JP2019090008A - Coloring curable resin composition - Google Patents

Abstract

【選択図】なしThe present invention provides a colored curable resin composition capable of forming a color filter having improved lightness or light resistance.
For example, a coloring agent includes any one of a compound represented by the formula (IX) and a red pigment: pigment red 177, 202, 254, 269, and a brominated diketopyrrolopyrrole pigment. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the content of the red pigment is 1% by mass or more and 95% by mass or less based on the total amount of the colorant.

【Selection chart】 None

Description

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

  Color filters used for display devices such as liquid crystal display devices, electroluminescent display devices and plasma displays, and solid-state imaging devices such as CCDs and CMOS sensors are manufactured from a colored curable resin composition. 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

  The color filter formed from the above-mentioned colored curable resin composition conventionally known is not satisfactory in lightness. Moreover, the color filter formed from said colored curable resin composition conventionally known was not able to be satisfied of light resistance.

The gist of the present invention is as follows.
[1] containing a colorant, a resin, a polymerizable compound and a polymerization initiator,
The coloring agent includes a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)).
Colored curable resin composition whose content rate of a red pigment is 1 mass% or more and 95 mass% or less with respect to the coloring agent whole quantity.

[In the formula (I),
R ^{1 to} R ¹⁰ each independently represent 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 is substituted with a halogen atom It is also good.
R ^{11 to} R ¹⁶ each independently represent a hydroxy 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, and is included in the saturated hydrocarbon group The hydrogen atom may be substituted with a cyano group, a nitro group, a hydroxy group or a halogen atom, and the hydrogen atom contained in the phenyl group and the benzyl group is a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom It may be substituted by a cyano group or a vinyl group.
R ¹¹ and R ¹² , R ¹³ and R ^14, and R ¹⁵ and R ¹⁶ may be respectively linked to form a 3- to 6-membered heterocyclic ring containing a nitrogen atom,
R ¹ and R ¹¹ , R ² and R ¹² , R ⁴ and R ¹³ , R ⁵ and R ¹⁴ , R ⁸ and R ¹⁵ , R ¹⁰ and R ¹⁶ , R ⁷ and R ⁸ and R ⁹ and R ¹⁰ respectively They may be linked to form a 6-membered ring.
A ^q- represents a q-valent anion, and q represents an integer of 1 to 14.
p represents a coefficient that keeps the charge neutral in the compound represented by the formula (I). ]
[2] including a colorant, a resin, a polymerizable compound and a polymerization initiator,
The coloring agent includes a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)).
Colored curable resin composition whose content rate of a red pigment is 30 mass% or more and 95 mass% or less with respect to the coloring agent whole quantity.

[In the formula (I),
R ^{1 to} R ¹⁰ each independently represent 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 is substituted with a halogen atom It is also good.
R ^{11 to} R ¹⁶ each independently represent a hydroxy 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, and is included in the saturated hydrocarbon group The hydrogen atom may be substituted with a cyano group, a nitro group, a hydroxy group or a halogen atom, and the hydrogen atom contained in the phenyl group and the benzyl group is a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom It may be substituted by a cyano group or a vinyl group.
R ¹¹ and R ¹² , R ¹³ and R ^14, and R ¹⁵ and R ¹⁶ may be respectively linked to form a 3- to 6-membered heterocyclic ring containing a nitrogen atom,
R ¹ and R ¹¹ , R ² and R ¹² , R ⁴ and R ¹³ , R ⁵ and R ¹⁴ , R ⁸ and R ¹⁵ , R ¹⁰ and R ¹⁶ , R ⁷ and R ⁸ and R ⁹ and R ¹⁰ respectively They may be linked to form a 6-membered ring.
A ^q- represents a q-valent anion, and q represents an integer of 1 to 14.
p represents a coefficient that keeps the charge neutral in the compound represented by the formula (I). ]
[3] An anion in which A ^q- contains at least one atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom, a halide anion, a perchlorate ion, a chlorate ion, a thiocyanate ion Selected from hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion, organic carboxylate anion, organic sulfonate anion, organic phosphate anion, organic imide anion, organic methide anion, organic methide anion, and metal complex anion Colored curable resin composition as described in [1] or [2].
[4] The colored curable resin composition according to any one of [1] to [3], wherein the colorant further contains a yellow pigment (excluding the compound represented by the formula (I)).
[5] A color filter formed from the colored curable resin composition according to any one of [1] to [4].
[6] A display device including the color filter according to [5].

  According to the colored curable resin composition of the present invention, a color filter excellent in lightness can be formed. Moreover, according to the colored curable resin composition of this invention, the color filter excellent in light resistance can be formed.

The colored curable resin composition of the present invention comprises a colorant (hereinafter sometimes referred to as a colorant (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter referred to as a polymerizable compound). And (C)), and a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)).
The coloring agent (A) contains a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)), and the content of the red pigment is relative to the total amount of the coloring agent And 1% by mass to 95% by mass.
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 each component can be used alone or in combination of two or more kinds unless otherwise noted.

<Colorant (A)>
The colorant (A) includes a compound represented by the formula (I) and a red pigment (except for the compound represented by the formula (I)).
The compounds represented by formula (I) are as follows.

[In the formula (I),
R ^{1 to} R ¹⁰ each independently represent 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 is substituted with a halogen atom It is also good.
R ^{11 to} R ¹⁶ each independently represent a hydroxy 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, and is included in the saturated hydrocarbon group The hydrogen atom may be substituted with a cyano group, a nitro group, a hydroxy group or a halogen atom, and the hydrogen atom contained in the phenyl group and the benzyl group is a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom It may be substituted by a cyano group or a vinyl group.
R ¹¹ and R ¹² , R ¹³ and R ^14, and R ¹⁵ and R ¹⁶ may be respectively linked to form a 3- to 6-membered heterocyclic ring containing a nitrogen atom,
R ¹ and R ¹¹ , R ² and R ¹² , R ⁴ and R ¹³ , R ⁵ and R ¹⁴ , R ⁸ and R ¹⁵ , R ¹⁰ and R ¹⁶ , R ⁷ and R ⁸ and R ⁹ and R ¹⁰ respectively They may be linked to form a 6-membered ring.
A ^q- represents a q-valent anion, and q represents an integer of 1 to 14.
p represents a coefficient that keeps the charge neutral in the compound represented by the formula (I). ]

The saturated hydrocarbon group having 1 to 8 carbon atoms representing R ^{1 to} R ¹⁰ and R ^{11 to} R ¹⁶ may be linear, branched or cyclic. As a linear or branched saturated hydrocarbon group, linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and octyl group; isopropyl group, isobutyl group, isopentyl And branched alkyl groups such as neopentyl group and 2-ethylhexyl group. The carbon number of the saturated hydrocarbon group is preferably 1 to 6, and 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 group, cyclobutyl group, cyclopentyl group and cyclohexyl group. The carbon number of the cyclic saturated hydrocarbon group is preferably 3 to 8, more preferably 6 to 8.
Among them, a linear saturated hydrocarbon group is preferable, and a methyl group, an ethyl group and a propyl group are particularly preferable.

The hydrogen atom contained in the said saturated hydrocarbon group may be substituted by the halogen atom.
As the halogen atom, fluorine, chlorine, bromine, iodine and the like can be mentioned. When the halogen atom is a fluorine atom, the halogen atom is preferably substituted so as to form a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit or a heptafluoropropyl unit.

In R ¹¹ to R ^16, hydrogen atoms contained in a saturated hydrocarbon group having 1 to 8 carbon atoms, a cyano group, a nitro group, may be substituted by a hydroxy group or a halogen atom.

In R ¹¹ to R ^16, hydrogen atoms contained in the phenyl group and benzyl group, a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, may be substituted with a cyano group or a vinyl group.
The saturated hydrocarbon group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom contained in the phenyl group and benzyl group of R ^{11 to} R ¹⁶ is selected from the above-mentioned saturated hydrocarbon groups having 1 to 8 carbon atoms. The thing similar to a C1-C4 thing is mentioned.

R ¹ and R ¹¹ , R ² and R ¹² , R ⁴ and R ¹³ , R ⁵ and R ¹⁴ , R ⁸ and R ¹⁵ , R ¹⁰ and R ¹⁶ , R ⁷ and R ⁸ and R ⁹ and R ¹⁰ respectively They may be linked 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.

R ¹¹ and R ¹² , R ¹³ and R ^14, and R ¹⁵ and R ¹⁶ may be respectively 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 heterocyclic rings such as pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring, thiomorpholine ring, pyrrole ring, imidazole ring, imidazolidine ring, pyrazolidine ring, isothiazolidine ring and the like And preferably, nitrogen-containing aliphatic heterocycles having only one nitrogen atom as a hetero atom such as a pyrrolidine ring and a piperidine ring.

R ^{1 to} R ⁶ , R ⁸ and R ¹⁰ each independently represent a hydrogen atom, R ⁷ and R ⁹ each independently represent a hydrogen atom or a halogen atom, and R ^{11 to} R ¹⁶ each independently represent Independently, it is preferable that it is a C1-C8 saturated hydrocarbon group,
R ^{1 to} R ⁶ , R ⁸ and R ¹⁰ each independently represent a hydrogen atom, R ⁷ and R ⁹ each independently represent a halogen atom, and R ^{11 to} R ¹⁶ each independently represent And a saturated hydrocarbon group having 1 to 6 carbon atoms is more preferable.

A ^q- is a q-valent anion, and is a monovalent to tetravalent anion.
That is, q represents 1 to 14, preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, particularly preferably 1 or 2.
p represents a coefficient that keeps the charge neutral in 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 carboxylic acid anions, organic sulfonic acid anions, organic phosphoric acid anions, organic imide acid anions, organic methide acid anions, metal complex anions and the like.

The halide anion includes chloride ion, bromide ion, iodide ion, fluoride ion and the like.
As the inorganic anion, perchlorate ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion (hereinafter sometimes referred to as "anion (VII)"), hexafluoroantimonate ion, tetrafluoroborate ion, etc. Can be mentioned.
In addition, as the inorganic anion, an anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom can be mentioned. An anion containing a tungsten atom and an oxygen atom is preferred from the viewpoint of heat resistance.
An anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom may be α- [PW ₁₂ O ₄₀ ] ^3- (hereinafter referred to as “anion (IX)” .) Keggin phosphotungstic acid ion such _{as; α- [P 2 W 18 O} 62] 6-, β- [P 2 W 18 O 62] 6- , etc. Dawson type phosphotungstic acid ion; α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^{4- and} other Keggin-type silicotungstic acid ions; [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ! ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O _{36 ^{] 8-, α- [SiW 11 O}} 39] 8-, β- [SiW 11 O 39] 8-; [W 6 O 19] 2-, [W 10 O 32] 4-, WO ₄ tungsten-containing ^2-like isopolyacids ion; silicate ions; phosphate ion, and the like.

Acetic acid ion etc. are mentioned as an organic carboxylic acid anion.
As an organic sulfonate anion, methanesulfonic acid ion, dodecylsulfonic acid ion, benzenesulfonic acid ion, toluenesulfonic acid ion, naphthalenesulfonic acid ion, diphenylamine-4-sulfonic acid ion, 2-amino-4-methyl-5-one Examples thereof include chlorobenzenesulfonic acid ion, 2-amino-5-nitrobenzenesulfonic acid ion, phthalocyanine sulfonic acid ion, sulfonic acid ion having a polymerizable substituent, benzenedisulfonic acid anion, and naphthalenedisulfonic acid anion.

  As an organic phosphate anion, octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylenebis (4,6-di-t-butylphenyl) Phosphonate ion etc. are mentioned.

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

  As a metal complex anion, for example, C.I. I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161; I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99; I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 225, 233, 234, 243; C.I. I. Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61; I. Solvent blue 137; C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63; I. Acid Yellow 59, 121; C.I. I. Acid Orange 74, 162; C.I. I. Acid Red 211, anions derived from metal complex salt dyes described in JP-A-2010-170117.

Examples of the molecule (ligand) include an azo molecule, a methine molecule and the like, and an azo molecule is preferable.
Examples of the metal atom include chromium, cobalt, nickel and the like, with chromium and cobalt being preferable.

As a specific metal complex anion, the anion represented by Formula (VIII) is mentioned.

Among them, as A ^q- , an anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and an oxygen atom, an organic carboxylic acid anion, an organic sulfonic acid anion, an organic imide acid anion, an organic acid A methide acid anion and a metal complex anion are preferable, and an anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom, and a metal complex anion are more preferable.
Further, a fluorine-containing organic carboxylic acid anion, a fluorine-containing organic sulfonic acid anion, a fluorine-containing organic imide acid anion, and a fluorine-containing organic methide acid anion (hereinafter collectively referred to as a fluorine-containing anion) are more preferable.

Examples of the fluorine-containing anion include CF ₃ CO ₂ ^— and an anion represented by the formula (III), (IV), (V) or (VI).

[In Formula (III), W ³ and W ⁴ independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ together form a carbon number It represents 1 to 4 fluorinated alkanediyl groups. ]

Wherein (IV), W ⁵ ~W ^7, independently of each other, represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. ]

Wherein (V), Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms. ]

[In Formula (VI), Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms. ]

In formulas (III), (IV) and (VI), a perfluoroalkyl group is preferable as the fluorinated alkyl group having 1 to 4 carbon atoms. As the perfluoroalkyl group, —CF ₃ , —CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₃ , —CF (CF ₃ ) ₂ , —CF ₂ CF ₂ CF ₂ CF ₃ , —CF ₂ CF (CF _{3) ) 2, -C (CF 3)} 3 and the like.

In formula (III) and (V), as the fluorinated alkanediyl group having 1 to 4 carbon atoms, perfluoro alkanediyl group is _{preferred, -CF 2 -, - CF 2} CF 2 -, - CF 2 CF 2
_{CF 2 -, - C (CF} 3) 2 -, - CF 2 CF 2 CF 2 CF 2 - , and the like.

  As the anion represented by the formula (III) (hereinafter sometimes referred to as "anion (III)"), the anion represented by the formula (III-1) to the formula (III-6) (hereinafter referred to as "anion III-1) "to" anion (III-6) "may be mentioned.

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

  As the anion represented by the formula (V) (hereinafter sometimes referred to as "anion (V)"), the anion represented by the formula (V-1) to the formula (V-4) (hereinafter referred to as "anion (V)" -1) "to" anion (V-4) "may be mentioned.

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

The fluorine-containing anion may be at least one anion selected from the group consisting of CF ₃ CO ₂ ⁻ , anion (III), anion (IV), anion (V) and anion (VI). Among them, CF ₃ CO ₂ ⁻ , anion (III-1), anion (III-2), anion (III-6), anion (IV-1), anion (V-1), anion (VI-1), The anion (VI-2) and the anion (VI-3) are preferable, and CF ₃ CO ₂ ⁻ , the anion (III-2), the anion (IV-1) and the anion (VI-1) are more preferable.

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

(In formula (I-A), R ⁷ , R ⁹ , R ^{11 to} R ¹⁶ , p, q and A ^q- are as defined above.)
In Tables 1 to 10 below, Me is a methyl group, Et is an ethyl group, Pro is a propyl group, III-1 to III-6, V-1, V-2, VII, VIII, and IX have the above formula (III). -1) An anion represented by Formula (III-6), an anion represented by Formula (V-1), an anion represented by Formula (V-2), an anion represented by Formula (VII), The anion represented by Formula (VIII), the anion represented by Formula (IX) are represented.

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

  Among them, compounds represented by Formula (I-97) to Formula (I-192), and compounds represented by Formula (I-289) to Formula (I-324) are preferable, and Formula (I-97) to Formula The compounds represented by (I-128) and the compounds represented by formulas (I-289) to (I-324) are more preferable, and are represented by formulas (I-97) to (I-120) The compounds, the compounds represented by the formulas (I-289) to the formulas (I-324) are more preferable, the compounds represented by the formula (I-104), the compounds represented by the formula (I-308) The compound represented by I-312) is particularly preferable.

  The compounds represented by formula (I) can be produced, for example, with reference to the method described in WO 2014/196464.

  The content of the compound represented by the formula (I) is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass, with respect to the total amount of the colorant. More preferably, it is 3% by mass to 30% by mass.

The content of the compound represented by the formula (I) is preferably 0.2% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 15% by mass or less with respect to the total solid content. Is more preferable, and 1% by mass or more and 12% by mass or less is more preferable.
Here, "solid content whole amount" in this specification means the quantity which remove | eliminated content of the solvent from coloring curable resin composition whole quantity. The total solid content and the content of each component relative thereto can be measured, for example, by a known analysis means such as liquid chromatography or 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, for example, among pigments classified into pigments by Color Index (published by The Society of Dyers and Colourists) And those classified into red. Two or more may be combined. However, the compound represented by formula (I) is remove | excluded.

  Specifically, C.I. I. 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, And red pigments such as 265, 266, 268, 269, 273.

  Among the red pigments, anthraquinone pigments, azo pigments, quinacridone pigments, perylene pigments and diketopyrrolopyrrole pigments are preferable, and C.I. I. Pigment red 177, 179, 202, 208, 242, 254, 269, brominated diketopyrrolopyrrole pigments are preferred, and C.I. I. Pigment red 177, 202, 254, 269, more preferably a brominated diketopyrrolopyrrole pigment.

The content of the red pigment is 1% by mass to 95% by mass, preferably 30% by mass to 95% by mass, and preferably 40% by mass to 90% by mass, with respect to the total amount of the colorant. Is more preferably 50% by mass or more, still more preferably 60% by mass or more.
Containing a red pigment in the case where the RGB color-coded OLEDs that generate RGB from each pixel by laminating each pixel of RGB are generated on the substrate instead of generating RGB from the white light emitting layer through the color filter The rate can be, for example, 1% by mass or more and 95% by mass or less (preferably 1% by mass or more and less than 30% by mass) to obtain a red-colored coated film excellent in light resistance.

Furthermore, the total content of the compound represented by the 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. It is.
When the colored curable resin composition of the present invention contains a colorant (A1) described later, the total content of the compound represented by the formula (I) and the red pigment is preferably 40 mass% with respect to the total amount of colorant. % Or more, more preferably 50% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less.

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

  The colored curable resin composition of the present invention contains, as the colorant (A), a colorant other than the compound represented by the formula (I) and the red pigment (hereinafter sometimes referred to as a colorant (A1)) It may be The colorant (A1) may contain one or more colorants.

  The colorant (A1) may be a dye or a pigment. Dyes include the known dyes described in the Color Index (The Society of Dyers and Colourists, published) and Dyeing Notes (Color Dyes). Further, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes (excluding compounds represented by formula (I)), cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, Examples include azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes and phthalocyanine dyes. Among these, organic solvent soluble dyes are preferred. Two or more of these dyes may be used in combination.

Specifically, the following dyes having a color index (CI) number may be mentioned. 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, 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, 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, 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, 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. Basic Green 1;
C. I. Bat green 1 grade.

As the pigment, known pigments can be used, and examples thereof include pigments classified into pigments by Color Index (published by The Society of Dyers and Colourists). Two or more may be combined. However, the compound represented by formula (I) is remove | excluded.
Specifically, 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;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like;
C. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60, etc. blue pigment;
C. I. Violet pigments such as CI pigment violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment green 7, 36, 58, 59 green pigments.

  As the colorant (A1), a yellow pigment is preferable, and C.I. I. Pigment yellow 138, 139, 150, 185 and 231 are more preferable.

  When the yellow pigment is contained, the content is preferably 1% by mass to 50% by mass, and more preferably 3% by mass to 45% by mass, based on the total amount of the colorant.

  The content of the yellow pigment is preferably 0.2% by mass to 25% by mass, and more preferably 0.6% by mass to 20% by mass, with respect to the total solid content.

  The compound represented by the formula (I), the red pigment and the pigment in the colorant (A1) (hereinafter sometimes referred to as a pigment etc.) may be subjected to rosin treatment, or to which an acidic group or a basic group is introduced, as necessary. Surface treatment using coloring agent derivative etc., grafting treatment to the surface of pigment etc. with polymer compound etc., atomization treatment by sulfuric acid atomization method etc., washing treatment with organic solvent or water to remove impurities, ionicity The removal process etc. of the impurity by the ion exchange method etc. may be given. The particle sizes of the pigment and the like are preferably substantially uniform. A pigment etc. will be in the state disperse | distributed uniformly in the dispersion liquid by containing a dispersing agent and performing a dispersion process.

  The dispersing agent may, for example, be a surfactant, and may be any of cationic, anionic, nonionic and amphoteric surfactants. Specifically, polyester based, polyamine based and acrylic based surfactants and the like can be mentioned. You may use resin (B) mentioned later as another dispersing agent. These dispersants may be used alone or in combination of two or more. As a dispersing agent, when it represents with a brand name, KP (Shin-Etsu Chemical Co., Ltd. product), Floren (Kyoeisha Chemical Co., Ltd. product), Sols spars (trademark) (Zeneca product), EFKA (trademark) (Manufactured by BASF), AZISPAR (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BIC-Chemie), BYK (registered trademark) (manufactured by BIC-Chemie), and the like.

  When a dispersant is used, the amount of the dispersant used is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment and the like. When the amount of the dispersant used is in the above range, the colorant-containing liquid in a more uniform dispersion state 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, based on the total solid content. Is 15% by mass or more and 50% by mass or less.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and at least one kind (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter "(a)" The resin having a structural unit derived from Further, the resin (B) 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, Structural units derived from monomers (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter sometimes referred to as “(c)”), and side It is preferable to have at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the chain.

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono [2- (meth) Acryloyloxyethyl] and the like, with preference given to acrylic acid, methacrylic acid and maleic anhydride.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. The notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

(B) is 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, vinyl benzyl glycidyl ether, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, 3-ethyl-3- Examples thereof include (meth) acryloyloxymethyl oxetane, tetrahydrofurfuryl (meth) acrylate and the like, preferably glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ( Meta) acrylate, 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 [5.2.1.0 ^2,6 ] decane-8. -Yl (meth) acrylate benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, styrene, vinyl toluene and the like, preferably styrene, Preferred are vinyl toluene, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide and the like.

  In the resin having a structural unit having an ethylenically unsaturated bond in the side chain, either (b) is added to the copolymer of (a) and (c) or the copolymer of (b) and (c) Can be produced by adding (a) to 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 polystyrene equivalent weight average molecular weight of the resin (B) 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, and more preferably 1.2 to 4.

  The acid value of the resin (B) is preferably 50 to 170 mg KOH / g, more preferably 60 to 150 mg KOH / g, and still more preferably 70 to 135 mg KOH / g, in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g 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, with respect to the total solid content.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound which can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenic unsaturated bond and the like, and is preferably Is a (meth) acrylic acid ester compound.

  Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. As such a polymerizable compound, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( Meta) acrylate and the like.

  The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, 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, still more preferably 11 to 40% by mass, based on the total mass of the solid content. .

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids and the like by the action of light and heat and initiating polymerization, and known polymerization initiators can be used. As a polymerization initiator which generates an active radical, for example, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) ) Octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, 2-methyl-2-morpholino-1- (one) 4-Methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis (trichloromethyl) ) -6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyl Diphenyl phosphine oxide, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole.

  The polymerization initiator is preferably a polymerization initiator containing at least one selected from the group consisting of triazine compounds, acyl phosphine oxide compounds, alkyl phenone compounds, O-acyl oxime compounds and biimidazole compounds, and includes O-acyl oxime compounds A polymerization initiator is more preferred.

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

  The content of the O-acyloxime compound is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more based on the total amount of the polymerization initiator (D). And particularly preferably 95% by mass or more. If the content of the O-acyloxime compound is within the above range, it tends to be possible to produce a high brightness color filter even when the sensitivity at the time of forming a colored pattern, the developability, and the colorant content is high.

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

<Polymerization start assistant (D1)>
The polymerization initiation auxiliary (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
As the polymerization initiation auxiliary (D1), 4,4′-bis (dimethylamino) benzophenone (generally called Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone N-phenylglycine etc. are mentioned.

  When using these polymerization start adjuvants (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably, it is 1 to 20 parts by mass. When the amount of the polymerization initiator (D1) is in 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 solvents commonly used in the relevant field can be used. For example, ester solvents (solvents containing -COO- in the molecule but not -O-), ether solvents (solvents containing -O- in the molecule and not -COO-), ether ester solvents (in molecules) Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- in the molecule but not -COO-), alcohol solvents (containing OH in the molecule, -O-,- Solvents not containing CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

As the solvent, ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone (intramolecular Solvents containing -COO- and not -O-); ether solvents 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 A solvent containing -O- in the molecule and not containing -COO-);
Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (in the molecule -COO- Solvents containing and -O-);
Ketone solvents such as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, cyclohexanone and the like (a solvent containing -CO- in the molecule but not -COO-); Alcohol solvents such as butanol, cyclohexanol, propylene glycol (including OH in the molecule, and solvents not containing -O-, -CO- and -COO-); and the like. Aromatic hydrocarbon solvents such as benzene, toluene, xylene and mesitylene may be mentioned.
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone are mentioned.

  As the solvent, diacetone alcohol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone and ethyl 3-ethoxypropionate are more preferable.

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

  The content of the solvent to be combined with propylene glycol monomethyl ether acetate is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, and still more preferably 5% by mass with respect to the total amount of the solvent. It is mass% or more and 30 mass% or less.

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

<Other ingredients>
The colored curable resin composition of the present invention is known in the art as needed, such as leveling agents, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc. Additives of the following.

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

<Method of manufacturing color filter>
As a method of manufacturing a coloring pattern from the coloring curable resin composition of this invention, a photolithographic method, the inkjet method, the printing method, etc. are mentioned. Among them, photolithographic method is preferred. In the photolithography method, a colored coating film which is a cured product of the above-mentioned coloring composition layer can be formed by not using a photo mask at the time of exposure and / or not developing. The colored pattern and the colored coating film thus formed are the color filter of the present invention.

  The colored curable resin composition of the present invention can produce a color filter excellent in lightness. 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.

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples. Unless otherwise indicated, "%" and "parts" in the examples are% by mass and parts by mass.
In the following synthesis examples, compounds were identified by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type) or elemental analysis (VARIO-EL; (Elemental Co., Ltd.)).

Synthesis example 1
Synthesis of bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ N ⁻ ) salt 2.5 parts of compound S-1 represented by the following formula, 2.5 parts of diethylaminophenol, and 3.3 parts of sulfuric acid Were mixed and stirred at 140.degree. C. 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 three times with water, and then 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 (yield 52%) of a leuco body.

  27 parts of the above-mentioned leuco body, 184.4 parts of p-chloranil, 15 parts of acetic acid and 0.9 parts of hydrochloric acid were mixed and stirred at 60 ° C. for 1 hour. The solid was removed by filtration, chloroform was added to the filtrate, and the aqueous layer was neutralized with aqueous sodium hydrogen carbonate solution. After salt exchange with the addition of 1.4 parts of potassium bis (trifluoromethanesulfonyl) imide, the reaction solution was washed with water to evaporate the solvent from the organic layer. The residue is purified by silica gel column chromatography (developing solvent: chloroform: ethyl acetate = 1: 1) to obtain 11.5 parts of a compound represented by the formula (I-X) (compound represented by the formula (I-104)) (Yield 27%) was obtained.

Synthesis example 2
Synthesis of Hydrochloride 4.0 parts of the leuco body, 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 removed by filtration, the organic layer was washed with water, sodium sulfate was added and dried, and the solvent was evaporated. The mixture was added with 200 parts of concentrated hydrochloric acid and stirred for 6 hours, then added dropwise to 600 parts of 10% saline and stirred overnight. The precipitated solid was collected by filtration, 5% aqueous sodium hydroxide solution was added to the filtrate to neutralize to pH 4, and the precipitated solid was also collected by filtration. The combined solid was dispersed and washed with water and filtered, and then the solid was dried in a vacuum oven at 60 ° C. to obtain 4.1 parts (yield 95%) of a compound represented by formula (I-XI).

Synthesis example 3
Synthesis of phosphotungstate salt 3.00 parts of a compound (a compound represented by the formula (I-XI)) and 515 parts of methanol are mixed, and while stirring at room temperature, phosphotungstic acid hydrate (manufactured by SIGMA-ALDRICH) A solution of 30.1 parts and 30.5 parts of methanol was added dropwise and stirred for 3 hours after the addition. The precipitated solid is collected by filtration, dispersed and washed three times with 50.0 parts of methanol, and then dried in a vacuum oven at 60 ° C. to give 10.6 parts of a compound represented by formula (I-312) (yield 60%).

Synthesis example 4
Synthesis of Solvent Yellow 21 salt 0.20 parts of a compound (a compound represented by the formula (I-XI)), 0.11 parts of Solvent Yellow 21, and 4.8 parts of N, N-dimethyl sulfoxide are mixed, Stir for 3 hours. The reaction solution was added dropwise to 40 parts of 20% brine, and the precipitated solid was collected by filtration. The solid was dissolved in chloroform, and the organic layer was washed with water and then sodium sulfate was added to dryness, and then the solvent was distilled off. It dried in 60 degreeC vacuum oven and obtained 0.43 parts (yield 85%) of compounds represented by Formula (I-308).

Synthesis example 5
Sodium tert-amyl alcoholate was synthesized by reacting 174 parts of tert-amyl alcohol and 22.2 parts of metallic sodium at 130 ° C. under a nitrogen atmosphere. The mixture is heated to 60 ° C., 91.0 parts of 4-bromobenzonitrile, 71.05 parts of oxalic acid di-tert-amyl ester and 108.9 parts of tert-amyl alcohol are added, and the solution temperature becomes 85 ° C. or less The mixture was stirred for 2 hours. The suspension was further stirred for 18 hours or more, and then added to a mixture of 200 parts of methanol, 1000 parts of water, and 49.21 parts of sulfuric acid cooled to -10 ° C. After the addition of the suspension was completed, the reaction was completed by maintaining the temperature at 0 ° C. and stirring for 5 hours, and then the solid was filtered. The solids were washed repeatedly with methanol and water until the color of the filtrate was gone and salt deposition was gone. Thereafter, the solid content was dried in a vacuum drier at 80 ° C. for 18 hours to obtain the target red pigment 1. The yield was 107 parts.

Synthesis example 6
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed and nitrogen was replaced, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were charged and heated to 85 ° C. while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ² ,, ⁶ ] A mixed solution of 25 parts of a mixture of deca-9-yl acrylate (content ratio is 1: 1), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate is added dropwise over 5 hours did. 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 solution was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a 25.6% solid copolymer (resin (B-1)) solution. The weight average molecular weight Mw of the produced | generated copolymer was 8000, dispersion degree 2.1, and the acid value of solid content conversion were 111 mg-KOH / g. Resin (B-1) has the following structural unit.

Synthesis example 7
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed to make a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 80 ° C. while stirring. Then, in the flask, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. A solution of 289 parts of a mixture of 1.0 ^2,6 ] decane-9-yl acrylate (content ratio is 1: 1) dissolved in 125 parts of propylene glycol monomethyl ether acetate was dropped over about 5 hours using a dropping pump . On the other hand, a solution of 33 parts of polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate is dropped into the flask over about 6 hours using another dropping pump did. After completion of the dropwise addition, the temperature was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) with a solid content of 35.1%. The weight average molecular weight Mw of the produced | generated copolymer was 9200, dispersion degree 2.08, and the acid value of solid content conversion were 77 mg-KOH / g. Resin (B-2) has the following structural unit.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was performed under the following conditions using a GPC method.
Device: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corp.)
The ratio (Mw / Mn) of the weight average molecular weight in terms of polystyrene and the number average molecular weight obtained above was taken as the degree of dispersion.

[Preparation of Dispersion 1 (Br-DPP)]
A mixture of 28 parts of a red pigment 1 compound, 10 parts of a dispersant (byk company BYKLPN-6919 in terms of solid content), 8 parts of a resin (B-2) (in terms of solid content) and 154 parts of propylene glycol monomethyl ether acetate Then, 600 parts of 0.4 μm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain Dispersion 1.

Preparation of Dispersion 2 (Y138)
C. I. Mix 24 parts of CI Pigment Yellow 138, 11 parts of dispersant (BYKPEN BYKLPN-6919, converted to solid content), 5 parts of resin (B-2) (converted to solid content), and 160 parts of propylene glycol monomethyl ether acetate, 600 parts of 0.4 μm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain Dispersion 2.

[Preparation of Dispersion 3 (Y 231)]
C. I. Mix 24 parts of CI Pigment Yellow 231, 11 parts of dispersant (BYKPN BY 6 6 5 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 7 600 parts of 0.4 μm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain Dispersion 3.

Preparation of Dispersion 4 (Y185)
C. I. 20 parts of CI Pigment Yellow 185, 11 parts of a dispersing agent (byk company BYKLPN-6919 on solid basis), 5 parts of resin (B-2) (on solid basis), and 160 parts of propylene glycol monomethyl ether acetate are mixed. 600 parts of 0.4 μm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain dispersion 4.

Preparation of Dispersion 5 (R177)
C. I. Mix 26 parts of pigment red 177, 7 parts of dispersant (BYKPN BY 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 7 7 600 parts of 0.4 μm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain Dispersion 5.

Preparation of Dispersion 6 (R 269)
C. I. 26 parts of pigment red 269, 11 parts of dispersant (BYKPN BY 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Shake for 1 hour using Thereafter, the zirconia beads were removed by filtration to obtain dispersion liquid 6.

[Preparation of Dispersion 7 (R 254)]
C. I. 30 parts of CI Pigment Red 254, 6 parts of a dispersing agent (BYKPN-6919 solid content conversion made by BYK), 14 parts of a resin (B-2) (solid content conversion), and 150 parts of propylene glycol monomethyl ether acetate are mixed. 600 parts of 0.4 μm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain dispersion liquid 7.

[Preparation of Dispersion 8 (Y139)]
C. I. 24 parts of pigment yellow 139, 8 parts of dispersing agent (BYKPN BY 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 7 6 7 7 resin (B-2) (solid content conversion) 8 parts, 10 parts of propylene glycol monomethyl ether, propylene glycol monomethyl ether 150 parts of acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and shaken using a paint conditioner (manufactured by LAU) for 1 hour. Thereafter, the zirconia beads were removed by filtration to obtain dispersion liquid 8.

[Preparation of Dispersion 9 (D2428-PWA I-312)]
10 parts of the compound (I-312), 12 parts of a dispersing agent (BYKPN-6919 (solid content conversion) made by BYK), 8 parts of a resin (B-2) (solid content conversion), 20 parts of diacetone alcohol, propylene glycol 150 parts of monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and shaken using a paint conditioner (manufactured by LAU) for 1 hour. Thereafter, the zirconia beads were removed by filtration to obtain a dispersion liquid 9.

[Preparation of Dispersion 10 (R202)]
C. I. 24 parts of pigment red 202, 11 parts of dispersant (BYKP BYKLPN-6919 solid content conversion), 8 parts of resin (B-2) (solid content conversion), 20 parts of propylene glycol monomethyl ether, propylene glycol monomethyl ether 136 parts of acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and shaken using a paint conditioner (manufactured by LAU) for 1 hour. Thereafter, the zirconia beads were removed by filtration to obtain a dispersion liquid 10.

[Examples 1 to 10, Comparative Examples 1 to 2]
[Preparation of Colored Curable Resin Composition]
Each component shown in Tables 11 and 12 was mixed to obtain each colored curable resin composition.

Resin (B-1): Resin B-1 (solid content conversion)
Polymerizable compound (C-1): dipentaerythritol hexaacrylate (Shin-Nakamura Chemical Co., Ltd. product "A9550" solid content conversion)
Polymerization initiator (D-1): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IRGACURE (registered trademark) OXE 01; manufactured by BASF)
Solvent (E-1): Propylene glycol monomethyl ether acetate solvent (E-2): Diacetone alcohol solvent (E-3): Ethyl lactate leveling agent (F-1): Polyether modified silicone oil (solid content conversion) Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.

<Preparation of color filter (colored coating film)>
The colored curable resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After leaving to cool, the colored composition layer was irradiated with light at an exposure dose of 60 mJ / cm ² (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Thereafter, post-baking was performed in an oven at 230 ° C. for 20 minutes to obtain a color filter.

[Film thickness measurement]
The film thickness of the obtained color filter was measured using a film thickness measurement device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 13.

[Chromaticity evaluation]
About the obtained color filter, the spectrum is measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity in the XYZ color system of CIE using the color matching function of the C light source The coordinates (x, y) and the stimulus value Y were measured. The larger the value of Y, the higher the lightness. The results are shown in Table 13.

<Light resistance evaluation>
A UV cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya; cut light of 380 nm or less) is disposed on the obtained colored coating film, and a light resistance tester (Suntest CPS +: manufactured by Toyo Seiki Co., Ltd.) The xenon lamp light was irradiated for 48 hours.
Before and after irradiation, xy chromaticity coordinates (x, y) and Y are measured, and the color difference ΔEab * is calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Calculation method of color difference). Is shown in Table 14. As ΔEab * is smaller, it means that the color change is smaller. Moreover, if the light resistance of a colored coating film is favorable, it can be said that the light resistance is also favorable for the colored pattern produced from the same colored curable resin composition.

Claims (5)

Containing a coloring agent, a resin, a polymerizable compound and a polymerization initiator,
The coloring agent includes a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)).
Colored curable resin composition whose content rate of a red pigment is 1 mass% or more and 95 mass% or less with respect to the coloring agent whole quantity.

[In the formula (I),
R ^{1 to} R ¹⁰ each independently represent 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 is substituted with a halogen atom It is also good.
R ^{11 to} R ¹⁶ each independently represent a hydroxy 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, and is included in the saturated hydrocarbon group The hydrogen atom may be substituted with a cyano group, a nitro group, a hydroxy group or a halogen atom, and the hydrogen atom contained in the phenyl group and the benzyl group is a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom It may be substituted by a cyano group or a vinyl group.
R ¹¹ and R ¹² , R ¹³ and R ^14, and R ¹⁵ and R ¹⁶ may be respectively linked to form a 3- to 6-membered heterocyclic ring containing a nitrogen atom,
R ¹ and R ¹¹ , R ² and R ¹² , R ⁴ and R ¹³ , R ⁵ and R ¹⁴ , R ⁸ and R ¹⁵ , R ¹⁰ and R ¹⁶ , R ⁷ and R ⁸ and R ⁹ and R ¹⁰ respectively They may be linked to form a 6-membered ring.
A ^q- represents a q-valent anion, and q represents an integer of 1 to 14.
p represents a coefficient that keeps the charge neutral in the compound represented by the formula (I). ] A ^q- is tungsten, molybdenum, anion containing at least one atom and an oxygen atom selected from the group consisting of silicon and phosphorus, halide anions, perchlorate ion, chlorate ion, thiocyanate ion, hexafluoro A phosphate ion, a hexafluoroantimonate ion, a tetrafluoroborate ion, an organic carboxylate anion, an organic sulfonate anion, an organic phosphate anion, an organic imide acid anion, an organic methide acid anion, and a metal complex anion; The colored curable resin composition according to Item 1.   The colored curable resin composition according to claim 1 or 2, wherein the colorant further contains a yellow pigment (excluding the compound represented by the formula (I)).   A color filter formed from the colored curable resin composition according to any one of claims 1 to 3.   A display device comprising the color filter according to claim 4.