WO2019093797A2 - Coloring curable resin composition, color filter, and display device - Google Patents

Abstract

The present invention relates to a coloring curable resin composition, a color filter, and a display device, wherein the coloring curable resin composition comprises a colorant, a resin, a polymerizable compound, and a polymerization initiator, the colorant containing a compound represented by formula (I) and a red pigment (but excluding a compound represented by formula (I)), the content percent of the red pigment being equal to or more than 1 mass% and equal to or less than 95 mass% relative to the total weight of the colorant.

Description

Coloring curable resin composition, color filter and display device

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

Display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays, and color filters used in solid-state image pickup devices such as CCDs and CMOS sensors are made of a colored curable resin composition. As such a color-curable resin composition, a composition containing only a compound represented by the following formula as a coloring agent is known.

(International Publication No. 2014/196464)

The color filter formed from the conventionally known colored curable resin composition does not satisfy the brightness. In addition, the color filter formed of the above-mentioned conventionally known colored curable resin composition can not satisfy the light resistance.

The gist of the present invention is as follows.

[1] A colorant comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,

Wherein the colorant comprises a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)),

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.

[In the formula (I)

Each of R ¹ to R ¹⁰ 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.

R ¹¹ to R ¹⁶ each independently represent 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, and the hydrogen atom contained in the saturated hydrocarbon group, A cyano group, a nitro group, a hydroxyl group or a halogen atom, and the hydrogen atom contained in the phenyl group and the benzyl group may be substituted with a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, 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 connected 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 are each To form a 6-membered ring.

A ^q- represents an anion of q, and q represents an integer of 1-14.

p represents the coefficient that the compound represented by the formula (I) holds the charge neutral.

[2] A colorant comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,

Wherein the colorant comprises a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)),

Wherein the content of the red pigment is 30 mass% or more and 95 mass% or less with respect to the total amount of the coloring agent.

[In the formula (I)

Each of R ¹ to R ¹⁰ 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.

R ¹¹ to R ¹⁶ each independently represent 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, and the hydrogen atom contained in the saturated hydrocarbon group A nitro group, a hydroxyl group or a halogen atom, and the hydrogen atom contained in the phenyl group and the benzyl group may be substituted with a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, 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 connected 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 are each To form a 6-membered ring.

A ^q- represents an anion of q, and q represents an integer of 1-14.

p represents the coefficient that the compound represented by the formula (I) holds the charge neutral.

[3] A ^q- is 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 ion, a chlorate ion, a thiocyanate ion, Wherein the metal ion is selected from the group consisting of a metal ion, a borate ion, a hexafluoroantimonate ion, a tetrafluoroborate ion, an organic carbonic acid anion, an organic sulfonic acid anion, an organic phosphate anion, an organic imidic acid anion, ] Or [2].

[4] The colored curable resin composition according to any one of [1] to [3], wherein the coloring agent further comprises 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 comprising 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. Further, according to the colored curable resin composition of the present invention, a color filter excellent in light resistance can be formed.

The colored curable resin composition of the present invention is a colored curable resin composition comprising a colorant (hereinafter may be referred to as a colorant (A)), a resin (hereinafter sometimes referred to as a resin (B) ), And a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)).

The colorant (A) comprises a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)), wherein the content of the red pigment is 1% by mass or more to 95% % Or less.

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 respective components may be used singly or in combination of plural kinds, unless otherwise specified.

≪ Colorant (A) >

The colorant (A) includes a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)).

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

[In the formula (I)

Each of R ¹ to R ¹⁰ 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.

R ¹¹ to R ¹⁶ each independently represent 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, and the hydrogen atom contained in the saturated hydrocarbon group A nitro group, a hydroxyl group or a halogen atom, and the hydrogen atom contained in the phenyl group and the benzyl group may be substituted with a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, 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 connected 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 are each To form a 6-membered ring.

A ^q- represents an anion of q, and q represents an integer of 1-14.

p represents the coefficient that the compound represented by the formula (I) holds the charge neutral.

The saturated hydrocarbon group having 1 to 8 carbon atoms representing R ¹ to R ¹⁰ and R ¹¹ to R ¹⁶ may be any of straight chain, branched chain and cyclic. Examples of the linear or branched saturated hydrocarbon group include straight chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and octyl group; isopropyl group, isobutyl group, isopentyl group, neopentyl group , And a branched chain alkyl group such as a 2-ethylhexyl group. The number of carbon atoms in 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 3 to 8, and more preferably 6 to 8.

Among them, a straight chain 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 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, it is preferable that a halogen atom is substituted as in the case of forming a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, or a heptafluoropropyl unit.

In R ¹¹ to R ¹⁶ , the hydrogen atom contained in the 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.

In R ¹¹ to R ¹⁶ , the hydrogen atom contained in the phenyl group and the benzyl group may be substituted with a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or a vinyl group.

The saturated hydrocarbon group having 1 to 4 carbon atoms which may be substituted with the hydrogen atom included in the phenyl group and the benzyl group represented by R ¹¹ to R ¹⁶ includes the same saturated hydrocarbon group having 1 to 4 carbon atoms as the saturated hydrocarbon group having 1 to 8 carbon atoms .

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 are each To form a 6-membered ring.

Examples of the 6-membered ring include a benzene ring, a piperidine ring, a pyridine ring, a phylimidine 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 linked together to form a 3- to 6-membered heterocyclic ring containing a nitrogen atom.

Examples of the 3- to 6-membered heterocyclic ring include pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring, thiomorpholine ring, pyrrole ring, imidazole ring, imidazolidine ring, pyrazolidine ring, Nitrogen-containing heterocycle such as pyridine ring, pyridine ring and the like, and preferably nitrogen-containing aliphatic heterocycle having only one nitrogen atom as a hetero atom such as pyrrolidine ring and piperidine ring.

Wherein R ¹ to R ⁶ , R ⁸ and R ¹⁰ are each independently a hydrogen atom, R ⁷ and R ⁹ are each independently a hydrogen atom or a halogen atom, and R ¹¹ to R ¹⁶ each independently represent a hydrogen atom, Is preferably a saturated hydrocarbon group of 1 to 8 carbon atoms,

Each of R ¹ to R ⁶ , R ⁸ and R ¹⁰ is independently a hydrogen atom, R ⁷ and R ⁹ are each independently a halogen atom, and R ¹¹ to R ¹⁶ are each independently an alkyl group having 1 to 6 carbon atoms Of saturated hydrocarbon groups.

A ^q- is an anion of q, and an anion of any one of 1 to 14.

In other words, 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 the coefficient that the compound represented by the formula (I) holds the charge neutral. 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 anion, other inorganic anion, organic carbonic acid anion, organic sulfonic acid anion, organic phosphate anion, organic imidic acid anion, organic methidic acid anion, and metal complex anion.

Examples of the halide anion include a chloride ion, a bromide ion, an iodide ion, and a fluoride ion.

Examples of the inorganic anion include a perchlorate ion, a chlorate ion, a thiocyanate ion, a hexafluorophosphate ion (hereinafter also referred to as "anion VII"), a hexafluoroantimonic acid ion, a tetrafluoroborate ion, .

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, anions containing tungsten atoms and oxygen atoms are preferred.

Examples of the anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom include? - [PW ₁₂ O ₄₀ ] ^3- (hereinafter also referred to as "anion (IX) Tungstate ions such as? - [P ₂ W ₁₈ O ₆₂ ] ^6- and? - [P ₂ W ₁₈ O ₆₂ ] ^6- ; tungstate ions such as α- [SiW ₁₂ O _{40 ^{] 4-, β- [SiW 12 O}} 40] 4-, γ- [SiW 12 O 40] 4- , etc. Kane ginhyeong silicon tungstate _{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] containing tungsten such as ^4-, WO ₄ ^2- An isophosphoric acid ion, a silicate ion, and a phosphate ion.

Examples of the organic carbonic acid anion include acetic acid ion and the like.

Examples of the organic sulfonic acid anion include methanesulfonate ion, dodecylsulfonate ion, benzenesulfonate ion, toluenesulfonate ion, naphthalenesulfonate ion, diphenylamine-4-sulfonate ion, 2- A 2-amino-5-nitrobenzenesulfonic acid ion, a phthalocyanine sulfonic acid ion, a sulfonic acid ion having a polymerizable substituent, a benzene disulfonic acid anion, and a naphthalene disulfonic acid anion.

Examples of the organic phosphate anion include octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylenebis (4,6-di-t-butylphenyl) And the like.

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

Examples of the metal complex anion include CI Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, CI Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, CI Solvent Violet 2, 21, 21: 1, 46, 49, 49, 51, 51, 51, , 58, 61, CI Solvent Blue 137, CI Solvent Brown 28, 42, 43, 44, 53, 62, 63, CI Acid Yellow 59, 121, CI Acid Orange 74, 162, CI Acid Red 211, And anions derived from the metal complex salt dyes described in JP-A-170117.

Examples of the molecule (ligand) include azo molecules and methine molecules, and azo molecules are preferred.

Examples of the metal atom include chromium, cobalt, and nickel, and chromium and cobalt are preferable.

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

Among them, A ^q- is preferably an anion containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom, an organic carbonic acid anion, an organic sulfonic acid anion, an organic imidic acid anion, Acid anions and metal complex anions are preferable, and anion and metal complex anions containing at least one atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom are more preferable.

Further, a fluorine-containing organic acid anion, a fluorine-containing organic sulfonic acid anion, a fluorine-containing organic imidic acid anion and a fluorine-containing organic acid anion (hereinafter collectively referred to as a fluorine anion) are more preferable.

Examples of fluorine anions include CF ₃ CO ₂ ^- and anions represented by formulas (III), (IV), (V) or (VI).

Wherein W ³ and W ⁴ independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms or W ³ and W ⁴ together form an alkyl fluoride group having 1 to 4 carbon atoms Represents a diary.]

[In the formula (IV), W ⁵ to W ⁷ independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms.]

[In the formula (V), Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms.]

[In the formula (VI), Y ² represents an alkyl fluoride group having 1 to 4 carbon atoms.]

In the formulas (III), (IV) and (VI), as the fluorinated alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group is preferable. Examples in the art 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 ), and the _2, -C (CF _{3) 3.}

In the formulas (III) and (V), as the fluorinated alkanediyl group having 1 to 4 carbon atoms, a perfluoroalkanediyl group is preferable, and -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.

Examples of the anion represented by the formula (III) (hereinafter also referred to as "anion (III)") include anions represented by the formulas (III-1) to (III- Quot; to " anion (III-6) ").

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

The anions represented by the formulas (V-1) to (V-4) (hereinafter, referred to as "anions (V-1)" - " anion (V-4) ").

The anions represented by the formulas (VI-1) to (VI-4) (hereinafter, referred to as "anions (VI-1)") as the anions represented by the formula (VI) - " anion (VI-4) ").

The fluorine 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 these, CF ₃ CO ₂ ^-, an anion (III-1), anionic (III-2), anions (III-6), anions (IV-1), anionic (V-1), anionic (VI-1) , The anion (VI-2) and the anion (VI-3) are preferable and the 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 (I-A).

(In the formula (IA), R ⁷ , R ⁹ , R ¹¹ to R ¹⁶ , p, q and A ^q- have the same meanings as defined above)

In the following Tables 1 to 10, 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, 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) (IX).

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

(Table 1)

(Table 2)

(Table 3)

(Table 4)

(Table 5)

(Table 6)

(Table 7)

(Table 8)

(Table 9)

(Table 10)

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

The compound represented by the formula (I) can be prepared, for example, by referring to the method described in International Publication No. 2014/196464.

The content of the compound represented by the formula (I) is preferably from 1 to 50 mass%, more preferably from 2 to 40 mass%, and still more preferably from 3 to 30 mass% More preferable.

The content of the compound represented by the formula (I) is preferably 0.2 mass% or more and 20 mass% or less, more preferably 0.5 mass% or more and 15 mass% or less, and 1 mass% or more and 12 mass% or less More preferable.

Here, the "total solid content" in the present specification means the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total solid content and the content of each component in the solid content can be measured by known analytical 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. For example, among the pigments classified as pigments in the color index (The Society of Dyers and Colourists), red . Two or more species may be used in combination. However, the compounds represented by the formula (I) are excluded.

Specifically, CI 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 and diketopyrrolopyrrole pigments are preferable, and C.I. Pigment Red 177, 179, 202, 208, 242, 254, 269, brominated diketopyrrolopyrrole pigments are preferred, and C.I. Pigment Red 177, 202, 254, 269, brominated diketopyrrolopyrrole pigments are more preferable.

The content of the red pigment is preferably 1% by mass or more and 95% by mass or less, more preferably 30% by mass or more and 95% by mass or less, more preferably 40% by mass or more and 90% by mass or less relative to the total amount of the colorant, more preferably 50% And still more preferably at least 60% by mass.

Instead of generating RGB from the white light emitting layer through the color filter, the RGB color pixels are stacked on the substrate, and the red, green, and blue R, G, 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), a red colored coating film excellent in light resistance can be obtained.

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

When the colored curable resin composition of the present invention contains the following colorant (A1), the total content of the compound represented by the formula (I) and the red pigment is preferably 40% by mass or more, Is not less than 50% by mass, preferably not more than 99% by mass, more preferably not more than 95% by mass.

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

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

The colorant (A1) may be a dye or a pigment. Examples of the dyes include known dyes described in Color Index (published by The Society of Dyers and Colourists) and dyeing notes (Colored Yarn). According to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes (except compounds represented by formula (I)), cyanine dyes, naphthoquinone dyes, quinone imine dyes, , Azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes and phthalocyanine dyes. Of these, organic solvent-soluble dyes are preferred. These dyes may be used in combination of two or more.

Specifically, dyes having the following color index (CI) numbers can be mentioned. C. I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

CI 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;

CI 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;

CI 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;

CI 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 1st.

As the pigment, a known pigment can be used, and for example, a pigment classified as pigment in the color index (The Society of Dyers and Colourists) can be mentioned. Two or more species may be used in combination. Provided that the compound represented by the formula (I) is excluded.

Specifically, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;

C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments of Pigment Green 7, 36, 58 and 59. [

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

When a 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, based on the total amount of the colorant.

The content of the yellow pigment is preferably 0.2% by mass or more and 25% by mass or less, and more preferably 0.6% by mass or more and 20% by mass or less, based on the entire 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) may be subjected to a rosin treatment, a coloring agent derivative into which an acidic group or a basic group has been introduced Surface treatment using a polymer compound, graft treatment to a surface such as a pigment such as a pigment, atomization treatment using a sulfuric acid atomization method and the like, cleaning treatment with an organic solvent or water for removing impurities, ion exchange treatment with ionic impurities, . The particle diameters of the pigment and the like are preferably substantially uniform. The pigment or the like is dispersed uniformly in the dispersion by carrying out dispersing treatment with a dispersant.

As the dispersing agent, a surfactant or the like can be enumerated, and any of cationic, anionic, nonionic or amphoteric surfactants may be used. Specific examples thereof include surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants. As another dispersing agent, a resin (B) described below may be used. These dispersants may be used alone or in combination of two or more. Examples of the dispersing agent include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), fluorene (manufactured by Kyowa Chemical Industry Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (registered trademark) (Manufactured by BASF), ADISPER (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.) and Disperbyk (registered trademark) (manufactured by BICKEMISA) and BYK (registered trademark) (manufactured by BICKEMISA).

When a dispersing agent is used, the amount of the dispersing agent to be used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the pigment and the like. When the amount of the dispersing agent used is within the above range, there is a tendency to obtain a coloring agent-containing liquid in a more uniform dispersion state.

The content of the colorant (A) in the colored curable resin composition is usually 10 to 60 mass%, preferably 12 to 55 mass%, more preferably 15 to 15 mass% 50% by mass or less.

&Lt; Resin (B) &gt;

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and at least one kind (a) (hereinafter referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride Is more preferable. The resin (B) may further contain a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)") (Hereinafter sometimes referred to as &quot; (c) &quot;) which is copolymerizable with the monomer (c) (provided that (a) and (b) are different), and a structural unit derived from an ethylenically unsaturated bond Having at least one kind of structural unit selected from the group consisting of structural units having the above-mentioned structural units.

(meth) acrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono [2- (meth) acryloyl And monooxyethyl], and the like, preferably acrylic acid, methacrylic acid, maleic anhydride.

In the present specification, the term "(meth) acrylic acid" refers to at least one kind selected from the group consisting of acrylic acid and methacrylic acid. "(Meth) acryloyl" and " The notation also has the same meaning.

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

(meth) acrylate, vinylbenzyl glycidyl ether, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, 3-ethyl (Meth) acryloyloxymethyl oxetane, tetrahydrofurfuryl (meth) acrylate and the like, and preferred examples thereof include glycidyl (meth) acrylate, 3,4-epoxy tricyclo [ 5.2.1.0 ^2,6 ] decyl (meth) acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane.

(meth) acrylate, butyl (meth) acrylate cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 Acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, Vinyl toluene, and the like. Styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferable.

The resin having a structural unit having an ethylenically unsaturated bond in the side chain may be obtained by adding (b) to the copolymer of (a) and (c), or by adding (a) to the copolymer of (b) . The resin may be a resin obtained by adding (a) to a copolymer of (b) and (c) and further reacting with a carbonic 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, 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 for neutralizing 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

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

&Lt; Polymerizable compound (C) &gt;

The polymerizable compound (C) is a compound capable of being polymerized by an active radical and / or an acid generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenic unsaturated bond, 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. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) 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 mass%, more preferably 5 to 50 mass%, and still more preferably 11 to 40 mass%, based on the entire solid content.

&Lt; Polymerization initiator (D) &gt;

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical or an acid by the action of light or heat and capable of initiating polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- 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-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis 2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, and the like.

The polymerization initiator is preferably a polymerization initiator comprising at least one member selected from the group consisting of a triazine compound, an acylphosphine oxide compound, an alkylphenone compound, an O-acyloxime compound and a nonimidazole compound, and O- A polymerization initiator comprising a compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and 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 of the color filter tends to be shortened and the exposure time is shortened.

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 90% by mass or more based on the total amount of the polymerization initiator (D) By mass is 95% by mass or more. When the content of the O-acyloxime compound is within the above range, there is a tendency that a color filter having high sensitivity can be produced even when the sensitivity, developability and colorant content in forming a colored pattern are high.

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

&Lt; Polymerization initiator (D1) &gt;

The polymerization initiator (D1) is a compound or a sensitizer used for promoting polymerization of a polymerizable compound initiated by polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator (D1) include 4,4'-bis (dimethylamino) benzophenone (commonly referred to as Mihiraazuketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethyl thioxanthone N-phenylglycine, and the like.

When these polymerization initiator (D1) is used, its content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Mass part. When the amount of the polymerization initiator (D1) is within this range, it is possible to form a colored pattern 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.

&Lt; Solvent (E) &gt;

The solvent (E) is not particularly limited, and a solvent commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (containing OH in the molecule, O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide, and the like.

Examples of the solvent include ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetone and γ-butyrolactone Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol Ether solvents such as dimethyl ether and diethylene glycol methyl ethyl ether (solvents containing -O- in the molecule and 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 and diethylene glycol monoethyl ether acetate A solvent containing -COO- and -O-);

Ketone solvents such as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, cyclohexanone Alcohol solvents such as butanol, cyclohexanol and propylene glycol (solvents containing OH in the molecule and containing no -O-, -CO- and -COO-), and the like . Aromatic hydrocarbon solvents such as benzene, toluene, xylene and mesitylene.

Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

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. Examples of the solvent to be combined with propylene glycol monomethyl ether acetate include diacetone alcohol, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl Methoxybutyl acetate, 3-methoxy-1-butanol and 4-hydroxy-4-methyl-2-pentanone are preferable, and diacetone alcohol, propylene glycol monomethyl ether, dipropylene glycol methyl Ethoxyacetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate are more preferable, and diacetone alcohol, ethyl lactate, 4-hydroxy- - pentanone and propylene glycol monomethyl ether are more preferred.

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 relative to the total amount of the solvent, 5 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, 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 characteristics are not insufficient when the color filter is formed, so that display characteristics tend to be good.

<Other components>

The colored curable resin composition of the present invention may contain additives known in the art such as leveling agents, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, if necessary.

&Lt; Process for producing colored curable resin composition &gt;

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

<Manufacturing Method of Color Filter>

Examples of the method for producing a colored pattern with the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Among them, a photolithographic method is preferable. In the photolithographic method, a colored coating film which is a cured product of the colored composition layer can be formed by not using a photomask at the time of exposure and / or not developing it. The coloring pattern or 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. Such a color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

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

In the following Synthesis Examples, the compounds were identified by mass analysis (LC: Agilent 1200 type, MASS: Agilent LC / MSD type) or elemental analysis (VARIO-EL;

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 占 폚 for 8 hours. The reaction solution was added dropwise to an aqueous solution of sodium hydroxide, the organic matter was extracted with toluene, washed with water three times, and 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 isomer.

27 parts of the leucite, 184.4 parts of p-chloranyl, 15 parts of acetic acid and 0.9 part of hydrochloric acid were mixed and stirred at 60 DEG 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 hydrogencarbonate solution. And 1.4 parts of bis (trifluoromethanesulfonyl) imide potassium were added thereto. After salt exchange, the mixture was washed with water, and the solvent was distilled off 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 (yield: 27%) of a compound represented by formula (I-104) .

Synthesis Example 2

Synthesis of hydrochloride

4.0 parts of the above-mentioned leucite, 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, and the precipitated solid was removed by filtration. The organic layer was washed with water, and then sodium sulfate was added, dried, and the solvent was distilled off. 200 parts of concentrated hydrochloric acid was added, stirred for 6 hours, dropped into 600 parts of 10% saline, and stirred overnight. The precipitated solid was filtered, and a 5% aqueous solution of sodium hydroxide was added to the filtrate to neutralize it to pH 4, and the precipitated solid was also filtered. The combined solids were dispersed washed with water, filtered, and the solid was dried in a 60 deg. C vacuum oven to obtain 4.1 parts (yield 95%) of the compound represented by the formula (I-XI).

Synthesis Example 3

Synthesis of phosphotungstate

, 3.00 parts of the compound represented by the formula (I-XI) and 515 parts of methanol were mixed and 30.1 parts of phosphotungstic acid hydrate (manufactured by SIGMA-ALDRICH) and 30.5 parts of methanol were added dropwise while stirring at room temperature, After stirring for 3 hours. The precipitated solid was filtered off, washed with 50.0 parts of methanol three times, and then the solid was dried in a 60 ° C vacuum oven to obtain 10.6 parts (yield: 60%) of a compound represented by the formula (I-312).

Synthesis Example 4

Synthesis of Solvent Yellow 21 Salt

0.20 parts of a compound represented by the formula (I-XI), 0.11 part of Solvent Yellow 21 and 4.8 parts of N, N-dimethylsulfoxide were mixed and stirred at 50 ° C for 3 hours. The reaction solution was added dropwise to 40 parts of 20% saline, and the precipitated solid was filtered. The solid was dissolved in chloroform, and the organic layer was washed with water. Sodium sulfate was added, dried, and the solvent was distilled off. And dried in a 60 DEG C vacuum oven to obtain 0.43 part (yield: 85%) of a compound represented by the formula (I-308).

Synthesis Example 5

174 parts of tert-amyl alcohol and 22.2 parts of metallic sodium were reacted at 130 占 폚 in a nitrogen atmosphere to synthesize sodium tert-amyl alcohol. This was heated to 60 占 폚, and then 91.0 parts of 4-bromobenzonitrile, 71.05 parts of di-tert-amyl ester succinate and 108.9 parts of tert-amyl alcohol were added and stirred for 2 hours so that the liquid temperature was 85 占 폚 or lower. This suspension was further stirred for 18 hours or longer, and then added to a mixture of 200 parts of methanol cooled at -10 DEG C, 1000 parts of water and 49.21 parts of sulfuric acid. After completion of the addition of the suspension, the mixture was kept at 0 캜 and stirred for 5 hours to complete the reaction, followed by filtration of the solid component. The solid component was washed repeatedly with methanol and water until the color of the filtrate was removed and precipitation of the salt was eliminated. Thereafter, the solid content was dried in a vacuum drier at 80 DEG C for 18 hours to obtain the aimed red pigment 1. The yield was 107 parts.

Synthesis Example 6

A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen and replaced with a nitrogen atmosphere. Then, 141 parts of ethyl lactate and 178 parts of propyleneglycol monomethylether acetate were added and heated to 85 캜 with 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 ] dec-9- A mixed solution of 25 parts of a mixture (content of 1: 1), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution obtained by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) having a solid content of 25.6%. The resulting copolymer had a weight average molecular weight Mw of 8000, a dispersion degree of 2.1, and an acid value in terms of solid content of 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 put into a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 DEG C with stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane- 9-yl acrylate (content: 1: 1) in 125 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours using a dropping pump. On the other hand, a solution obtained by dissolving 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was dropped into the flask over about 6 hours using another dropping pump. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-2)) having a solid content of 35.1%. The resulting copolymer had a weight-average molecular weight Mw of 9200, a degree of dispersion of 2.08, and an acid value in terms of solid content of 77 mg-KOH / g. Resin (B-2) has the following structural unit.

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

Apparatus: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 占 폚

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL / min

Detector; RI

TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

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

[Preparation of dispersion 1 (Br-DPP)]

, 28 parts of a red pigment 1 compound, 10 parts of a dispersant (BYKLPN-6919 solid content converted by BYK), 8 parts of a resin (B-2) (in terms of solid content) and 154 parts of propylene glycol monomethyl ether acetate were mixed, Of zirconium oxide beads (600 parts) were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconium oxide beads were removed by filtration to obtain dispersion 1.

[Preparation of dispersion 2 (Y138)]

, 24 parts of CI Pigment Yellow 138, 11 parts of a dispersant (BYKLPN-6919 solid content converted by BYK), 5 parts of a resin (B-2) (in terms of solid content) and 160 parts of propylene glycol monomethyl ether acetate, 600 parts of zirconium oxide zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, zirconium oxide beads were removed by filtration to obtain dispersion 2.

[Preparation of Dispersion Liquid 3 (Y231)]

24 parts of CI Pigment Yellow 231, 11 parts of a dispersant (BYKLPN-6919 solid content converted by BYK), 5 parts of a resin (B-2) (in terms of solid content) and 160 parts of propylene glycol monomethyl ether acetate, 600 parts of zirconium oxide zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconium oxide beads were removed by filtration to obtain dispersion 3.

[Preparation of dispersion 4 (Y185)]

, 20 parts of CI Pigment Yellow 185, 11 parts of a dispersant (BYKLPN-6919 solid content converted by BYK Co.), 5 parts of a resin (B-2) (in terms of solid content) and 160 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of zirconium oxide zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, zirconium oxide beads were removed by filtration to obtain dispersion 4.

[Preparation of Dispersion 5 (R177)]

, 26 parts of CI Pigment Red 177, 7 parts of a dispersant (BYKLPN-6919 solid content converted by BYK Co.), 10 parts of a resin (B-2) (in terms of solid content) and 157 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of zirconium oxide zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconium oxide beads were removed by filtration to obtain dispersion 5.

[Preparation of dispersion 6 (R269)]

, 26 parts of CI Pigment Red 269, 11 parts of a dispersant (BYKLPN-6919 solid content converted by BYK Co., Ltd.) and 164 parts of propylene glycol monomethyl ether acetate were mixed and 600 parts of zirconium oxide beads of 0.4 탆 were added. Ltd.) for 1 hour. Thereafter, the zirconium oxide beads were removed by filtration to obtain dispersion 6.

[Preparation of dispersion 7 (R254)]

, 30 parts of CI Pigment Red 254, 6 parts of a dispersant (BYKLPN-6919 converted to BYK's 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 zirconium oxide zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconium oxide beads were removed by filtration to obtain dispersion 7.

[Preparation of dispersion 8 (Y139)]

, 24 parts of CI Pigment Yellow 139, 8 parts of dispersant (BYKLPN-6919 converted to solid content by BYK), 8 parts of resin (B-2) (in terms of solid content), 10 parts of propylene glycol monomethyl ether, And 150 parts of ether acetate were mixed, 600 parts of zirconium oxide beads having a thickness of 0.4 mu m were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconium oxide beads were removed by filtration to obtain dispersion 8.

[Preparation of dispersion 9 (D2428-PWA I-312)]

10 parts of the compound (I-312), 12 parts of a dispersant (BYKLPN-6919 converted to BYK's solid content), 8 parts of the resin (B-2) (in terms of solid content), 20 parts of diacetone alcohol, Acetate were mixed and 600 parts of zirconium oxide beads having a thickness of 0.4 mu m were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconium oxide beads were removed by filtration to obtain dispersion 9.

[Preparation of Dispersion 10 (R202)]

, 24 parts of CI Pigment Red 202, 11 parts of dispersant (BYKLPN-6919 in terms of solid content BYK), 8 parts of resin (B-2) (in terms of solid content), 20 parts of propylene glycol monomethyl ether, And 136 parts of ether acetate were mixed and 600 parts of zirconium oxide beads of 0.4 mu m were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconium oxide beads were removed by filtration to obtain dispersion 10.

[Examples 1 to 10 and Comparative Examples 1 and 2]

[Preparation of colored curable resin composition]

The components shown in Tables 11 and 12 were mixed to obtain respective colored curable resin compositions.

(Table 11)

(Table 12)

Resin (B-1): Resin B-1 (in terms of solid content)

Polymerizable compound (C-1): dipentaerythritol hexaacrylate ("A9550", produced by Shin-Nakamura Chemical Co., Ltd.)

Polymerization initiator (D-1): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,

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 (in terms of solid content) (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.)

&Lt; Fabrication of color filter (colored coating film) &gt;

The colored curable resin composition was coated on a glass substrate (Eagle 2000; Corning) having a 5 cm edge by a spin coating method, and then prebaked at 100 占 폚 for 3 minutes to form a coloring composition layer. After cooling, the coloring composition layer was irradiated with light at an exposure amount of 60 mJ / cm 2 (365 nm standard) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). Thereafter, post-baking was performed in an oven at 230 캜 for 20 minutes to obtain a color filter.

[Measurement of film thickness]

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

[Chromaticity evaluation]

The obtained color filter was measured for spectroscopy using a colorimeter (OSP-SP-200, manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) of the CIE XYZ table colorimeter, y) and stimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 13.

&Lt; Evaluation of light resistance &

(COLORED OPTICAL GLASS L38, manufactured by Hoya Co., Ltd., light cut at 380 nm or less) was placed on the obtained colored coating film, and a xenon lamp light was irradiated with a light resistance tester (acid test CPS + I investigated.

The xy chromaticity coordinates (x, y) and Y were measured before and after the irradiation, and the color difference DELTA Eab * was calculated from the measured values by the method described in JIS Z 8730: 2009 (Method for calculating color difference) . The smaller the value of? Eab *, the smaller the color change. When the light resistance of the colored coating film is good, the colored pattern made of the same colored curable resin composition can also be said to have good light resistance.

(Table 13)

(Table 14)

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

Claims (5)

A colorant, a resin, a polymerizable compound and a polymerization initiator, Wherein the colorant comprises a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)), 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.

[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 may be substituted with a halogen atom, R ¹¹ to R ¹⁶ each independently represent 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, and the hydrogen atom contained in the saturated hydrocarbon group A nitro group, a hydroxyl group or a halogen atom, and the hydrogen atom contained in the phenyl group and the benzyl group may be substituted with a saturated hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, 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 connected 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 are each To form a 6-membered ring, A ^q- represents an anion of q, q represents an integer of 1 to 14, p represents the coefficient that the compound represented by the formula (I) holds the charge neutral.   The method according to claim 1, A ^q- is 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 ion, a chlorate ion, a thiocyanate ion, a hexafluorophosphate ion , A hexafluoroantimonic acid ion, a tetrafluoroboric acid ion, an organic carbonic acid anion, an organic sulfonic acid anion, an organic phosphate anion, an organic imidic acid anion, an organic methidic acid anion, and a metal complex anion. The method according to claim 1, Wherein the coloring agent further comprises 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.