [M+H] ⁺ 802
Exact Mass: 801

Lumogen (registered trademark) F Orange 240 (compound represented by the following formula (x)) was obtained from Tokyo Chemical Industry Co., Ltd.

[Synthesis Example 5]
A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^{2, 6} ] A mixed solution of 289 parts of a mixture of decane-9-yl acrylate (content ratio is 1:1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution prepared by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition was completed, it was held at 80° C. for 4 hours, then cooled to room temperature, and a copolymer (resin B1) solution with a solid content of 35.1% and a viscosity of 125 mPa·s measured with a Brookfield viscometer (23° C.) was obtained. got The resulting copolymer had a weight average molecular weight Mw of 9.2×10 ³ , a dispersity of 2.08, and an acid value of 77 mg-KOH/g in terms of solid content. Resin B1 has the following structural units.

<Example 1>
(1) Preparation of colored resin composition Each component was mixed in the following proportions to obtain a colored resin composition 1.
(A) Colorant: 2.6 parts of compound represented by 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, each component was mixed in the following proportions to obtain a colored curable resin composition 1.
Colored resin composition 1 478 parts (C) polymerizable compound: dipentaerythritol hexaacrylate
(Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts (D) polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation) 2 parts (F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd.) 0.15 parts

(3) Preparation of colored coating film (color filter) On a 5 cm square glass substrate (Eagle XG; manufactured by Corning), the colored curable resin composition is spin-coated so that the film thickness after post-baking is 2 μm. After coating according to the method, pre-baking was performed at 100° C. for 3 minutes to form a colored composition layer. After cooling, the colored composition layer formed on the substrate is exposed to light at an exposure amount of 80 mJ/cm ² (365 nm standard) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). irradiated. After light irradiation, post-baking was performed in an oven at 230° C. for 30 minutes to obtain a colored coating film.
The film thickness of the resulting colored coating film was measured using DEKTAK3 (manufactured by Nippon Vacuum Engineering Co., Ltd.) and found to be 2 μm.
The chromaticity evaluation of the colored coating film is performed by measuring the spectrum using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and using the characteristic function of the C light source, the xy color in the CIE XYZ color system. It was done by measuring the degree coordinates (x, y) and the stimulus value Y.

(4) Heat resistance test The resulting colored coating film was heated in an oven at 230°C for 120 minutes in an air atmosphere. The color difference ΔE ^* ab was calculated from the xy chromaticity coordinates (x, y) and Y measurement values before and after the test by the method described in JIS Z 8730:2009 (7. Color difference calculation method). It means that the smaller the color difference ΔE ^* ab, the smaller the color change ^. Moreover, if the heat resistance of the colored coating film is good, the colored pattern produced from the same colored curable resin composition can also be said to have good heat resistance. Table 2 shows the results.

(5) Light resistance test An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya; cuts light of 380 nm or less) is placed on the obtained colored coating film, and a light resistance tester (SUNTEST CPS +: Toyo Seiki Co., Ltd. (manufacturer) and irradiated with xenon lamp light for 48 hours. The color difference ΔE ^* ab was calculated from the xy chromaticity coordinates (x, y) and Y measurement values before and after the test by the method described in JIS Z 8730:2009 (7. Color difference calculation method). Incidentally, the smaller the color difference ΔE ^* ab, the smaller the color change ^. In addition, if the colored coating film has good light resistance, it can be said that the colored pattern produced from the same colored curable resin composition also has good light resistance. Table 2 shows the results.

<Examples 2 to 4 and Comparative Example 1>
2. Instead of 6 parts of compound (I-19),
2.6 parts of compound (I-17) (Example 2),
2.6 parts of compound (I-22) (Example 3),
Same as Example 1 except 2.6 parts of compound (I-18) (Example 4) or 2.6 parts of Lumogen® F Orange 240 (Comparative Example 1) were used as the colorant. to obtain a colored curable resin composition. Further, a colored coating film was prepared in the same manner as in Example 1, and the above heat resistance test and light resistance test were conducted. Table 2 shows the results.

Claims (4)

A colored resin composition containing a coloring agent and a resin, wherein the coloring agent contains a compound represented by formula (I).

[in the formula (I),
R ¹ to R ¹¹ each independently represent a hydrogen atom, -R ^a1 , -OR ^a1 , halogen atom, hydroxy group, carboxy group, -CO-O-R ^a1 , -O-CO-R ^a1 , -CO- represents R ^a1 or a nitro group, and R ⁷ and R ⁸ may combine with each other to form a ring;
E represents CH, ^{CR a1} or N;
R ^a1 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms. ] The colored resin composition according to claim 1, further comprising a polymerizable compound and a polymerization initiator. A color filter formed from the colored resin composition according to claim 1 or 2. A display device comprising the color filter according to claim 3 .