CN111295416B

CN111295416B - Colored curable resin composition, color filter, and display device

Info

Publication number: CN111295416B
Application number: CN201880071011.5A
Authority: CN
Inventors: 中山智博; 高石悠; 赤坂哲郎; 冈本信之
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2017-11-10
Filing date: 2018-11-08
Publication date: 2022-01-07
Anticipated expiration: 2038-11-08
Also published as: TWI748137B; CN111295416A; TW201922944A; WO2019093797A2; WO2019093797A3

Abstract

The present invention relates to a colored curable resin composition, a color filter, and a display device, wherein the colored curable resin composition comprises a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant comprises a compound represented by formula (I) and a red pigment (except for the compound represented by formula (I)), and the content of the red pigment is 1 mass% or more and 95 mass% or less with respect to the total amount of the colorant.

Description

Colored curable resin composition, color filter, and display device

Technical Field

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

Background

Color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, and solid-state imaging elements such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor) sensors are made of colored curable resin compositions. As such a colored curable resin composition, a composition containing only a compound represented by the following formula as a colorant is known.

(International publication No. 2014/196464, etc.)

Disclosure of Invention

Technical subject

The color filter formed by the above-mentioned colored curable resin composition known in the prior art cannot satisfy the brightness. In addition, the color filter formed from the above-mentioned colored curable resin composition known in the art cannot satisfy light resistance.

Means for solving the problems

The gist of the present invention is as follows.

[1] A colored curable resin composition comprising: a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant comprises a compound represented by formula (I) and a red pigment (except for the compound represented by formula (I)), and the content of the red pigment is 1% by mass or more and 95% by mass or less relative to the total amount of the colorant;

[ in the formula (I),

R¹～R¹⁰each independently represents a hydrogen atom, a halogen atom, or a saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom;

R¹¹～R¹⁶each independently represents a hydroxyl group, a halogen atom, a cyano group, a nitro group, a saturated hydrocarbon group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, wherein a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a cyano group, a nitro group, a hydroxyl group or a halogen atom, and a hydrogen atom contained in the phenyl group or the benzyl group may be substituted by a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, a cyano group or a vinyl group;

R¹¹and R¹²、R¹³And R¹⁴And R¹⁵And R¹⁶Can be connected to form a bagA 3-to 6-membered heterocyclic ring containing a nitrogen atom,

R¹and R¹¹、R²And R¹²、R⁴And R¹³、R⁵And R¹⁴、R⁸And R¹⁵、R¹⁰And R¹⁶、R⁷And R⁸And R⁹And R¹⁰May each be joined to form a 6-membered ring;

A^q-q represents an anion having a valence of q, q represents an integer of 1 to 14;

p represents a coefficient for keeping the charge neutral of the compound represented by the formula (I) ].

[2] A colored curable resin composition comprising: a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant comprises a compound represented by formula (I) and a red pigment (except for the compound represented by formula (I)), and the content of the red pigment is 30 to 95 mass% based on the total amount of the colorant;

[ in the formula (I),

R¹¹and R¹²、R¹³And R¹⁴And R¹⁵And R¹⁶Can be independently linked to form a 3-to 6-membered heterocyclic ring containing a nitrogen atom,

[3]Such as [1]]Or [2]]The colored curable resin composition, wherein A^q-Selected from the following: an anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom, a halide anion, a perchlorate anion, a chlorate ion, a thiocyanate ion, a hexafluorophosphate ion, a hexafluoroantimonate ion, a tetrafluoroborate ion, an organocarboxylate anion, an organosulfonate anion, an organophosphate anion, an organoimidinate anion, an organomomethylate anion, and a metal complex anion.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the colorant further comprises a yellow pigment (except for the compound represented by the formula (I)).

[5] A color filter comprising the colored curable resin composition according to any one of [1] to [4 ].

[6] A display device comprising the color filter of [5 ].

Effects of the invention

According to the colored curable resin composition of the present invention, a color filter having excellent brightness can be formed. In addition, according to the colored curable resin composition of the present invention, a color filter having excellent light resistance can be formed.

Detailed Description

The colored curable resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as a colorant (a)), a resin (hereinafter, sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, sometimes referred to as a polymerizable compound (C)), and a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)).

The colorant (A) contains a compound represented by the formula (I) and a red pigment (except for the compound represented by the formula (I)), and the content of the red pigment is 1 to 95 mass% based on the total amount of the colorant.

The colored curable resin composition of the present invention preferably further contains a solvent.

The colored curable resin composition of the present invention may contain a leveling agent.

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

< colorant (A) >)

The colorant (A) contains a compound represented by the formula (I) and a red pigment (except for the compound represented by the formula (I)).

The compound represented by the formula (I) is as follows.

[ in the formula (I),

Represents R¹～R¹⁰And R¹¹～R¹⁶The saturated hydrocarbon group having 1 to 8 carbon atoms may be any of straight chain, branched chain and cyclic. Examples of the linear or branched saturated hydrocarbon group include: linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups. The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 4.

The cyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include: cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 3 to 8, more preferably 6 to 8.

Among them, linear saturated hydrocarbon groups are preferable, and methyl, ethyl, and propyl groups are particularly preferable.

The hydrogen atom contained in the above-mentioned saturated hydrocarbon group may be substituted with a halogen atom.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. When the halogen atom is a fluorine atom, the halogen atom is preferably substituted so as to form a perfluoroalkyl group unit such as a trifluoromethyl group unit, a pentafluoroethyl group unit, or a heptafluoropropyl group unit.

R¹¹～R¹⁶In the above formula, a hydrogen atom contained in a saturated hydrocarbon group having 1 to 8 carbon atoms may be substituted with a cyano group, a nitro group, a hydroxyl group or a halogen atom.

R¹¹～R¹⁶Wherein the hydrogen atom in the phenyl group and benzyl group may be substituted by a C1-4 saturated hydrocarbon group or a halogenAn element atom, cyano group or vinyl group.

Can be aligned with R¹¹～R¹⁶Examples of the C1-4 saturated hydrocarbon group substituted with a hydrogen atom contained in the phenyl group and the benzyl group include the same groups as those of the C1-4 saturated hydrocarbon group in the C1-8 saturated hydrocarbon group.

R¹And R¹¹、R²And R¹²、R⁴And R¹³、R⁵And R¹⁴、R⁸And R¹⁵、R¹⁰And R¹⁶、R⁷And R⁸And R⁹And R¹⁰May each be joined to form a 6-membered ring.

Examples of the 6-membered ring include a benzene ring, a piperidine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, and an isoquinoline ring.

R¹¹And R¹²、R¹³And R¹⁴And R¹⁵And R¹⁶Can be independently linked to form a 3-to 6-membered heterocyclic ring containing a nitrogen atom.

Examples of the 3-to 6-membered heterocyclic ring include: nitrogen-containing heterocycles such as a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperazine ring, a thiomorpholine ring, a pyrrole ring, an imidazole ring, an imidazolidine ring, a pyrazolidine ring, and an isothiazolidine ring, and preferred examples thereof include nitrogen-containing aliphatic heterocycles having only one nitrogen atom as a heteroatom such as a pyrrolidine ring and a piperidine ring.

Preferably R¹～R⁶、R⁸、R¹⁰Each independently is a hydrogen atom, R⁷、R⁹Each independently is a hydrogen atom, a halogen atom, R¹¹～R¹⁶Each independently a saturated hydrocarbon group having 1 to 8 carbon atoms,

more preferably R¹～R⁶、R⁸、R¹⁰Each independently is a hydrogen atom, R⁷、R⁹Each independently being a halogen atom, R¹¹～R¹⁶Each independently is a saturated hydrocarbon group having 1 to 6 carbon atoms.

A^q-Is an anion having a valence of q, and is an anion having any one of valences 1 to 14.

That is, q represents 1 to 14, preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 3, and particularly preferably 1 or 2.

p represents a coefficient for keeping the charge neutral by the compound represented by the formula (I). Specifically, p is 1 to 14, preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 1 or 2.

Examples of the anion include: halide anions, other inorganic anions, organic carboxylate anions, organic sulfonate anions, organic phosphate anions, organic imide acid anion, organic methide acid anion, metal complex anions, and the like.

As halide anions, mention may be made of: chloride ions, bromide ions, iodide ions, fluoride ions, and the like.

As the inorganic anion, there can be mentioned: perchlorate ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion (hereinafter sometimes referred to as "anion (VII)"), hexafluoroantimonate ion, tetrafluoroborate ion, and the like.

Examples of the inorganic anion include anions containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom. From the viewpoint of heat resistance, an anion containing a tungsten atom and an oxygen atom is preferable.

As the anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom, there can be mentioned: alpha- [ PW₁₂O₄₀]^3-(hereinafter sometimes referred to as "anion (IX)") and the like; alpha- [ P ]₂W₁₈O₆₂]^6-、β-[P₂W₁₈O₆₂]^6-Wait for Dawson type phosphotungstic acid radical ion; alpha- [ SiW₁₂O₄₀]^4-、β-[SiW₁₂O₄₀]^4-、γ-[SiW₁₂O₄₀]^4-Waiting for Keggin type silicotungstic acid radical ions; [ P ]₂W₁₇O₆₁]^10-、[P₂W₁₅O₅₆]^12-、[H₂P₂W₁₂O₄₈]^12-、[NaP₅W₃₀O₁₁₀]^14-、α-[SiW₉O₃₄]^10-、γ-[SiW₁₀O₃₆]^8-、α-[SiW₁₁O₃₉]^8-、β-[SiW₁₁O₃₉]^8-；[W₆O₁₉]^2-、[W₁₀O₃₂]^4-、WO₄ ^2-Isopolyoxolate ions containing tungsten; silicate ions; phosphate ions, and the like.

Examples of the organic carboxylate anion include acetate ion.

As organic sulfonate anions, mention may be made of: methanesulfonate ion, dodecylsulfonate ion, benzenesulfonate ion, toluenesulfonate ion, naphthalenesulfonate ion, diphenylamine-4-sulfonate ion, 2-amino-4-methyl-5-chlorobenzenesulfonate ion, 2-amino-5-nitrobenzenesulfonate ion, phthalocyanine sulfonate ion, sulfonate ion having a polymerizable substituent, benzenedisulfonate anion, naphthalenedisulfonate anion, and the like.

As the organic phosphate anion, there can be mentioned: octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphonate ion, and the like.

The metal complex anion is an anion obtained by coordinating a molecule having a group capable of coordinating with a metal atom in the molecule with the metal atom.

Examples of the metal complex anion include anions derived from: c.i. solvent yellow 13, 19, 21, 25: 1. 62, 79, 81, 82, 83: 1. 88, 89, 90, 151, 161; c.i. solvent orange 5, 11, 20, 40: 1. 41, 45, 54, 56, 58, 62, 70, 81, 99; c.i. solvent red 8, 35, 83: 1. 84: 1. 90, 90: 1. 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243; c.i. solvent violet 2, 21: 1. 46, 49, 58, 61; c.i. solvent blue 137; c.i. solvent brown 28, 42, 43, 44, 53, 62, 63; c.i. acid yellow 59, 121; c.i. acid orange 74, 162; C.I. acid Red 211, and a metal complex dye described in Japanese patent application laid-open No. 2010-170117.

Examples of the molecule (ligand) include an azo molecule and a methine molecule, and an azo molecule is preferable.

Examples of the metal atom include: chromium, cobalt, nickel and the like, and preferably chromium and cobalt.

Specific examples of the metal complex anion include anions represented by the formula (VIII).

Wherein, as A^q-Preferably, the anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom, an organic carboxylate anion, an organic sulfonate anion, an organic imidic acid anion, an organic methide acid anion, a metal complex anion, and more preferably, the anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom, a metal complex anion.

Further, more preferred are a fluorine-containing organic carboxylate anion, a fluorine-containing organic sulfonate anion, a fluorine-containing organic imidic acid anion, and a fluorine-containing organic methide acid anion (hereinafter, these are also collectively referred to as a fluorine-containing anion).

Examples of the fluorine-containing anion include: CF (compact flash)₃CO₂ ^-And an anion represented by the formula (III), the formula (IV), the formula (V) or the formula (VI).

[ in the formula (III), W³And W⁴Independently represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W³And W⁴Together represent a carbon atom1 to 4 moles of fluorinated alkanediyl.]

[ in the formula (IV), W⁵～W⁷Independently represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.]

[ in the formula (V), Y¹Represents a fluorinated alkanediyl group having 1 to 4 carbon atoms.]

[ in the formula (VI), Y²Represents a fluorinated alkyl group having 1 to 4 carbon atoms.]

In the formulae (III), (IV) and (VI), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include: -CF₃、-CF₂CF₃、-CF₂CF₂CF₃、-CF(CF₃)₂、-CF₂CF₂CF₂CF₃、-CF₂CF(CF₃)₂、-C(CF₃)₃And the like.

In the formulae (III) and (V), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, and examples thereof include: -CF₂-、-CF₂CF₂-、-CF₂CF₂CF₂-、-C(CF₃)₂-、-CF₂CF₂CF₂CF₂-and the like.

As the anion represented by the formula (III) (hereinafter, sometimes referred to as "anion (III)"), anions represented by the formulae (III-1) to (III-6) (hereinafter, sometimes referred to as "anion (III-1)" to "anion (III-6)") can be each exemplified.

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

As the anion represented by the formula (V) (hereinafter sometimes referred to as "anion (V)"), anions represented by the formulae (V-1) to (V-4) (hereinafter sometimes referred to as "anion (V-1)" to "anion (V-4)") can be respectively exemplified.

As the anion represented by the formula (VI) (hereinafter sometimes referred to as "anion (VI)"), anions represented by the formulae (VI-1) to (VI-4) (hereinafter sometimes referred to as "anion (VI-1)" to "anion (VI-4)") can be mentioned, respectively.

The fluorine-containing anion may be at least one anion selected from the group consisting of: CF (compact flash)₃CO₂ ^-Anion (III), anion (IV), anion (V) and anion (VI). Among them, CF is preferable₃CO₂ ^-Anion (III-1), anion (III-2), anion (III-6), anion (IV-1), anion (V-1), anion (VI-2), anion (VI-3); more preferably CF₃CO₂ ^-Anion (III-2), anion (IV-1) and anion (VI-1).

The compound represented by the formula (I) is preferably a compound represented by the formula (I-A).

(in the formula (I-A),R⁷、R⁹、R¹¹～R¹⁶、p、q、A^q-the same as described above)

In the following tables 1 to 10, Me represents a methyl group, Et represents an ethyl group, Pro represents a propyl group, III-1 to III-6, V-1, V-2, VII, VIII, and IX represent anions represented by the above-mentioned formulae (III-1) to (III-6), an anion represented by the formula (V-1), an anion represented by the formula (V-2), an anion represented by the formula (VII), an anion represented by the formula (VIII), and an anion represented by the formula (IX).

The compound represented by the formula (I-A) is preferably a compound represented by the formula (I-1) to the formula (I-324).

[ Table 1]

R⁷

R⁹

R¹¹

R¹²

R¹³

R¹⁴

R¹⁵

R¹⁶

p

q

A^q-

(I-1)

H

Me

1

III-1

(I-2)

H

Cl

Me

1

III-1

(I-3)

Cl

H

Me

1

III-1

(I-4)

Cl

Me

1

III-1

(I-5)

H

Me

1

III-2

(I-6)

H

Cl

Me

1

III-2

(I-7)

Cl

H

Me

1

III-2

(I-8)

Cl

Me

1

III-2

(I-9)

H

Me

1

III-3

(I-10)

H

Cl

Me

1

III-3

(I-11)

Cl

H

Me

1

III-3

(I-12)

Cl

Me

1

III-3

(I-13)

H

Me

1

III-4

(I-14)

H

Cl

Me

1

III-4

(I-15)

Cl

H

Me

1

III-4

(I-16)

Cl

Me

1

III-4

(I-17)

H

Me

1

III-5

(I-18)

H

Cl

Me

1

III-5

(I-19)

Cl

H

Me

1

III-5

(I-20)

Cl

Me

1

III-5

(I-21)

H

Me

1

III-6

(I-22)

H

Cl

Me

1

III-6

(I-23)

Cl

H

Me

1

III-6

(I-24)

Cl

Me

1

III-6

(I-25)

H

Me

2

V-1

(I-26)

H

Cl

Me

2

V-1

(I-27)

Cl

H

Me

2

V-1

(I-28)

Cl

Me

2

V-1

(I-29)

H

Me

2

V-2

(I-30)

H

Cl

Me

2

V-2

(I-31)

Cl

H

Me

2

V-2

(I-32)

Cl

Me

2

V-2

[ Table 2]

R⁷

R⁹

R¹¹

R¹²

R¹³

R¹⁴

R¹⁵

R¹⁶

p

q

A^q-

(I-33)

H

Me

1

III-1

(I-34)

H

F

Me

1

III-1

(I-35)

F

H

Me

1

III-1

(I-36)

F

Me

1

III-1

(I-37)

H

Me

1

III-2

(I-38)

H

F

Me

1

III-2

(I-39)

F

H

Me

1

III-2

(I-40)

F

Me

1

III-2

(I-41)

H

Me

1

III-3

(I-42)

H

F

Me

1

III-3

(I-43)

F

H

Me

1

III-3

(I-44)

F

Me

1

III-3

(I-45)

H

Me

1

III-4

(I-46)

H

F

Me

1

III-4

(I-47)

F

H

Me

1

III-4

(I-48)

F

Me

1

III-4

(I-49)

H

Me

1

III-5

(I-50)

H

F

Me

1

III-5

(I-51)

F

H

Me

1

III-5

(I-52)

F

Me

1

III-5

(I-53)

H

Me

1

III-6

(I-54)

H

F

Me

1

III-6

(I-55)

F

H

Me

1

III-6

(I-56)

F

Me

1

III-6

(I-57)

H

Me

2

V-1

(I-58)

H

F

Me

2

V-1

(I-59)

F

H

Me

2

V-1

(I-60)

F

Me

2

V-1

(I-61)

H

Me

2

V-2

(I-62)

H

F

Me

2

V-2

(I-63)

F

H

Me

2

V-2

(I-64)

F

Me

2

V-2

[ Table 3]

R⁷

R⁹

R¹¹

R¹²

R¹³

R¹⁴

R¹⁵

R¹⁶

p

q

A^q-

(I-65)

H

Me

1

III-1

(I-66)

H

Br

Me

1

III-1

(I-67)

Br

H

Me

1

III-1

(I-68)

Br

Me

1

III-1

(I-69)

H

Me

1

III-2

(I-70)

H

Br

Me

1

III-2

(I-71)

Br

H

Me

1

III-2

(I-72)

Br

Me

1

III-2

(I-73)

H

Me

1

III-3

(I-74)

H

Br

Me

1

III-3

(I-75)

Br

H

Me

1

III-3

(I-76)

Br

Me

1

III-3

(I-77)

H

Me

1

III-4

(I-78)

H

Br

Me

1

III-4

(I-79)

Br

H

Me

1

III-4

(I-80)

Br

Me

1

III-4

(I-81)

H

Me

1

III-5

(I-82)

H

Br

Me

1

III-5

(I-83)

Br

H

Me

1

III-5

(I-84)

Br

Me

1

III-5

(I-85)

H

Me

1

III-6

(I-86)

H

Br

Me

1

III-6

(I-87)

Br

H

Me

1

III-6

(I-88)

Br

Me

1

III-6

(I-89)

H

Me

2

V-1

(I-90)

H

Br

Me

2

V-1

(I-91)

Br

H

Me

2

V-1

(I-92)

Br

Me

2

V-1

(I-93)

H

Me

2

V-2

(I-94)

H

Br

Me

2

V-2

(I-95)

Br

H

Me

2

V-2

(I-96)

Br

Me

2

V-2

[ Table 4]

R⁷

R⁹

R¹¹

R¹²

R¹³

R¹⁴

R¹⁵

R¹⁶

p

q

A^q-

(I-97)

H

Et

1

III-1

(I-98)

H

Cl

Et

1

III-1

(I-99)

Cl

H

Et

1

III-1

(I-100)

Cl

Et

1

III-1

(I-101)

H

Et

1

III-2

(I-102)

H

Cl

Et

1

III-2

(I-103)

Cl

H

Et

1

III-2

(I-104)

Cl

Et

1

III-2

(I-105)

H

Et

1

III-3

(I-106)

H

Cl

Et

1

III-3

(I-107)

Cl

H

Et

1

III-3

(I-108)

Cl

Et

1

III-3

(I-109)

H

Et

1

III-4

(I-110)

H

Cl

Et

1

III-4

(I-111)

Cl

H

Et

1

III-4

(I-112)

Cl

Et

1

III-4

(I-113)

H

Et

1

III-5

(I-114)

H

Cl

Et

1

III-5

(I-115)

Cl

H

Et

1

III-5

(I-116)

Cl

Et

1

III-5

(I-117)

H

Et

1

III-6

(I-118)

H

Cl

Et

1

III-6

(I-119)

Cl

H

Et

1

III-6

(I-120)

Cl

Et

1

III-6

(I-121)

H

Et

2

V-1

(I-122)

H

Cl

Et

2

V-1

(I-123)

Cl

H

Et

2

V-1

(I-124)

Cl

Et

2

V-1

(I-125)

H

Et

2

V-2

(I-126)

H

Cl

Et

2

V-2

(I-127)

Cl

H

Et

2

V-2

(I-128)

Cl

Et

2

V-2

[ Table 5]

R⁷

R⁹

R¹¹

R¹²

R¹³

R¹⁴

R¹⁵

R¹⁶

p

q

A^q-

(I-129)

H

Et

1

III-1

(I-130)

H

F

Et

1

III-1

(I-131)

F

H

Et

1

III-1

(I-132)

F

Et

1

III-1

(I-133)

H

Et

1

III-2

(I-134)

H

F

Et

1

III-2

(I-135)

F

H

Et

1

III-2

(I-136)

F

Et

1

III-2

(I-137)

H

Et

1

III-3

(I-138)

H

F

Et

1

III-3

(I-139)

F

H

Et

1

III-3

(I-140)

F

Et

1

III-3

(I-141)

H

Et

1

III-4

(I-142)

H

F

Et

1

III-4

(I-143)

F

H

Et

1

III-4

(I-144)

F

Et

1

III-4

(I-145)

H

Et

1

III-5

(I-146)

H

F

Et

1

III-5

(I-147)

F

H

Et

1

III-5

(I-148)

F

Et

1

III-5

(I-149)

H

Et

1

III-6

(I-150)

H

F

Et

1

III-6

(I-151)

F

H

Et

1

III-6

(I-152)

F

Et

1

III-6

(I-153)

H

Et

2

V-1

(I-154)

H

F

Et

2

V-1

(I-155)

F

H

Et

2

V-1

(I-156)

F

Et

2

V-1

(I-157)

H

Et

2

V-2

(I-158)

H

F

Et

2

V-2

(I-159)

F

H

Et

2

V-2

(I-160)

F

Et

2

V-2

[ Table 6]

R⁷

R⁹

R¹¹

R¹²

R¹³

R¹⁴

R¹⁵

R¹⁶

p

q

A^q-

(I-161)

H

Et

1

III-1

(I-162)

H

Br

Et

1

III-1

(I-163)

Br

H

Et

1

III-1

(I-164)

Br

Et

1

III-1

(I-165)

H

Et

1

III-2

(I-166)

H

Br

Et

1

III-2

(I-167)

Br

H

Et

1

III-2

(I-168)

Br

Et

1

III-2

(I-169)

H

Et

1

III-3

(I-170)

H

Br

Et

1

III-3

(I-171)

Br

H

Et

1

III-3

(I-172)

Br

Et

1

III-3

(I-173)

H

Et

1

III-4

(I-174)

H

Br

Et

1

III-4

(I-175)

Br

H

Et

1

III-4

(I-176)

Br

Et

1

III-4

(I-177)

H

Et

1

III-5

(I-178)

H

Br

Et

1

III-5

(I-179)

Br

H

Et

1

III-5

(I-180)

Br

Et

1

III-5

(I-181)

H

Et

1

III-6

(I-182)

H

Br

Et

1

III-6

(I-183)

Br

H

Et

1

III-6

(I-184)

Br

Et

1

III-6

(I-185)

H

Et

2

V-1

(I-186)

H

Br

Et

2

V-1

(I-187)

Br

H

Et

2

V-1

(I-188)

Br

Et

2

V-1

(I-189)

H

Et

2

V-2

(I-190)

H

Br

Et

2

V-2

(I-191)

Br

H

Et

2

V-2

(I-192)

Br

Et

2

V-2

[ Table 7]

R⁷

R⁹

R¹¹

R¹²

R¹³

R¹⁴

R¹⁵

R¹⁶

p

q

A^q-

(I-193)

H

Pro

1

III-1

(I-194)

H

Cl

Pro

1

III-1

(I-195)

Cl

H

Pro

1

III-1

(I-196)

Cl

Pro

1

III-1

(I-197)

H

Pro

1

III-2

(I-198)

H

Cl

Pro

1

III-2

(I-199)

Cl

H

Pro

1

III-2

(I-200)

Cl

Pro

1

III-2

(I-201)

H

Pro

1

III-3

(I-202)

H

Cl

Pro

1

III-3

(I-203)

Cl

H

Pro

1

III-3

(I-204)

Cl

Pro

1

III-3

(I-205)

H

Pro

1

III-4

(I-206)

H

Cl

Pro

1

III-4

(I-207)

Cl

H

Pro

1

III-4

(I-208)

Cl

Pro

1

III-4

(I-209)

H

Pro

1

III-5

(I-210)

H

Cl

Pro

1

III-5

(I-211)

Cl

H

Pro

1

III-5

(I-212)

Cl

Pro

1

III-5

(I-213)

H

Pro

1

III-6

(I-214)

H

Cl

Pro

1

III-6

(I-215)

Cl

H

Pro

1

III-6

(I-216)

Cl

Pro

1

III-6

(I-217)

H

Pro

2

V-1

(I-218)

H

Cl

Pro

2

V-1

(I-219)

Cl

H

Pro

2

V-1

(I-220)

Cl

Pro

2

V-1

(I-221)

H

Pro

2

V-2

(I-222)

H

Cl

Pro

2

V-2

(I-223)

Cl

H

Pro

2

V-2

(I-224)

Cl

Pro

2

V-2

[ Table 8]

R⁷

R⁹

R¹¹

R¹²

R¹³

R¹⁴

R¹⁵

R¹⁶

p

q

A^q-

(I-225)

H

Pro

1

III-1

(I-226)

H

F

Pro

1

III-1

(I-227)

F

H

Pro

1

III-1

(I-228)

F

Pro

1

III-1

(I-229)

H

Pro

1

III-2

(I-230)

H

F

Pro

1

III-2

(I-231)

F

H

Pro

1

III-2

(I-232)

F

Pro

1

III-2

(I-233)

H

Pro

1

III-3

(I-234)

H

F

Pro

1

III-3

(I-235)

F

H

Pro

1

III-3

(I-236)

F

Pro

1

III-3

(I-237)

H

Pro

1

III-4

(I-238)

H

F

Pro

1

III-4

(I-239)

F

H

Pro

1

III-4

(I-240)

F

Pro

1

III-4

(I-241)

H

Pro

1

III-5

(I-242)

H

F

Pro

1

III-5

(I-243)

F

H

Pro

1

III-5

(I-244)

F

Pro

1

III-5

(I-245)

H

Pro

1

III-6

(I-246)

H

F

Pro

1

III-6

(I-247)

F

H

Pro

1

III-6

(I-248)

F

Pro

1

III-6

(I-249)

H

Pro

2

V-1

(I-250)

H

F

Pro

2

V-1

(I-251)

F

H

Pro

2

V-1

(I-252)

F

Pro

2

V-1

(I-253)

H

Pro

2

V-2

(I-254)

H

F

Pro

2

V-2

(I-255)

F

H

Pro

2

V-2

(I-256)

F

Pro

2

V-2

[ Table 9]

R⁷

R⁹

R¹¹

R¹²

R¹³

R¹⁴

R¹⁵

R¹⁶

p

q

A^q-

(I-257)

H

Pro

1

III-1

(I-258)

H

Br

Pro

1

III-1

(I-259)

Br

H

Pro

1

III-1

(I-260)

Br

Pro

1

III-1

(I-261)

H

Pro

1

III-2

(I-262)

H

Br

Pro

1

III-2

(I-263)

Br

H

Pro

1

III-2

(I-264)

Br

Pro

1

III-2

(I-265)

H

Pro

1

III-3

(I-266)

H

Br

Pro

1

III-3

(I-267)

Br

H

Pro

1

III-3

(I-268)

Br

Pro

1

III-3

(I-269)

H

Pro

1

III-4

(I-270)

H

Br

Pro

1

III-4

(I-271)

Br

H

Pro

1

III-4

(I-272)

Br

Pro

1

III-4

(I-273)

H

Pro

1

III-5

(I-274)

H

Br

Pro

1

III-5

(I-275)

Br

H

Pro

1

III-5

(I-276)

Br

Pro

1

III-5

(I-277)

H

Pro

1

III-6

(I-278)

H

Br

Pro

1

III-6

(I-279)

Br

H

Pro

1

III-6

(I-280)

Br

Pro

1

III-6

(I-281)

H

Pro

2

V-1

(I-282)

H

Br

Pro

2

V-1

(I-283)

Br

H

Pro

2

V-1

(I-284)

Br

Pro

2

V-1

(I-285)

H

Pro

2

V-2

(I-286)

H

Br

Pro

2

V-2

(I-287)

Br

H

Pro

2

V-2

(I-288)

Br

Pro

2

V-2

[ Table 10]

R⁷

R⁹

R¹¹

R¹²

R¹³

R¹⁴

R¹⁵

R¹⁶

p

q

A^q-

(I-289)

H

Me

1

VII

(I-290)

H

Cl

Me

1

VII

(I-291)

Cl

H

Me

1

VII

(I-292)

Cl

Me

1

VII

(I-293)

H

Me

1

VIII

(I-294)

H

Cl

Me

1

VIII

(I-295)

Cl

H

Me

1

VIII

(I-296)

Cl

Me

1

VIII

(I-297)

H

Me

3

IX

(I-298)

H

Cl

Me

3

IX

(I-299)

Cl

H

Me

3

IX

(I-300)

Cl

Me

3

IX

(I-301)

H

Et

1

VII

(I-302)

H

Cl

Et

1

VII

(I-303)

Cl

H

Et

1

VII

(I-304)

Cl

Et

1

VII

(I-305)

H

Et

1

VIII

(I-306)

H

Cl

Et

1

VIII

(I-307)

Cl

H

Et

1

VIII

(I-308)

Cl

Et

1

VIII

(I-309)

H

Et

3

IX

(I-310)

H

Cl

Et

3

IX

(I-311)

Cl

H

Et

3

IX

(I-312)

Cl

Et

3

IX

(I-313)

H

Pro

1

VII

(I-314)

H

Cl

Pro

1

VII

(I-315)

Cl

H

Pro

1

VII

(I-316)

Cl

Pro

1

VII

(I-317)

H

Pro

1

VIII

(I-318)

H

Cl

Pro

1

VIII

(I-319)

Cl

H

Pro

1

VIII

(I-320)

Cl

Pro

1

VIII

(I-321)

H

Pro

3

IX

(I-322)

H

Cl

Pro

3

IX

(I-323)

Cl

H

Pro

3

IX

(I-324)

Cl

Pro

3

IX

Among them, preferred are compounds represented by the formulae (I-97) to (I-192) and compounds represented by the formulae (I-289) to (I-324); more preferably compounds represented by the formulae (I-97) to (I-128) and compounds represented by the formulae (I-289) to (I-324); more preferably compounds represented by the formulae (I-97) to (I-120), compounds represented by the formulae (I-289) to (I-324); particularly preferred are compounds represented by the formula (I-104), compounds represented by the formula (I-308) and compounds represented by the formula (I-312).

The compound represented by formula (I) can be produced, for example, by the method described in international publication No. 2014/196464.

The content of the compound represented by formula (I) is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 40% by mass or less, and still more preferably 3% by mass or more and 30% by mass or less, relative to the total amount of the colorant.

The content of the compound represented by formula (I) is preferably 0.2% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and still more preferably 1% by mass or more and 12% by mass or less, based on the total solid content.

The "total solid content" in the present specification means an amount obtained by removing the solvent content from the total amount of the colored curable resin composition. The total solid content and the content of each component relative to the total solid content can be measured by a known analysis device such as a liquid chromatography or a gas chromatography.

< Red pigment >

As The red pigment contained in The colored curable resin composition of The present invention, known pigments can be used, and examples thereof include compounds classified into red among pigments classified into pigments (pigments) in The color Index (color Index) (published by The Society of Dyers and Colourists). Two or more kinds may be combined. However, the compound represented by the formula (I) is excluded.

Specifically, there may be mentioned: pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and the like.

Among the red pigments, anthraquinone pigments, azo pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments are preferable; preferably c.i. pigment red 177, 179, 202, 208, 242, 254, 269, brominated diketopyrrolopyrrole pigment; more preferred are c.i. pigment red 177, 202, 254, 269, brominated diketopyrrolopyrrole pigments.

The content of the red pigment is 1 mass% or more and 95 mass% or less, preferably 30 mass% or more and 95 mass% or less, more preferably 40 mass% or more and 90 mass% or less, further preferably 50 mass% or more, and further more preferably 60 mass% or more, based on the total amount of the colorant.

Instead of forming RGB from a white Light Emitting layer via a color filter, forming an OLED (Organic Light Emitting Diode) by laminating pixels of RGB on a substrate and forming RGB separately from each pixel directly, coating RGB, the content of a red pigment is, for example, 1 mass% or more and 95 mass% or less (preferably 1 mass% or more and less than 30 mass%) when the OLED is used as a Light source, a red colored coating film having excellent Light resistance can be obtained.

The total content of the compound represented by formula (I) and the red pigment is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 100% by mass or less, based on the total amount of the colorant.

When the colored curable resin composition of the present invention contains the colorant (a1) described later, the total content of the compound represented by formula (I) and the red pigment is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less, relative to the total amount of the colorant.

The content of the red pigment is preferably 0.1 mass% or more and 30 mass% or less, and more preferably 1 mass% or more and 20 mass% or less, based on the total solid content.

The colored curable resin composition of the present invention may contain, as the colorant (a), a compound represented by formula (I) and a colorant other than a red pigment (hereinafter, sometimes referred to as a colorant (a 1)). The colorant (a1) may contain one or two or more colorants.

The colorant (A1) may be a dye or a pigment. Examples of the dye include known dyes described in color index (published by dyers' society) and dyeing manual (color dyeing company). In addition, depending on the chemical structure, there may be mentioned: azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes (except for the compounds represented by formula (I)), cyanine dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, and the like. Among them, organic solvent-soluble dyes are preferable. Two or more of these dyes may be used in combination.

Specifically, the following color index (c.i.) numbered dyes are listed.

C.i. solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

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. reactive yellow 2, 76, 116;

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. disperse yellow 51, 54, 76;

c.i. solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

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. reactive orange 16;

c.i. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

c.i. solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

c.i. acid red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;

c.i. acid violet 34, 102;

c.i. disperse violet 26, 27;

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

c.i. solvent blue 14, 18, 35, 36, 45, 58, 59: 1. 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

c.i. acid blue 25, 27, 40, 45, 78, 80, 112;

c.i. direct blue 40;

c.i. disperse blue 1, 14, 56, 60;

c.i. solvent green 1,3,5, 28, 29, 32, 33;

c.i. acid green 3,5, 9, 25, 27, 28, 41;

c.i. alkaline green 1;

c.i. vat green 1, etc.

As the pigment, a known pigment can be used, and for example, a pigment classified as a pigment in color index (published by association of dyers) can be cited. Two or more kinds may be combined. However, the compound represented by the formula (I) is excluded.

Specifically, there may be mentioned: c.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and the like;

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

c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60, etc. blue pigments;

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

c.i. pigment green 7, 36, 58, 59 and the like.

The colorant (a1) is preferably a yellow pigment, and more preferably c.i. pigment yellow 138, 139, 150, 185, 231.

When the yellow pigment is contained, the content thereof is preferably 1% by mass or more and 50% by mass or less, and more preferably 3% by mass or more and 45% by mass or less, with respect to the total amount of the colorant.

The content of the yellow pigment is preferably 0.2 mass% or more and 25 mass% or less, and more preferably 0.6 mass% or more and 20 mass% or less, based on the total solid content.

The compound represented by the formula (I), the red pigment and the pigment (hereinafter, sometimes referred to as a pigment or the like) in the colorant (a1) may be subjected to the following treatment as needed: rosin treatment, surface treatment using a colorant derivative or the like into which an acidic group or a basic group is introduced, grafting treatment on the surface of a pigment or the like with a polymer compound or the like, microparticulation treatment with a sulfuric acid microparticulation method or the like, cleaning treatment with an organic solvent or water or the like for removing impurities, removal treatment with an ionic impurity such as an ion exchange method, and the like. The particle diameters of the pigment and the like are preferably substantially uniform. The pigment or the like is dispersed uniformly in the dispersion liquid by adding a dispersant and performing dispersion treatment.

The dispersant may be a surfactant or the like, and may be any of cationic, anionic, nonionic and amphoteric surfactants. Specifically, surfactants such as polyester, polyamine, and acrylic surfactants are included. As the other dispersant, the resin (B) described later can be used. These dispersants may be used alone or in combination of two or more. As the dispersant, when it is expressed by a trade name, there are listed: KP (manufactured by shin-Etsu chemical industries, Ltd.), flowen (manufactured by Kyoho chemical industries, Ltd.), Solsperse (registered trademark) (manufactured by Jielikang (Zeneca), EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-technique) (manufactured by Ltd.), Disperbyk (registered trademark) (manufactured by ByK-Chemie), BYK (registered trademark) (manufactured by Bikk chemical Co., Ltd.), and the like.

When the dispersant is used, the amount of the dispersant used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the pigment or the like. When the amount of the dispersant used is within the above range, a more uniformly dispersed solution containing the colorant tends to be obtained.

In the colored curable resin composition, the content of the colorant (a) is usually 10% by mass or more and 60% by mass or less, preferably 12% by mass or more and 55% by mass or less, and more preferably 15% by mass or more and 50% by mass or less in the total solid content.

< resin (B) >

The resin (B) is not particularly limited, and is preferably an alkali-soluble resin, and more preferably a resin having a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. The resin (B) further preferably has at least one structural unit selected from the group consisting of the structural units wherein the structural unit is: a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, a structural unit derived from a monomer (c) (different from (a) and (b)) (hereinafter sometimes referred to as "(c)") copolymerizable with (a), and a structural unit having an ethylenically unsaturated bond in a side chain.

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, and mono [ 2- (meth) acryloyloxyethyl ] succinate, with acrylic acid, methacrylic acid, and maleic anhydride being preferred.

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

(b) Preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth) acryloyloxy group.

Examples of (b) include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, and 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester, 3-ethyl-3- (meth) acryloyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate, etc., preferably glycidyl (meth) acrylate, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester, 3-ethyl-3- (meth) acryloyloxymethyl oxetane.

Examples of (c) include methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [ meth ] acrylate5.2.1.0^2,6]Decane-8-yl ester, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like, and preferably styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like.

The resin having a structural unit having an ethylenically unsaturated bond in a side chain can be produced by adding (b) to the copolymer of (a) and (c) or adding (a) to the copolymer of (b) and (c). The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting a carboxylic acid anhydride.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000.

The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170mg-KOH/g, more preferably 60 to 150mg-KOH/g, and still more preferably 70 to 135mg-KOH/g in terms of solid content. The acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be determined, for example, by titration using an aqueous solution of potassium hydroxide.

The content of the resin (B) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 17 to 40% by mass, based on the total solid content.

< polymerizable Compound (C) >)

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include: trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, and still more preferably 11 to 40% by mass, based on the total solid content.

< polymerization initiator (D) >)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates active radicals include: n-benzoyloxy-1- (4-phenylsulfonylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfonylphenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfonylphenyl) -3-cyclopentylpropane-1-one-2-imine, 2-methyl-2-morpholino-1- (4-methylsulfonylphenyl) propane-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 1-hydroxycyclohexylphenylone, N-benzoyloxy-1- (4-phenylsulfonylphenyl) octan-1-one, N-benzoyloxy-2-methyl-1- (4-phenylsulfonylphenyl) propane-1-one, N-methyl-2-methyl-1-amino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, N-ethylcarbonyloxy-1- (4-phenylsulfonylphenyl) octan-1-one, N-2-cyclopentylphenyloxy-imine, N-1-methylo-1-one, N-methyl-2-carbonyloxy-2-imine, N-methyl-1-morpholinophenyl-1-one, N-2-one, N-methyl-one, N-one, N-benzoyloxy-1-one, N-one, N-one, N-one, N-1-2-N, N-one, N-N, N-one, N-2-N-2-one, N-2-one, N-1-one, N-N, N-one, N-2-N, N-N, N-2-1-2-N, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbenzimidazole and the like.

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

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be short, so that the productivity of the color filter tends to be improved.

The content of the O-acyloxime compound is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total amount of the polymerization initiator (D). When the content of the O-acyloxime compound is within the above range, the following tendency is exhibited: the color filter has excellent sensitivity and developing property when forming a colored pattern, and can manufacture a color filter with high brightness even if the content of the colorant is high.

The colored curable resin composition of the present invention may also contain a polymerization initiation aid.

< polymerization initiation assistant (D1) >)

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

Examples of the polymerization initiation aid (D1) include: 4,4' -bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4' -bis (diethylamino) benzophenone, 9, 10-dimethoxyanthracene, 2, 4-diethylthioxanthone (2,4-diethyl thioxanthone), N-phenylglycine, and the like.

When the polymerization initiator aid (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiator aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

The colored curable resin composition of the present invention preferably contains a solvent.

< solvent (E) >

The solvent (E) is not particularly limited, and a solvent generally used in the art may be used. Examples thereof include: an ester solvent (a solvent containing-COO-and not-O-in the molecule), an ether solvent (a solvent containing-O-and not-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and not-O-in the molecule), a ketone solvent (a solvent containing-CO-and not-COO-in the molecule), an alcohol solvent (a solvent containing OH and not-O-, -CO-, and-COO-, in the molecule), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, and the like.

Examples of the solvent include: ester solvents (solvents containing-COO-in the molecule and not containing-O-) such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone; ether solvents (solvents containing-O-in the molecule and not containing-COO-) such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, etc.;

ether ester solvents (solvents containing-COO-and-O-in the molecule) such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate;

ketone solvents (solvents containing-CO-in the molecule and not containing-COO-) such as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, and cyclohexanone; alcohol solvents such as butanol, cyclohexanol and propylene glycol (solvents containing OH in the molecule and not containing-O-, -CO-and-COO-), and the like. Examples thereof include aromatic hydrocarbon solvents such as benzene, toluene, xylene and mesitylene.

Examples thereof include amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

The solvent is more preferably diacetone alcohol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone, and ethyl 3-ethoxypropionate.

The solvent is preferably a mixed solvent containing propylene glycol monomethyl ether acetate. Preferred solvents to be combined with propylene glycol monomethyl ether acetate are diacetone alcohol, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and 4-hydroxy-4-methyl-2-pentanone; more preferably diacetone alcohol, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate; further preferred are diacetone alcohol, ethyl lactate, 4-hydroxy-4-methyl-2-pentanone and propylene glycol monomethyl ether.

The content of the solvent in combination with propylene glycol monomethyl ether acetate is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 40% by mass or less, and still more preferably 5% by mass or more and 30% by mass or less, based on the total amount of the solvent.

When the solvent (E) is contained, the content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density does not become insufficient at the time of forming a color filter, so that the display characteristics tend to become good.

< other ingredients >

The colored curable resin composition of the present invention may optionally contain additives known in the art, such as a leveling agent, a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent.

< method for producing colored curable resin composition >

The colored curable resin composition of the present invention can be prepared by mixing the colorant (a), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the solvent (E) if necessary, and other components.

< method for manufacturing color filter >

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include photolithography, ink jet printing, and printing. Among them, photolithography is preferable. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and/or without performing development at the time of exposure. The colored pattern or the colored coating film thus formed is the color filter of the present invention.

The colored curable resin composition of the present invention can produce a color filter having excellent brightness. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL (electroluminescence) device, electronic paper, or the like) or a solid-state imaging device.

Modes for carrying out the invention

Hereinafter, the colored curable resin composition of the present invention will be described in more detail with reference to examples. In the examples, "%" and "part" are% by mass and part by mass unless otherwise specified.

In the following synthesis examples, compounds were identified by MASS analysis (LC; MASS model 1200 manufactured by Agilent; LC/MSD model manufactured by Agilent) or elemental analysis (VARIO-EL; manufactured by Eimeria (Elementar Co., Ltd.)).

Synthesis example 1

Bis (trifluoromethanesulfonyl) imide ((CF)₃SO₂)₂N^-) Synthesis of salts

12.5 parts of compound S-represented by the following formula, 2.5 parts of diethylaminophenol, and 3.3 parts of sulfuric acid were mixed and stirred at 140 ℃ for 8 hours. The reaction solution was added dropwise to an aqueous sodium hydroxide solution, and the organic matter was extracted with toluene and washed with water 3 times, after which the solvent was distilled off from the organic layer. The residue was purified by silica gel column chromatography (developing solvent: chloroform) to obtain 2.7 parts of colorless substance (leuco form) (yield 52%).

27 parts of the colorless substance, 184.4 parts of p-chloranil (p-chloranil), 15 parts of acetic acid and 0.9 part of hydrochloric acid were mixed and stirred at 60 ℃ for 1 hour. The solid was separated and removed by filtration, chloroform was added to the filtrate, and the aqueous layer was neutralized with an aqueous sodium bicarbonate solution. 1.4 parts of potassium bis (trifluoromethanesulfonyl) imide was added and subjected to salt exchange, and then washed with water to distill off the solvent from the organic layer. The residue was purified by silica gel column chromatography (developing solvent: chloroform: ethyl acetate ═ 1: 1) to obtain 11.5 parts of the compound represented by formula (I-X) (compound represented by formula (I-104)) (yield 27%).

Synthesis example 2

Synthesis of hydrochloride

4.0 parts of the colorless substance, 3.2 parts of p-chloranil, and 19.4 parts of acetonitrile were mixed and stirred at room temperature for 12 hours. Chloroform was added, the precipitated solid was separated by filtration and removed, the organic layer was washed with water, sodium sulfate was added thereto and dried, and then the solvent was distilled off. 200 parts of concentrated hydrochloric acid was added thereto and stirred for 6 hours, and then added dropwise to 600 parts of 10% saline solution and stirred overnight. The precipitated solid was collected by filtration, and a 5% aqueous sodium hydroxide solution was added to the filtrate to neutralize the solution to a pH of 4, and the precipitated solid was collected by filtration. All the solids were dispersion-washed with water, and after filtration, the solids were dried in a reduced-pressure oven at 60 ℃ to obtain 4.1 parts (yield 95%) of the compound represented by the formula (I-XI).

Synthesis example 3

Synthesis of phosphotungstate

A solution of 30.1 parts of phosphotungstic acid hydrate (SIGMA ALDRICH (SIGMA-ALDRICH)) and 30.5 parts of methanol was added dropwise while mixing 3.00 parts of the compound (the compound represented by formula (I-XI)) and 515 parts of methanol at room temperature, followed by stirring for 3 hours. The precipitated solid was collected by filtration, washed with 50.0 parts of methanol for 3 times, and dried in a reduced-pressure oven at 60 ℃ to obtain 10.6 parts of the compound represented by the formula (I-312) (yield 60%).

Synthesis example 4

Synthesis of solvent yellow 21 salt

0.20 part of a compound (a compound represented by the formula (I-XI)), 210.11 parts of a solvent yellow, and 4.8 parts of N, N-dimethyl sulfoxide were mixed and stirred at 50 ℃ for 3 hours. The reaction mixture was added dropwise to 40 parts of 20% saline solution, and the precipitated solid was collected by filtration. The solid was dissolved in chloroform, and the organic layer was washed with water, then sodium sulfate was added thereto and dried, and the solvent was distilled off. Drying was performed in a reduced-pressure oven at 60 ℃ to obtain 0.43 part (yield 85%) of the compound represented by the formula (I-308).

Synthesis example 5

174 parts of t-amyl alcohol were reacted with 22.2 parts of sodium metal at 130 ℃ under a nitrogen atmosphere to synthesize sodium t-amyl alcohol. This was heated to 60 ℃ and 91.0 parts of 4-bromobenzonitrile, 71.05 parts of di-tert-amyl succinate and 108.9 parts of tert-amyl alcohol were added thereto, and the mixture was stirred for 2 hours at a liquid temperature of 85 ℃ or lower. The suspension was further stirred for 18 hours or more, and then added to a mixed solution of 200 parts of methanol, 1000 parts of water and 49.21 parts of sulfuric acid, which was cooled to-10 ℃. After the addition of the suspension was completed, the reaction was terminated by keeping at 0 ℃ and stirring for 5 hours, and then the solid component was filtered. The solid was washed with methanol and water alternately and repeatedly until the filtrate was no longer colored and the salt was no longer precipitated. Thereafter, the solid content was dried for 18 hours by a vacuum drier at 80 ℃ to obtain the objective red pigment 1. The yield was 107 parts.

Synthesis example 6

An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and replaced with a nitrogen atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added thereto and heated to 85 ℃ while stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over a period of 5 hours^2,6]Decyl-8-yl ester with 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid^2,6]25 parts of mixture of decyl-9-yl ester (content ratio is 1: 1), 137 parts of cyclohexyl maleimide and methyl50 parts of 2-hydroxyethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution of 5 parts of 2, 2-azobisisobutyronitrile dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was held at this temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a solid content of 25.6%. The weight-average molecular weight Mw of the resulting copolymer was 8000, the degree of dispersion was 2.1, and the acid value in terms of solid content was 111 mg-KOH/g. The resin (B-1) has the following structural unit.

(Unit of resin (B-1))

Synthesis example 7

An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ℃ while stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise to the flask using a dropping pump over about 5 hours^2,6]Decan-8-yl ester with 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid^2,6]A mixture of decane-9-yl ester (content: 1)289 parts by weight was dissolved in 125 parts by weight of propylene glycol monomethyl ether acetate. On the other hand, a solution obtained by dissolving 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator in 235 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over about 6 hours using another dropping pump. After completion of the dropwise addition, the mixture was held at this temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) solution having a solid content of 35.1%. The weight-average molecular weight Mw of the resulting copolymer was 9200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. The resin (B-2) has the following structural unit.

(Unit of resin (B-2))

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

The device comprises the following steps: k2479 (manufactured by Shimadzu corporation)

Column: shimadzu Shim GPC-80M

Column temperature: 40 deg.C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

A detector: RI (Ri)

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

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

[ preparation of Dispersion 1(Br-DPP) ]

28 parts of red pigment 1 compound, 10 parts of a dispersant (BYKLPN-6919, manufactured by Bick corporation, in terms of solid content), 8 parts of resin (B-2) (in terms of solid content), and 154 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour by using a paint shaker (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion 1.

[ preparation of Dispersion 2(Y138) ]

13824 parts of C.I. pigment yellow, 11 parts of a dispersant (BYKLPN-6919 (manufactured by Bikk Co., Ltd., conversion of solid content)), 5 parts of a resin (B-2) (conversion of solid content), and 160 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of zirconia beads having a particle size of 0.4 μm were added, and the mixture was shaken for 1 hour by using a paint shaker (manufactured by LAU Co., Ltd.). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion 2.

[ preparation of Dispersion 3(Y231) ]

C.i. pigment yellow 23124 parts, a dispersant (BYKLPN-6919 manufactured by bike corporation, in solid content conversion) 11 parts, a resin (B-2) (in solid content conversion) 5 parts, and propylene glycol monomethyl ether acetate 160 parts were mixed, and then 600 parts of zirconia beads having a diameter of 0.4 μm were added thereto, followed by shaking for 1 hour using a paint conditioner (manufactured by LAU corporation). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion 3.

[ preparation of Dispersion 4(Y185) ]

C.I. pigment yellow 18520 parts, a dispersant (BYKLPN-6919, manufactured by Bikk corporation, in terms of solid content) 11 parts, a resin (B-2) (in terms of solid content) 5 parts, and propylene glycol monomethyl ether acetate 160 parts were mixed, and then 600 parts of 0.4 μm zirconia beads were added thereto, followed by shaking for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion 4.

[ preparation of Dispersion 5(R177) ]

C.I. pigment Red 17726 parts, a dispersant (BYKLPN-6919, manufactured by Bike corporation, in terms of solid content) 7 parts, a resin (B-2) (in terms of solid content) 10 parts, and propylene glycol monomethyl ether acetate 157 parts were mixed, and then 600 parts of zirconia beads having a particle size of 0.4 μm were added thereto, followed by shaking for 1 hour using a paint shaker (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion 5.

[ preparation of Dispersion 6(R269) ]

26926 parts of C.I. pigment Red, 11 parts of a dispersant (BYKLPN-6919 manufactured by Bikk, converted to solid content), and 164 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour by using a paint shaker (manufactured by LAU, Inc.). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion liquid 6.

[ preparation of Dispersion 7(R254) ]

25430 parts of C.I. pigment Red, 6 parts of a dispersant (BYKLPN-6919 (manufactured by Bikk Co., Ltd., in terms of solid content)), 14 parts of a resin (B-2) (in terms of solid content), and 150 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour by using a paint shaker (manufactured by LAU Co., Ltd.). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion 7.

[ preparation of Dispersion 8(Y139) ]

13924 parts of C.I. pigment yellow, 8 parts of a dispersant (BYKLPN-6919, manufactured by Bikk Co., Ltd., in terms of solid content), 8 parts of a resin (B-2) (in terms of solid content), 10 parts of propylene glycol monomethyl ether, and 150 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour by using a paint shaker (manufactured by LAU Co., Ltd.). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion 8.

[ preparation of Dispersion 9(D2428-PWA I-312) ]

10 parts of compound (I-312), 12 parts of a dispersant (BYKLPN-6919, manufactured by Bikk Co., Ltd., in terms of solid content), 8 parts of resin (B-2) (in terms of solid content), 20 parts of diacetone alcohol, and 150 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour by using a paint shaker (manufactured by LAU Co., Ltd.). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion 9.

[ preparation of Dispersion 10(R202) ]

C.i. pigment red 20224 parts, a dispersant (BYKLPN-6919 manufactured by bike corporation, in solid content conversion) 11 parts, a resin (B-2) (in solid content conversion) 8 parts, propylene glycol monomethyl ether 20 parts, and propylene glycol monomethyl ether acetate 136 parts were mixed, and then 600 parts of zirconia beads having a diameter of 0.4 μm were added, followed by shaking for 1 hour using a paint shaker (manufactured by LAU corporation). Thereafter, the zirconia beads were removed by filtration to obtain a dispersion 10.

[ examples 1 to 10, comparative examples 1 to 2]

[ preparation of colored curable resin composition ]

Each of the colored curable resin compositions was obtained by mixing the components shown in tables 11 and 12.

[ Table 11]

[ Table 12]

Resin (B-1): resin B-1 (conversion of solid content)

Polymerizable compound (C-1): dipentaerythritol hexaacrylate (manufactured by NONGZHONGvillage chemical industry Co., Ltd. "A9550", converted in terms of solid content)

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

Solvent (E-1): propylene glycol monomethyl ether acetate

Solvent (E-2): diacetone alcohol

Solvent (E-3): lactic acid ethyl ester

Leveling agent (F-1): polyether-modified Silicone oil (solid content conversion) (Toray Silicone SH 8400; manufactured by Toray Corning Co., Ltd.)

< production of color Filter (colored coating film) >

A curable color resin composition was applied to a 5cm square glass substrate (eagle 2000; manufactured by Corning corporation) by spin coating, and then prebaked at 100 ℃ for 3 minutes to form a color composition layer. After left to cool, the resultant was exposed to 60mJ/cm in an atmospheric air using an exposure machine (TME-150 RSK; manufactured by Topcon, Ltd.)²The exposure amount (365nm basis) of (b) is irradiated with light to the colored composition layer. Thereafter, post-baking was performed at 230 ℃ for 20 minutes in an oven, to obtain a color filter.

[ measurement of film thickness ]

The obtained color filter was measured for film thickness using a film thickness measuring apparatus (DEKTAK 3; manufactured by Japan vacuum technology Co., Ltd.). The results are shown in Table 13.

[ evaluation of color ]

The obtained color filter was measured for spectral components using a colorimeter (OSP-SP-200; manufactured by Olympus, ltd.) and for xy chromaticity coordinates (x, Y) and stimulus value Y in the XYZ color system of CIE (International Commission on Illumination) using an isochromatic function of a C light source. A larger value of Y indicates a higher luminance. The results are shown in Table 13.

< evaluation of light resistance >

An ultraviolet cut filter (color OPTICAL GLASS (L38; manufactured by HOYA corporation; cut off light of 380nm or less) was placed on the obtained COLORED coating film, and a xenon lamp light was irradiated on a light resistance tester (SUNTEST GPS +; manufactured by toyoyo seiki) for 48 hours.

Xy chromaticity coordinates (x, Y) and Y were measured before and after irradiation, and from the measured values, the x chromaticity coordinates were measured by JIS Z8730: 2009(7. method for calculating color difference) the color difference Δ Eab was calculated by the method described above, and the results are shown in table 14. Smaller Δ Eab means smaller color change. Further, when the light resistance of the colored coating film is good, it is considered that the light resistance of a colored pattern made of the same colored curable resin composition is also good.

[ Table 13]

	Film thickness (mum)	x	y	Y
					Example 1	2.0	0.679	0.313	14.3
Example 2	2.3	0.679	0.313	14.1
					Example 3	2.0	0.679	0.317	14.6
Example 4	1.7	0.679	0.317	13.8
					Example 5	1.7	0.679	0.317	13.8
Example 6	1.9	0.679	0.314	13.8
					Example 7	2.1	0.679	0.313	14.2
Example 8	2.3	0.679	0.315	14.2
					Example 9	3.3	0.679	0.320	14.9
Comparative example 1	4.3	0.679	0.261	2.7

[ Table 14]

	ΔEab*
		Example 10	17.1
Comparative example 2	21.3

Industrial applicability

According to the colored curable resin composition of the present invention, a color filter having excellent brightness can be formed. The colored curable resin composition of the present invention can form a color filter having excellent light resistance.

Claims

1. A colored curable resin composition comprising: a colorant, a resin, a polymerizable compound and a polymerization initiator,

the colorant comprises a compound represented by the formula (I) and a red pigment, wherein the red pigment is prepared by adding the compound represented by the formula (I) except the compound represented by the formula (I),

the content of the compound represented by the formula (I) is 2-40% by mass relative to the total amount of the colorant,

the content of the red pigment is 1 to 95 mass% based on the total amount of the colorant;

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

R¹¹～R¹⁶each independently represents a hydroxyl group, a halogen atom, a cyano group, a nitro group, a saturated hydrocarbon group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, wherein a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a cyano group, a nitro group, a hydroxyl group or a halogen atom, and wherein a hydrogen atom contained in the phenyl group or the benzyl group may be substituted by a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, a cyano group or a vinyl group;

A^q-to representA q-valent anion, q represents an integer of 1 to 14;

p represents a coefficient for keeping the charge neutral by the compound represented by the formula (I).

2. The colored curable resin composition according to claim 1, wherein A is^q-Selected from the following: an anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom, a halide anion, a perchlorate anion, a chlorate ion, a thiocyanate ion, a hexafluorophosphate ion, a hexafluoroantimonate ion, a tetrafluoroborate ion, an organocarboxylate anion, an organosulfonate anion, an organophosphate anion, an organoimidinate anion, an organomomethylate anion, and a metal complex anion.

3. The colored curable resin composition according to claim 1, wherein the colorant further comprises a yellow pigment except for the compound represented by formula (I).

4. A color filter comprising the colored curable resin composition according to any one of claims 1 to 3.

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