JP7063663B2 - Color curable resin composition, color filter and display device - Google Patents

Description

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

Color filters used in display devices such as liquid crystal displays, electroluminescence display devices and plasma displays, and solid-state image pickup devices such as CCDs and CMOS sensors are manufactured from colored curable resin compositions. As such a color-curable resin composition, a composition containing a compound represented by the following formula as a colorant is known (Patent Document 1).

Japanese Unexamined Patent Publication No. 2015-60154

The color filter formed from the above-mentioned color-curable resin composition known conventionally has not been satisfactory in brightness.

The gist of the present invention is as follows.
[1] Containing a colorant, a resin, a polymerizable compound and a polymerization initiator,
The colorant comprises a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)).
A coloring curable resin composition in which the content of the red pigment is 10% by mass or more and 95% by mass or less with respect to the total amount of the colorant.

[In formula (I),
R ¹ to R ¹¹ independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and are included in the saturated hydrocarbon group and the aryl group. The hydrogen atom is substituted with a halogen atom.
R ¹² to R ¹⁵ 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 are contained in the saturated hydrocarbon group. The hydrogen atom may be substituted with a halogen atom, and the phenyl group and the hydrogen atom contained in the benzyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group or a vinyl group. good.
R ¹ and R ¹³ , R ² and R ¹² , R ⁴ and R ¹⁵ and R ⁵ and R ¹⁴ may be linked to form a 6-membered ring containing a nitrogen atom, respectively, and R ¹² and R ¹³ and R ¹⁴ and R ¹⁵ may be linked to each other to form a 3- to 6-membered heterocycle containing a nitrogen atom.
A ^q- represents a q-valent anion and q represents 1 or 2.
p represents a coefficient by which the compound represented by the formula (I) keeps the charge neutral. ]
[2] The coloring curable resin composition according to [1], wherein the coloring agent further contains a yellow pigment (excluding the compound represented by the formula (I)).
[3] A color filter formed from the colored curable resin composition according to [1] or [2].
[4] A display device including the color filter according to [3].

According to the colored curable resin composition of the present invention, it is possible to form a color filter having excellent lightness.

The color-curable resin composition of the present invention includes a colorant (hereinafter, may be referred to as a colorant (A)), a resin (hereinafter, may be referred to as a resin (B)), and a polymerizable compound (hereinafter, a polymerizable compound). (C)) and a polymerization initiator (hereinafter, may be referred to as a polymerization initiator (D)).
The colorant (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 based on the total amount of the colorant. It is 10% by mass or more and 95% by mass 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 each component may be used alone or in combination of a plurality of 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 formula (I),
R ¹ to R ¹¹ independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and are included in the saturated hydrocarbon group and the aryl group. The hydrogen atom is substituted with a halogen atom.
R ¹² to R ¹⁵ 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 are contained in the saturated hydrocarbon group. The hydrogen atom may be substituted with a halogen atom, and the phenyl group and the hydrogen atom contained in the benzyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group or a vinyl group. good.
R ¹ and R ¹³ , R ² and R ¹² , R ⁴ and R ¹⁵ and R ⁵ and R ¹⁴ may be linked to form a 6-membered ring containing a nitrogen atom, respectively, and R ¹² and R ¹³ and R ¹⁴ and R ¹⁵ may be linked to each other to form a 3- to 6-membered heterocycle containing a nitrogen atom.
A ^q- represents a q-valent anion and q represents 1 or 2.
p represents a coefficient by which the compound represented by the formula (I) keeps the charge neutral. ]

The saturated hydrocarbon group having 1 to 8 carbon atoms representing R ¹ to R ¹⁵ may be linear, branched or cyclic. Linear or branched saturated hydrocarbon groups include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and octyl group; isopropyl group, isobutyl group and isopentyl group. Examples thereof include a branched chain alkyl group such as a group, a neopentyl group and a 2-ethylhexyl group. The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and preferably 1 to 4 carbon atoms.
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 cyclic saturated hydrocarbon group preferably has 3 to 8 carbon atoms, more preferably 6 to 8 carbon atoms.
Of these, a linear saturated hydrocarbon group is preferable, and a methyl group, an ethyl group, and a propyl group are particularly preferable.

Examples of the aryl group having 6 to 20 carbon atoms of R ¹ to R ¹¹ include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group and the like, and phenyl is preferable. It is a group, a naphthyl group, a tolyl group, a xylyl group, and particularly preferably a phenyl group. The aryl group has 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 12 carbon atoms.

The hydrogen atom contained in the saturated hydrocarbon group and the aryl 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 the halogen atom is substituted so as to form a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, or a heptafluoropropyl unit.

The compound represented by the formula (I) preferably has 1 or more and 5 or less halogen atoms, more preferably 1 or more and 3 or less halogen atoms, and further preferably 1 or 2 halogen atoms. .. The halogen atom may include one in which a hydrogen atom is substituted.

Among them, at least one of R ¹ to R ¹¹ is preferably a halogen atom, and at least one of R ⁷ to R ¹¹ is more preferably a halogen atom, and any one of R ⁷ to R ¹¹ is more preferable. It is more preferable that one is a halogen atom. If two of R ¹ to R ¹¹ are halogen atoms, then R ⁷ and R ⁸ , R ⁷ and R ⁹ , R ⁷ and R ¹⁰ , R ⁷ and R ¹¹ , R ⁸ and R ⁹ , and R ⁸ It is more preferred that R ¹⁰ , R ⁸ and R ¹¹ , R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , or R ¹⁰ and R ¹¹ are halogen atoms. Among them, it is even more preferable that R ⁷ , R ⁷ and R ⁸ , R ⁷ and R ⁹ , R ⁹ and R ¹¹ are halogen atoms, and R ⁷ , R ⁷ and R ⁸ , R ⁹ and R ¹¹ are halogen atoms. Is particularly preferable.
Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, but chlorine is most preferable.

In R ¹² to R ¹⁵ , the hydrogen atom contained in the phenyl group and the benzyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group or a vinyl group.
The hydrogen atom contained in the phenyl group and the benzyl group of R ¹² to R ¹⁵ may be substituted, and the alkyl group having 1 to 4 carbon atoms has the number of carbon atoms among the saturated hydrocarbon groups having 1 to 8 carbon atoms. The same as those of 1 to 4 can be mentioned.

R ¹ and R ¹³ , R ² and R ¹² , R ⁴ and R ¹⁵ , and R ⁵ and R ¹⁴ may be linked to form a 6-membered ring containing a nitrogen atom.
Examples of the 6-membered ring include a tetrahydropyridine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring and the like.

R ¹² and R ¹³ and R ¹⁴ and R ¹⁵ may be linked to form a 3- to 6-membered heterocycle containing a nitrogen atom, respectively.
Examples of the 3- to 6-membered heterocycle include a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperazine ring, a thiomorpholine ring, a pyrrol ring, an imidazole ring, an imidazolidine ring, a pyrazolidine ring, an isothiazolidin ring and the like. However, a nitrogen-containing aliphatic heterocycle having only one nitrogen atom as a heteroatom such as a pyrrolidine ring and a piperidine ring is preferable.

Both R ¹ to R ⁶ are hydrogen atoms, at least one of R ⁷ to R ¹¹ is a halogen atom, and R ¹² to R ¹⁵ are independently saturated hydrocarbon groups having 1 to 8 carbon atoms. Is preferable,
R ¹ to R ⁶ are both hydrogen atoms, one or two of R ⁷ to R ¹¹ are halogen atoms, and R ¹² to R ¹⁵ are independent linear chains having 1 to 8 carbon atoms. More preferably, it is a state-saturated hydrocarbon group.
R ¹ to R ⁶ are both hydrogen atoms, and any one of R ⁷ to R ¹¹ is a halogen atom, or R ⁷ and R ⁸ , R ⁷ and R ⁹ , R ⁷ and R ¹⁰ , R ⁷ and R ¹¹ , R ⁸ and R ⁹ , R ⁸ and R ¹⁰ , R ⁸ and R ¹¹ , R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , or R ¹⁰ and R ¹¹ are halogen atoms and R ¹² It is more preferable that each of ~ R ¹⁵ is an alkyl group having 1 to 4 carbon atoms independently.
It is preferable that both R ⁷ to R ¹¹ representing a non-halogen atom are hydrogen atoms.

A ^q- represents a q-valent anion and q represents 1 or 2.
p represents a coefficient by which the compound represented by the formula (I) keeps the charge neutral. Specifically, p is preferably 1 to 14, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 1 or 2. be.

Examples of the anion include halide anions, other inorganic anions, organic carboxylic acid anions, organic sulfonic acid anions, organic phosphate anions, organic imidoic acid anions, organic methidoic acid anions, and organic chromic acid anions.

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

Examples of the inorganic anion include perchlorate ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion (hereinafter sometimes referred to as "anion (VII)"), hexafluoroantimonate ion, tetrafluoroborate ion and the like. Can be mentioned.

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

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)”). .) And other kegin-type phosphotungstate ions; α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- and other Dawson-type phosphotungstate ions; α- [SiW ₁₂ ] O ₄₀ ] ^4- , ^β- [ _{SiW 12} O ₄₀ ] ^4- , _γ- [ _{SiW 12} O ₄₀ ] ^4- _etc . 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 ^2- , etc. Tungsten-containing isopolic acid ion; silicate ion; phosphate ion and the like can be mentioned.

Examples of the organic carboxylic acid anion include acetate ion, oxalate ion, benzoate ion and the like.

Examples of the organic sulfonic acid anion include methanesulfonic acid ion, dodecylsulfonic acid ion, benzenesulfonic acid ion, toluenesulfonic acid ion, naphthalenesulfonic acid ion, diphenylamine-4-sulfonic acid ion, and 2-amino-4-methyl-5. Examples thereof include chlorobenzene sulfonic acid ion, 2-amino-5-nitrobenzene sulfonic acid ion, phthalocyanine sulfonic acid ion, sulfonic acid ion having a polymerizable substituent, benzene disulfonic acid anion, naphthalenedi sulfonic acid anion and the like.
Examples of the organic phosphate anion include octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, and 2,2'-methylenebis (4,6-di-t-butylphenyl). Phosphate ions and the like can be mentioned.

Examples of the organic chromate anion include bis [(4,5-dihydro-3-methyl-5-oxo-1-phenyl-1H-pyrazole-4-yl) azo] benzoato] chromate ion (hereinafter referred to as “anion”). (VIII) "may be mentioned.) And the like.

Among them, as A ^q- , an inorganic anion, an organic carboxylic acid anion, an organic sulfonic acid anion, an organic imide acid anion, and an organic methidoic acid anion are preferable, and a hexafluorophosphate ion, a fluorine-containing organic carboxylic acid anion, and a fluorine-containing organic sulfone are preferable. Acid anions, fluorine-containing organic imidoic acid anions, and fluorine-containing organic methylated acid anions (hereinafter, these are collectively referred to as fluorine-containing anions) are more preferable.

Examples of the fluorine-containing anion include CF ₃ CO _2- ^and anions represented by the formulas (III), (IV), (V) or (VI).

[In formula (III), W ³ and W ⁴ represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms independently of each other, or W ³ and W ⁴ have a carbon number together. Represents 1 to 4 fluorinated alkanediyl groups. ]

[In formula (IV), W ⁵ to W ⁷ represent fluorine atoms or alkyl fluoride groups having 1 to 4 carbon atoms independently of each other. ]

[In the formula (V), Y ¹ represents an alkanediyl fluoride 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), the perfluoroalkyl group is preferable as the fluoroalkyl group having 1 to 4 carbon atoms. Examples of the perfluoroalkyl group include -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 , etc.

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

The anions represented by the formula (III) (hereinafter sometimes referred to as "anions (III)") include the anions represented by the formulas (III-1) to (III-6) (hereinafter, "anions (hereinafter referred to as" anions ()). III-1) ”to“ anion (III-6) ”) may be mentioned.

Examples of the anion represented by the formula (IV) (hereinafter, may be referred to as “anion (IV)”) include an anion (IV-1) represented by the formula (IV-1).

The anions represented by the formula (V) (hereinafter sometimes referred to as “anions (V)”) include the anions represented by the formulas (V-1) to (V-4) (hereinafter referred to as “anions (V)”). -1) ”to“ anion (V-4) ”).

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

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), Anions (VI-2) and anions (VI-3) are preferred, and CF ₃ CO _2- ^, anions (III-2), anions (IV-1) and anions (VI-1) are more preferred.

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

（式（Ｉ－Ａ）中、Ｒ⁷～Ｒ¹⁵、ｐ、ｑ、Ａ^q-は前記と同義である。）

(In the formula (IA), R ⁷ to R ¹⁵ , p, q, and A ^q- have the same meanings as described above.)

In Tables 1 to 8 below, Me is a methyl group, Et is an ethyl group, III-1 to III-6, VI-1, and VII are represented by the above formulas (III-1) to (III-6). Anion, an anion represented by the formula (VI-1), and an anion represented by the formula (VII).

The compound represented by the formula (IA) is preferably a compound represented by the formulas (I-1) to (I-480).

Among them, the compounds represented by the formulas (I-1) to (I-240) are preferable, and the compounds represented by the formulas (I-121) to (I-240) are more preferable, and the compounds represented by the formulas (I-126) are more preferable. )-The compound represented by the formula (I-150), the compound represented by the formula (I-226) to the formula (I-240) is more preferable, and the formula (I-136), the formula (I-141),. Compounds represented by formulas (I-142), formula (I-149), and formula (I-226) are particularly preferable, and formulas (I-136), formula (I-141), formula (I-149), and so on. The compound represented by the formula (I-226) is most preferable.

The content of the compound represented by the formula (I) is preferably 5% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 40% by mass or less, based on the total amount of the colorant. It is more preferably 5% by mass or more and 30% by mass or less.

The content of the compound represented by the formula (I) is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 15% by mass or less with respect to the total solid content. It is preferable that it is 2% by mass or more and 12% by mass or less.
Here, the "total amount of solid content" in the present specification means an amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component thereof can be measured by a known analytical means such as, for example, liquid chromatography or gas chromatography.

<Red pigment>
As the red pigment contained in the color curable resin composition of the present invention, known pigments can be used, and for example, among the pigments classified as pigments in the Color Index (The Society of Dyers and Colorists). , Those classified as red. Two or more types may be combined. However, the compound represented by the formula (I) is excluded.

Specifically, C.I. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, Examples thereof include red pigments such as 266, 268, 269, and 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. I. Pigment Red 177, 254, brominated diketopyrrolopyrrole pigments are more preferred.

The content of the red pigment is preferably 10% by mass or more and 95% by mass or less, preferably 30% by mass or more and 90% by mass or less, and more preferably 50% by mass or more with respect to the total amount of the colorant. It is more preferably 60% by mass or more.

When the color-curable resin composition of the present invention contains the colorant (A1) described later, the total content of the compound represented by the formula (I) and the red pigment is preferably 30% by mass with respect to the total amount of the colorant. % Or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, preferably 99% by mass or less, and more preferably 95% by mass or less.

The content of the red pigment is preferably 1% by mass or more and 60% by mass or less, and more preferably 2% by mass or more and 50% by mass or less with respect to the total solid content.

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

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

Specific examples thereof include dyes having the following color index (CI) numbers. C. I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68,
79, 81, 82, 83, 89, 94, 98, 99, 162;
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Reactive Yellow 2,76,116;
C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C. I. Disperse Yellow 51, 54, 76;
C. I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Reactive orange 16;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Acid Red 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 1st prize.

As the pigment, known pigments can be used, and examples thereof include pigments classified as pigments in the Color Index (The Society of Dyers and Colorists Publishing). Two or more types may be combined. However, the compound represented by the formula (I) is 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 other orange pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58, 59 green pigments can be mentioned.

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

When the yellow pigment is contained, the content thereof is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 40% by mass or less, and further preferably 5% by mass with respect to the total amount of the colorant. % Or more and 35% by mass or less.

The content of the yellow pigment is preferably 1% by mass or more and 25% by mass or less, more preferably 2% by mass or more and 20% by mass or less, and further preferably 3% by mass or more and 15% by mass or less, based on the total solid content. % Or less.

The compound represented by the formula (I), the red pigment and the pigment in the colorant (A1) (hereinafter, may be referred to as a pigment or the like) are introduced with a rosin treatment, an acidic group or a basic group, if necessary. Surface treatment using colorant derivatives, graft treatment on surfaces such as pigments with polymer compounds, atomization treatment by sulfuric acid atomization method, cleaning treatment with organic solvent or water to remove impurities, ionicity It may be removed by an ion exchange method or the like for impurities. It is preferable that the particle size of the pigment or the like is substantially uniform. Pigments and the like are uniformly dispersed in the dispersion liquid by containing a dispersant and performing a dispersion treatment.

Examples of the dispersant include a surfactant and the like, and any of a cationic type, anion type, nonionic type and amphoteric type surfactant may be used. Specific examples thereof include polyester-based, polyamine-based and acrylic-based surfactants. As another dispersant, the resin (B) described later may be used. These dispersants may be used alone or in combination of two or more. Dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), and EFKA (registered trademark). (BASF), Azisper (registered trademark) (Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (Big Chemie), BYK (registered trademark) (Big Chemie) and the like.

When a dispersant is used, the amount of the dispersant used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the pigment or the like. When the amount of the dispersant used is in the above range, a colorant-containing liquid in a more uniform dispersed state tends to be obtained.

The content of the colorant (A) in the color-curable resin composition is usually 20% by mass or more and 80% by mass or less, preferably 30% by mass or more and 70% by mass or less, more preferably, based on the total solid content. Is 40% by mass or more and 60% by mass or less.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (a) (hereinafter, “(a)”). A resin having a structural unit derived from) is more preferable. The resin (B) is 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, may be referred to as “(b)”). Structural units derived from the monomer (c) copolymerizable with (a) (however, 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.

Specifically, as (a), for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, succinic acid mono [2- (meth). ) Acryloyloxyethyl] and the like, preferably acrylic acid, methacrylic acid, maleic anhydride.
In addition, in this specification, "(meth) acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

As (b), 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 oxylan ring, an oxetane ring and a tetrahydrofuran ring) and a (meth) acryloyloxy group is preferable. ..
Examples of (b) include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, and 3-ethyl-3-. (Meta) acryloyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate and the like can be mentioned, and glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (preferably). Meta) acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane.

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. -Il (meth) acrylate benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like, preferably styrene, Vinyl toluene, 2-hydroxyethyl (meth) acrylate, 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 is obtained by adding (b) to the copolymer of (a) and (c) or by adding (b) to the copolymer of (b) and (c). It can be manufactured by adding (a) to. The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting with 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 even more preferably 5,000 to 30,000. ..
The dispersity [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 even 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 required to neutralize 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 1 to 60% by mass, more preferably 5 to 50% by mass, and further preferably 7 to 40% by mass with respect to the total solid content.

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

Above all, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (dipentaerythritol hexa). Meta) acrylate, etc. may be mentioned.

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 1% by mass or more and less than 30% by mass, more preferably 3% by mass or more and 28% by mass or less, still more preferably 5% by mass, based on the total solid content. % Or more and 20% by mass or less.

<Polymer Initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light or heat, and a known polymerization initiator can be used.
Examples of the polymerization initiator that generates an active radical include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl). ) Octane-1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-on-2-imine 2-methyl-2-morpholino-1- (4) -Methylsulfanylphenyl) Propane-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one, 1-hydroxycyclohexylphenylketone 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 so on.

The polymerization initiator is preferably a polymerization initiator containing at least one selected from the group consisting of a triazine compound, an acylphosphine oxide compound, an alkylphenone compound, an O-acyloxime compound and a biimidazole compound, and preferably contains an O-acyloxime compound. Polymerization initiators are more preferred.

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 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 within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

The content of the O-acyloxime compound is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, based on the total amount of the polymerization initiator (D). Particularly preferably, it 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 high-brightness color filter can be produced even when the sensitivity and developability at the time of forming a coloring pattern and the coloring agent content are high.

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

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, and 2,4-diethylthioxanthone. Examples thereof include N-phenylglycine.

When these polymerization initiation aids (D1) are used, the content thereof is preferably 0.1 to 30 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 preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

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

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent in the molecule). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxides, diacetone alcohols and the like.

Examples of the solvent include ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, 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, etc. (Solvent containing -O- and not -COO- in the molecule);
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 (intramolecular-COO- Solvent containing -O-);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, cyclohexanol (solvents containing -CO- and not -COO- in the molecule); butanol, cyclohexanol , Alcohol solvent such as propylene glycol (solvent containing OH in the molecule and not containing -O-, -CO- and -COO-); aromatic hydrocarbon solvent such as toluene and xylene; diacetone alcohol and the like. .. Examples thereof include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone, diacetone alcohol 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 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-. Preference is given to methoxy-1-butanol, diacetone alcohol, and 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-. 1-butanol, diacetone alcohol and ethyl 3-ethoxypropionate are more preferable, and ethyl lactate and diacetone alcohol are even more preferable.

The total content of the solvent to be combined with propylene glycol monomethyl ether acetate is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 0.3% by mass or more and 40% by mass or less, based on the total amount of the solvent. , More preferably 0.5% by mass or more.

When the solvent (E) is contained, the content of the solvent (E) is preferably 65 to 95% by mass, more preferably 70 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. be. In other words, the total solid content of the colored curable resin composition is preferably 5 to 35% by mass, more preferably 8 to 30% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good. ..

<Other ingredients>
The colored curable resin composition of the present invention is known in the art as a leveling agent, a filler, other polymer compounds, an adhesion accelerator, an antioxidant, a light stabilizer, a chain transfer agent, etc., if necessary. Additives may be included.

<Manufacturing method of colored curable resin composition>
The color-curable resin composition of the present invention is a mixture of a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E) and other components as necessary. Can be prepared by

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Of these, the photolithography method is preferable. In the photolithography 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 the photomask. The colored pattern and the colored coating film thus formed are the color filters of the present invention.

The color curable resin composition of the present invention can produce a color filter having excellent lightness. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples.
Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.

<Production Example 1: Synthesis of leuco body 1>
In an ice bath, N, N-dichloromethanephenol (18.9 parts) and 2,4-dichlorobenzaldehyde (10.0 parts) were added to sulfuric acid (40.2 parts), and the mixture was stirred at 125 ° C. for 2 days. After completion of the reaction, the reaction solution was poured into an aqueous sodium hydroxide solution in an ice bath, and the precipitated purple crystals were filtered. The obtained purple crystals were separated and purified by column chromatography to obtain 16.1 part (yield 60.0%) of the following leuco body 1.

<Production Example 2: Synthesis of leuco body 2>
The 2,4-dichlorobenzaldehyde of Production Example 1 was changed to 2,3-dichlorobenzaldehyde, and the same operation was carried out to obtain the following leuco compound 2 in a yield of 63.0%.

<Production Example 3: Synthesis of leuco body 3>
The 2,4-dichlorobenzaldehyde of Production Example 1 was changed to 2-chlorobenzaldehyde, and the same operation was carried out to obtain the following leuco compound 3 in a yield of 61.0%.

<Production Example 4: Synthesis of leuco body 4>
The 2,4-dichlorobenzaldehyde of Production Example 1 was changed to 2,6-dichlorobenzaldehyde, and the same operation was carried out to obtain the following leuco compound 4 in a yield of 30.0%.

<Production Example 5: Synthesis of compound (I-149)>
The leuco body 1 (6.5 parts) and chloranil (5.5 parts) were dissolved in acetonitrile (33.6 parts) and stirred at room temperature for 3 hours. The reaction mixture was diluted with chloroform and an aqueous sodium hydroxide solution was added. After filtering the precipitated solid, the filtrate was extracted with chloroform and washed with water, an aqueous solution of bis (trifluoromethanesulfonyl) imide potassium, and water in this order. After concentration, the residue was crystallized from methanol to obtain 4.76 parts (yield 42.5%) of the following compound (I-149) [compound represented by the formula (I-149)] as purple crystals.

<Production Example 6: Synthesis of compound (I-141)>
The leuco body 1 of Example 1 was changed to the leuco body 2 and the same operation was carried out to obtain the following compound (I-141) [compound represented by the formula (I-141)] in a yield of 34.9%. ..

<Production Example 7: Synthesis of compound (I-136)>
The leuco body 1 of Example 1 was changed to the leuco body 3 and the same operation was carried out to obtain the following compound (I-136) [compound represented by the formula (I-136)] in a yield of 44.0%. ..

<Production Example 8: Synthesis of compound (I-226)>
The leuco body 1 of Example 1 was changed to the leuco body 3, and the aqueous solution of bis (trifluoromethanesulfonyl) imide potassium was changed to the aqueous solution of potassium hexafluorophosphate. 226) [Compound represented by the formula (I-226)] was obtained.

<Production Example 9: Synthesis of compound (I-142)>
The leuco body 1 of Example 1 was changed to the leuco body 4, and the same operation was carried out to obtain the following compound (I-142) [compound represented by the formula (I-142)] in a yield of 41.8%. ..

< ^{1 1} H-NMR>
Each compound obtained above was dissolved in a deuterated solvent (CDCl ₃ ), and ¹ H-NMR (AVANCE (registered trademark) IIIHD400 manufactured by Bruker) was measured.
The results are shown in Table 9.

The maximum absorption wavelength (λmax) and the molar extinction coefficient (ε) of each compound obtained above were evaluated by the following procedure. The results are shown in Table 10.

<Maximum absorption wavelength (λmax) and molar extinction coefficient (ε)>
A 10 mg sample (each compound) was weighed, placed in a 100 ml volumetric flask, chloroform was added up to the marked line, and the mixture was shaken with ultrasonic waves for 10 minutes to obtain a homogenized solution. 2 ml was taken out from the obtained solution with a whole pipette, placed in an empty 50 ml volumetric flask, and chloroform was added to the marked line to prepare a measurement sample.
The following measurements were made on the above measurement sample with JASCO Corporation U-3900. That is, after measuring the chloroform baseline, the measurement sample was placed in a quartz cell having an optical path length of 1 cm, and the absorbance of the visible light region of 800 to 300 nm was measured at intervals of 0.5 nm at 300 nm / min, and the maximum was measured at 600 to 400 nm. The wavelength for absorbance was defined as λmax. In addition, the molar extinction coefficient ε was calculated from the absorbance of λmax and its molecular weight using Beer-Lambert's law.

Example of red pigment synthesis 174 parts of tert-amyl alcohol and 22.2 parts of metallic sodium were reacted at 130 ° C. under a nitrogen atmosphere to synthesize sodium tert-amyl alcoholate. This is heated to 60 ° C., 91.0 parts of 4-bromobenzonitrile, 71.05 parts of succinic acid di-tert-amyl ester, and 108.9 parts of tert-amyl alcohol are added, and the liquid temperature becomes 85 ° C. or lower. 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 mixture was kept at 0 ° C. and stirred for 5 hours to complete the reaction, and then the solid content was filtered. The solids were washed alternately with methanol and water until the filtrate was no longer colored and no salt was deposited. Then, the solid content was dried in a vacuum dryer at 80 ° C. for 18 hours to obtain the desired red pigment 1. The amount obtained was 107 parts.

Resin synthesis example 1
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 85 ° C. with stirring. Then 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] deca-8-ylacrylate and 3,4-epoxytricyclo [5.2.2.10 ^{2, 6} ] A mixed solution of 25 parts of a mixture of deca-9-ylacrylate (content ratio 1: 1), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethylmethacrylate, and 338 parts of propylene glycol monomethyl ether acetate is added dropwise over 5 hours. bottom. On the other hand, a mixed solution prepared 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 dropping, the mixture was kept at 85 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a solid content of 25.6%. The weight average molecular weight Mw of the produced copolymer was 8000, the dispersity was 2.1, and the acid value in terms of solid content was 111 mg-KOH / g. The resin (B-1) has the following structural units.

Resin synthesis example 2
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then, in the flask, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] A solution prepared by dissolving 289 parts of a mixture of decane-9-ylacrylate (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 prepared by dissolving 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate is dropped into the flask over about 6 hours using another dropping pump. bottom. After completion of the dropping, the mixture was kept at 80 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-2)) solution having a solid content of 35.1%. The weight average molecular weight Mw of the produced copolymer was 9200, the dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. The resin (B-2) has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin were measured by using the GPC method under the following conditions.
Equipment; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shima-pack GPC-80M
Column temperature; 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate; 1.0 mL / min
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was defined as the degree of dispersion.

[Preparation of dispersion liquid 1]
28 parts of red pigment 1, 7 parts of dispersant (BYKLPN-6919; solid content equivalent), 6 parts of resin (B-2) (solid content equivalent), and 159 parts of propylene glycol monomethyl ether acetate are mixed. , 600 parts of 0.4 μm diameter zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 1.

[Preparation of dispersion liquid 2]
C. I. 24 parts of Pigment Yellow 138, 11 parts of dispersant (BYKLPN-6919; solid content equivalent), 5 parts of resin (B-2) (solid content equivalent), and 160 parts of propylene glycol monomethyl ether acetate are mixed. , 600 parts of 0.4 μm diameter zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 2.

[Preparation of dispersion liquid 3]
C. I. 20 parts of Pigment Yellow 185, 14 parts of dispersant (BYKLPN-6919; solid content equivalent), 8 parts of resin (B-2) (solid content equivalent), and 158 parts of propylene glycol monomethyl ether acetate are mixed. , 600 parts of 0.4 μm diameter zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 3.

[Examples 1 to 7, Comparative Example 1]
[Preparation of Color Curable Resin Composition]
The components shown in Table 11 were mixed to obtain each colored curable resin composition.

Resin (B): Resin (B-1) (in terms of solid content)
Polymerizable compound (C): Dipentaerythritol hexaacrylate (“A9550” solid content equivalent manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
Polymerization Initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-on-2-imine (Irgacure® OXE 01; manufactured by BASF)
Solvent (E): E-1: Propylene glycol monomethyl ether acetate solvent (E): E-2: Ethyl lactate solvent (E): E-3: Diacetone alcohol leveling agent (F): Polyether-modified silicone oil (Solid content conversion)
(Torre Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Making color filters>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After allowing to cool, the colored composition layer was irradiated with light at an exposure amount of 60 mJ / cm ² (based on 365 nm) under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Then, post-baking was carried out 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 measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 12.

[Saturation evaluation]
The color filter on the obtained glass substrate was spectrally measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the CIE XYZ color system was used using the color matching function of the C light source. The xy chromaticity coordinates (x, y) and the stimulus value Y in the above were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 12.

Claims (4)

Contains colorants, resins, polymerizable compounds and polymerization initiators
The colorant comprises a compound represented by the formula (I) and a red pigment (excluding the compound represented by the formula (I)).
A coloring curable resin composition in which the content of the red pigment is 10% by mass or more and 95% by mass or less with respect to the total amount of the colorant.

[In formula (I),
R ¹ to R ¹¹ independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and are included in the saturated hydrocarbon group and the aryl group. The hydrogen atom may be substituted with a halogen atom .
At least one of R ⁷ to R ¹¹ is a halogen atom.
R ¹² to R ¹⁵ 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 are contained in the saturated hydrocarbon group. The hydrogen atom may be substituted with a halogen atom, and the phenyl group and the hydrogen atom contained in the benzyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group or a vinyl group. good.
R ¹ and R ¹³ , R ² and R ¹² , R ⁴ and R ¹⁵ and R ⁵ and R ¹⁴ may be linked to form a 6-membered ring containing a nitrogen atom, respectively, and R ¹² and R ¹³ and R ¹⁴ and R ¹⁵ may be linked to each other to form a 3- to 6-membered heterocycle containing a nitrogen atom.
A ^q- represents a q-valent anion and q represents 1 or 2.
p represents a coefficient by which the compound represented by the formula (I) keeps the charge neutral. ] The colored curable resin composition according to claim 1, 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 claim 1 or 2. A display device including the color filter according to claim 3.