WO2020162008A1 - Colored curable resin composition - Google Patents

Abstract

The present invention addresses the problem of providing a colored curable resin composition with which it is possible to form a color filter that exhibits superior heat resistance.　The present invention relates to a colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant includes a squarylium dye, and the resin includes a structural unit derived from fluoroalkyl (meth)acrylate.

Description

Colored curable resin composition

The present invention relates to a colored curable resin composition.

Color filters used for display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are manufactured from a colored resin composition. A squarylium dye is known as a colorant used in such a colored resin composition (Patent Documents 1 and 2).

JP, 2005-86379, A JP, 2005-86380, A

However, conventionally known, a color filter formed from a colored curable resin composition using a squarylium dye, heat resistance (preferably heat resistance and absorbance retention rate, or heat resistance and brightness) may not be sufficiently satisfied. there were. Therefore, an object of the present invention is to provide a colored curable resin composition capable of forming a color filter having excellent heat resistance (preferably heat resistance and absorbance retention, or heat resistance and brightness).

The gist of the present invention is as follows.
[1] contains a colorant, a resin, a polymerizable compound, and a polymerization initiator,
The colorant is a colorant containing a squarylium dye,
A colored curable resin composition, wherein the resin is a resin containing a structural unit derived from fluoroalkyl (meth)acrylate.
[2] The colored curable resin composition according to [1], wherein the squarylium dye is a compound represented by the formula (I).

[In the formula (I),
R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxy group.
Ar ¹ and Ar ² each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, or a group represented by the formula (i).

[In formula (i),
R ¹² is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent. And m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. When m is 2 or more, a plurality of R ^12's may be the same or different. * Represents a bond with the nitrogen atom. ]
R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i). An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. ]
[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].

The colored curable resin composition of the present invention can provide a color filter having excellent heat resistance (preferably heat resistance and absorbance retention, or heat resistance and lightness).

The colored curable resin composition of the present invention includes a colorant (hereinafter sometimes referred to as a colorant (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, a polymerizable compound). (C) and a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)).
Coloring agents include squarylium dyes.
The resin contains structural units derived from fluoroalkyl (meth)acrylate.
The colored curable resin composition of the present invention preferably further contains a solvent (hereinafter sometimes referred to as solvent (E)).
The colored curable resin composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as a leveling agent (F)).
In the present specification, the compounds exemplified as the respective components can be used alone or in combination of two or more kinds unless otherwise specified.

<Colorant (A)>
Examples of the squarylium dye contained in the colorant (A) include compounds described in JP2013-76926A.
The squarylium dye is preferably a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)).
Hereinafter, the compound (I) will be described in detail. The compound (I) is a compound obtained by rotating the resonance structure of the formula (I) or each group in the formula (I) around the bond axis of a single bond. Will also be included.

[In the formula (I),
R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxy group.
Ar ¹ and Ar ² each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i), and preferably a group represented by the formula ( represents a group represented by i).

[In formula (i),
R ¹² is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent. And m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. When m is 2 or more, a plurality of R ^12's may be the same or different. * Represents a bond with the nitrogen atom. ]
R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i). An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. ]

In formula (I), examples of the halogen atom for R ¹ to R ⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ , R ⁹ , R ¹⁰ , R ¹² , Ar ¹ and Ar ² include a methyl group, an ethyl group, a propyl group and a butyl group. , Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group, and other linear alkyl groups having 1 to 20 carbon atoms; isopropyl group, isobutyl group, sec-butyl group Group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, and other branched-chain alkyl groups having 3 to 20 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, trioctyl group Examples thereof include alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclodecyl group and adamantyl group.

Substituents for these saturated hydrocarbon groups include halogen atoms such as fluorine atom, chlorine atom and iodine; hydroxy group; carboxy group; -NR ^a R ^b (R ^a and R ^b are each independently a hydrogen atom or An alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; Examples of the monovalent saturated hydrocarbon group of 20 include groups represented by the following formula. In the following formula, * represents a bond.

Examples of groups in which an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting these saturated hydrocarbon groups include groups represented by the following formula. In the following formula, * represents a bond.

Examples of the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms in R ¹² include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group and decenyl group. To be

As the substituent of the unsaturated hydrocarbon group, a halogen atom such as a fluorine atom, a chlorine atom and iodine; a hydroxy group; a carboxy group; —NR ^c R ^d (R ^c and R ^d are each independently a hydrogen atom or A C1-C20 alkyl group); a nitro group; a C1-C10 alkoxy group such as a methoxy group and an ethoxy group; a C1-C10 alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; Etc.

As R ¹ to R ⁴ , a hydrogen atom, a hydroxy group and an alkyl group having 1 to 4 carbon atoms are preferable, a hydrogen atom, a hydroxy group and a methyl group are more preferable, and a hydrogen atom is still more preferable.

At least one of R ⁵ to R ⁸ is preferably a hydroxy group. More preferably, at least one of R ⁵ and R ⁶ is a hydroxy group, and at least one of R ⁷ and R ⁸ is a hydroxy group.

As R ⁹ and R ¹⁰ , an alkyl group having 3 to 14 carbon atoms which may have a substituent and a group represented by the formula (i) are preferable, and an alkyl group having 3 carbon atoms which may have a substituent. To 6 straight-chain alkyl groups, and C 7-14 straight-chain or branched alkyl groups which may have a substituent (eg, octyl group, nonyl group, decyl group, dodecyl group, 2 -Ethylhexyl group, etc.) and a group represented by the formula (i) are more preferable, and a linear alkyl group having a hydroxy group at a terminal and having 3 to 5 carbon atoms, and a group having a carboxy group at a terminal and having 3 to 5 carbon atoms A linear alkyl group and a 2-ethylhexyl group are more preferable.

The saturated hydrocarbon group for R ¹² is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group.
The unsaturated hydrocarbon group for R ¹² is preferably an alkenyl group having 2 to 4 carbon atoms, more preferably a vinyl group or an allyl group.
When m is 2 or more, at least one R ¹² is preferably a saturated hydrocarbon group. When m is 2 or more, an embodiment in which all R ¹² are saturated hydrocarbon groups or an embodiment in which some R ¹² are saturated hydrocarbon groups and some R ¹² are unsaturated hydrocarbon groups is more preferable. preferable.

m is preferably 1 to 5, more preferably 1 to 3.
Examples of the group represented by the formula (i) include the following groups. * Represents a bond with the nitrogen atom.

In formula (I),

A group represented by X ¹ ,

When the group represented by is represented by X ² , examples of the group represented by X ¹ and X ² include groups represented by formulas (A2-1) to (A2-9). * Represents a bond with a carbon atom.

Examples of the compound (I) include the compounds (AII-1) to (AII-27) shown in Table 1.

Compound (AII-10) to compound (AII-18) are more preferable.

The compound represented by formula (I) can be produced by reacting the compound represented by formula (pt1) with the compound represented by formula (pt2) and the compound represented by formula (pt3). .. In this reaction, the amount of the compound represented by the formula (pt3) used is preferably 0.05 with respect to 1 mol in total of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). The amount is not less than 0.8 and not more than 0.8, and more preferably not less than 0.1 and not more than 0.6.

In the formula, R ¹ to R ¹⁰ , Ar ¹ and Ar ² have the same meanings as described above.

The reaction temperature is preferably 30°C to 180°C, more preferably 80°C to 140°C. The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.

From the viewpoint of yield, it is preferable to carry out the reaction in an organic solvent. Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl. Examples thereof include ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone; and the like, and these may be mixed and used. Of these, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 1 part by mass of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). Is 30 parts by mass or more and 150 parts by mass or less.

The method for taking out the target compound (I) from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method may be mentioned in which the reaction mixture is cooled after completion of the reaction and the precipitated crystals are collected by filtration. The crystals collected by filtration are preferably washed with water or the like and then dried. If necessary, it may be further purified by a known method such as recrystallization.

After reacting the compound represented by formula (IV-2) with the compound represented by formula (IV-3) to produce the compound represented by formula (IV-4), the compound represented by formula (IV-4) By reacting the compound represented by the formula () with the compound represented by the formula (IV-5), the compound represented by the formula (pt1) can be produced.

In formulas (IV-2) to (IV-5), R ¹ , R ² , R ⁵ , R ⁶ , R ⁹ and Ar ¹ each have the same meaning as described above.

As a method for producing the compound represented by the formula (IV-4) from the compound represented by the formula (IV-2) and the compound represented by the formula (IV-3), various known methods can be used. For example, Eur.J. Org. Chem.2012,3105-3111. The method described in 1.

As a method for producing the compound represented by the formula (pt1) from the compound represented by the formula (IV-4) and the compound represented by the formula (IV-5), various known methods such as J PolymerScieneSciencePart A: Polymer Chemistry 2012, 50, 3788-3796.

A compound represented by the formula (pt2) can be produced by using the same method as described above.

The colorant (A) may contain a colorant different from the squarylium dye, in addition to the squarylium dye, and the colorant different from the squarylium dye is a dye (hereinafter sometimes referred to as dye (A1)). , And a pigment (hereinafter, sometimes referred to as a pigment (A2)), and the colorant different from the squarylium dye may include one or both of the dye (A1) and the pigment (A2). ..

The dye (A1) is not particularly limited as long as it does not include a squarylium dye, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes and mordant dyes. Examples of the dyes include compounds that are classified as having a hue other than pigment in the color index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Note (Shikisosha). To be Further, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, acridine dye, styryl dye, coumarin dye, quinoline dye. Examples thereof include dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, CI Solvent Yellow is omitted and only the numbers are shown), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99. 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like C.I. I. Solvent dye,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;
C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, C. 104, 105, 106, 109, etc. I. Acid dyes,
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. C. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. Direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. C. such as Disperse Blue 1, 14, 56, 60 and the like. I. Disperse dye,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. Basic Violet 2;
C. I. Basic Red 9;
C. I. C. such as Basic Green 1 I. Basic dye,
C. I. Reactive Yellow 2,76,116;
C. I. Reactive Orange 16;
C. I. C. such as Reactive Red 36 I. Reactive dye,
C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Mordan tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C. I. MODANT BLUE 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. C. such as Modern Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53. I. Modant dye, C.I. I. C. such as Bat Green 1 I. Examples include vat dyes and the like.
These dyes may be appropriately selected according to the desired spectrum of the color filter.

The pigment (A2) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Examples of the pigment include 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, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 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 Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and the like;
C. I. Pigment Blue 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 and other green pigments;
C. I. Pigment Brown 23, 25 and other brown pigments;
C. I. Pigment Black 1 and 7 and the like black pigments and the like.

The pigment may be rosin treated, surface treated with a pigment derivative having an acidic group or a basic group introduced therein, grafted on the surface of the pigment with a polymer compound, or atomized by a sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a treatment for removing ionic impurities by an ion exchange method, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out the dispersion treatment by incorporating the pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more kinds. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Sols Perth (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Azisper (Ajinomoto Fine Co., Ltd.) Techno Co., Ltd., Disperbyk (manufactured by Big Chemie), and the like.
When a pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A2). When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniform dispersed state tends to be obtained.

The content of the colorant (A) in the colored curable resin composition is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 60% by mass, based on the total amount of solids. It is not more than mass%, more preferably not less than 1 mass% and not more than 50 mass%. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, the pattern having sufficient mechanical strength can be formed.

Here, the “total amount of solids” in the present specification means the amount obtained by removing 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 relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

The content of the compound (I) in the total amount of the colorant (A) is preferably 1% by mass or more, more preferably 3% by mass or more, and may be 100% by mass, or 90% by mass. It may be the following, 60% by mass or less, or 40% by mass or less.

<Resin (B)>
The resin contains a resin containing a structural unit derived from fluoroalkyl (meth)acrylate. In addition, in this specification, "(meth)acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid. The notations such as “(meth)acryloyl” and “(meth)acrylate” have the same meaning.

By containing the resin in the colored curable resin composition of the present invention, the heat resistance of the color filter is improved.

The structural unit derived from fluoroalkyl (meth)acrylate is preferably a structural unit represented by the following formula (Bf).

[In the formula (Bf), R ^f1 represents a hydrogen atom or a methyl group. R ^f2 represents a fluoroalkyl group having 1 to 10 carbon atoms. ]

Examples of the fluoroalkyl group having 1 to 10 carbon atoms include a fluoroalkyl group having 1 carbon atom such as difluoromethyl group and trifluoromethyl group; 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2 2-trifluoroethyl group, perfluoroethyl group and other fluoroalkyl groups having 2 carbon atoms; 1,1,2,2-tetrafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 1,1 , 2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, perfluoropropyl group, perfluoroisopropyl group, 1-(trifluoromethyl)-2,2,2-trifluoroethyl group, perfluoropropyl group C3 fluoroalkyl group such as fluoropropyl group: 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2,2 , 3,3,4,4-octafluorobutyl group, perfluorobutyl group, perfluoro t-butyl group and other fluoroalkyl groups having 4 carbon atoms; 2-(perfluoropropyl)ethyl group, 1,1,2 , 2,3,3,4,4-octafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, perfluoropentyl group, 1,1,2,2 Fluoroalkyl having 5 carbon atoms such as 3,3,4,4,5,5-decafluoropentyl group and 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl group Group; 2-(perfluorobutyl)ethyl group, 1,1,2,2,3,3,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4 , 4,5,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group, and fluoroalkyl group having 6 carbon atoms such as perfluorohexyl group.

R ^f2 is preferably a fluoroalkyl group having 2 to 6 carbon atoms, and more preferably a fluoroalkyl group having 4 to 6 carbon atoms.

Structural units derived from fluoroalkyl (meth)acrylate include difluoromethyl (meth)acrylate, trifluoromethyl (meth)acrylate, 1,1-difluoroethyl (meth)acrylate, and 2,2-difluoroethyl (meth) Acrylate, 2,2,2-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, 1,1,2,2-tetrafluoropropyl (meth)acrylate, 2,2,3,3-tetrafluoro Propyl group (meth)acrylate, 1,1,2,2,3,3-hexafluoropropyl (meth)acrylate, perfluoroethylmethyl (meth)acrylate, perfluoropropyl (meth)acrylate, perfluoroisopropyl (meth) Acrylate, 1-(trifluoromethyl)-2,2,2-trifluoroethyl (meth)acrylate, 1,1,2,2-tetrafluorobutyl (meth)acrylate, 1,1,2,2,3,3 3-hexafluorobutyl (meth)acrylate, 1,1,2,2,3,3,4,4-octafluorobutyl (meth)acrylate, perfluorobutyl (meth)acrylate, perfluoro t-butyl (meth) Acrylate, 2-(perfluoropropyl)ethyl(meth)acrylate, 1,1,2,2,3,3,4,4-octafluoropentyl(meth)acrylate, 2,2,3,3,4,4 ,5,5-octafluoropentyl (meth)acrylate, perfluoropentyl (meth)acrylate, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl (meth)acrylate, 1 ,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl(meth)acrylate, 2-(perfluorobutyl)ethyl(meth)acrylate, 1,1,2,2,3 ,3,4,4,5,5-decafluorohexyl (meth)acrylate, 1,1,2,2,3,3,4,5,5,6,6-dodecafluorohexyl (meth)acrylate , Structural units derived from perfluoropentylmethyl (meth)acrylate, perfluorohexyl (meth)acrylate, and the like.

The resin (B) is preferably an alkali-soluble resin. Examples of the alkali-soluble resin (B) include the following resins [K1] to [K6].

Resin [K1]; a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides 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)”), and (meth)acrylic acid fluoro. A copolymer composed of structural units derived from alkyl (f) (hereinafter sometimes referred to as “(f)”);
Resin [K2]; Structural unit derived from (a), Structural unit derived from (b), Structural unit derived from (f), Monomer (c) (copolymerizable with (a) ( However, it is different from (a), (b) and (f).) (hereinafter sometimes referred to as "(c)"), a copolymer composed of structural units;
Resin [K3]; a copolymer comprising a structural unit derived from (a) and a structural unit derived from (f);
Resin [K4]; a copolymer comprising a structural unit derived from (a), a structural unit derived from (f), and a structural unit derived from (c);
Resin [K5]; a copolymer containing a structural unit derived from (a), a structural unit obtained by adding (a) to a structural unit derived from (b), and a structural unit derived from (f);
Resin [K6]: a structural unit derived from (a), a structural unit derived from (b) by adding (a) to the structural unit derived from (b), and a structural unit derived from (f). A copolymer containing a structural unit.

In the structural unit derived from (a) above, it is preferable that the carboxy group or carboxylic acid anhydride contained in (a) remains unreacted. Further, in the resins [K1] and [K2], it is preferable that the structural unit derived from (b) has a cyclic ether structure having 2 to 4 carbon atoms, which is contained in (b), remaining unreacted.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;
Unsaturated mono[(meth)acryloyloxyalkyl]esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), a monomer having an oxetanyl group and an ethylenically unsaturated bond. Examples include a monomer (b2) (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”). To be

Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)” And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p. -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene 2,2-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris (Glycidyloxymethyl)styrene and the like can be mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation, 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by the formula (BI) and a formula (BII) And the like.

[In the formulas (BI) and (BII), R ^e and R ^f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X ^e and X ^f is a single ^{bond, * - R g -, *} - R g -O -, * - represents the R ^g -S- or * -R ^g -NH-.
R ^g represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
Examples of the alkyl group having a hydrogen atom substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group and a 1-hydroxy group. Examples thereof include a 1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.
As R ^e and R ^f , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group and the like can be mentioned.
Examples of X ^e and X ^f include a single bond, a methylene group, an ethylene group, *—CH ₂ —O— and *—CH ₂ CH ₂ —O—, and a more preferred single bond, *—CH ₂ CH ₂ —O— can be mentioned (* represents a bond with O).

Examples of the compound represented by the formula (BI) include compounds represented by any of the formulas (BI-1) to (BI-15). Among them, formula (BI-1), formula (BI-3), formula (BII-5), formula (BI-7), formula (BI-9) or formula (BI-11) to formula (BI-15) The compound represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15) is more preferred.

Examples of the compound represented by the formula (BII) include compounds represented by any of the formulas (BII-1) to (BII-15). Among them, formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) to formula (BII-15) The compound represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) or the formula (BII-15) is more preferable.

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination of two or more kinds. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination, the content ratio thereof [the compound represented by the formula (BI): the compound represented by the formula (BII)] is The molar ratio is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane. , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and the like.

As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

As (b), (b1) is preferable because the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. Further, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

Examples of (c) include methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, sec-butyl(meth)acrylate, tert-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, Dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^{2, 6} ] Decane-8-yl(meth)acrylate (in the art, it is commonly called “dicyclopentanyl(meth)acrylate”. It may also be called “tricyclodecyl(meth)acrylate”. .), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (known in the art as a trivial name "dicyclopentenyl (meth)acrylate"), Dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth) ) (Meth)acrylic acid esters such as acrylates;
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and itaconic acid diethyl;
Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2] .1]Hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy -5-Methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2 1.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyl) Bicyclo unsaturated compounds such as oxycarbonyl)bicyclo[2.2.1]hept-2-ene;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate and N-(9-acridinyl)maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

In the resin [K1], the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K1],
Structural unit derived from (a); 2-55 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (f): 1 to 55 mol%
Is preferred,
Structural unit derived from (a); 5 to 50 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (f); 5 to 50 mol%
Is more preferable.
When the ratio of the structural unit of the resin [K1] is in the above range, the heat resistance of the color filter obtained from the colored curable resin composition can be further improved.

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

Specifically, a predetermined amount of (a), (b) and (f), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and oxygen is replaced by, for example, nitrogen to create a deoxygenated atmosphere, Examples of the method include heating and keeping heat while stirring. The polymerization initiator, solvent and the like used here are not particularly limited, and those usually used in the relevant field can be used. For example, as a polymerization initiator, an azo compound (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) The solvent may be any solvent that can dissolve each monomer, and examples thereof include the solvent described below as the solvent (E) of the colored curable resin composition of the present invention.

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

In the resin [K2], the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K2],
Structural unit derived from (a); 2-55 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (f): 1 to 55 mol%
Structural unit derived from (c); 1 to 65 mol%
Is preferred,
Structural unit derived from (a); 5 to 50 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (f); 5 to 50 mol%
Structural unit derived from (c); 5 to 60 mol%
Is more preferable.
When the ratio of the structural unit of the resin [K2] is within the above range, the heat resistance of the color filter obtained from the colored curable resin composition can be further improved.

The resin [K2] can be manufactured, for example, in the same manner as the method described as the method for manufacturing the resin [K1].

In the resin [K3], the ratio of the structural units derived from each is as follows:
Structural unit derived from (a); 2-70 mol%
Structural unit derived from (f); 30 to 98 mol%
Is preferred,
Structural unit derived from (a); 10 to 60 mol%
Structural unit derived from (f); 40 to 90 mol%
Is more preferable.
The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

In the resin [K4], the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K4],
Structural unit derived from (a); 2-55 mol%
Structural unit derived from (f): 1 to 55 mol%
Structural unit derived from (c); 1 to 65 mol%
Is preferred,
Structural unit derived from (a); 5 to 50 mol%
Structural unit derived from (f); 5 to 50 mol%
Structural unit derived from (c); 5 to 60 mol%
Is more preferable.

The resin [K4] can be manufactured, for example, in the same manner as the method described as the method for manufacturing the resin [K1].

As the resin [K5], as a first step, a copolymer of (a), (b) and (f) is obtained in the same manner as in the method for producing the resin [K1] described above. In the same manner as above, the obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratios of the structural units derived from (a), (b) and (f) are, respectively, with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (a); 2-55 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (f): 1 to 55 mol%
Is preferred,
Structural unit derived from (a); 5 to 50 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (f); 5 to 50 mol%
Is more preferable.

Next, the inside of the flask is made to be an air atmosphere, and a reaction catalyst (eg tris(, (Dimethylaminomethyl)phenol etc.) and a polymerization inhibitor (eg hydroquinone etc.) are put in a flask and reacted at, for example, 60 to 130° C. for 1 to 10 hours to give (a), (b) and (f). The resin [K5] can be obtained by reacting the cyclic ether derived from (b) included in the copolymer with the carboxylic acid or carboxylic acid anhydride included in (a).
The amount of (a) used to react with the above copolymer is preferably 5 to 80 mol per 100 mol of (b). (B1) is preferable as (b) used in the resin [K5] because the reactivity of the cyclic ether is high and the unreacted (b) hardly remains.

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (f). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (f).
Reaction conditions such as a charging method, reaction temperature and time can be appropriately adjusted in consideration of production equipment, the amount of heat generated by polymerization and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid/2,2,2-trifluoroethyl (meth)acrylate copolymer, 3,4- Epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/2,2,2-trifluoroethyl (meth)acrylate copolymer, 3,4-epoxycyclohexylmethyl (meth ) Acrylate/(meth)acrylic acid/2,2,3,3,4,4,5,5-octafluoropentyl(meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1. 0 ^2,6 ]decyl acrylate/(meth)acrylic acid/2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate copolymer resin [K1];
Glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid/2,2,2-trifluoroethyl (meth)acrylate copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid/2 ,2,2-Trifluoroethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/2,2,2- Trifluoroethyl (meth)acrylate/styrene copolymer, 3-methyl-3-(meth)acryloyloxymethyl oxetane/(meth)acrylic acid/styrene/2,2,2-trifluoroethyl (meth)acrylate Polymer, glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid/2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate copolymer, glycidyl ( (Meth)acrylate/styrene/(meth)acrylic acid/2,2,3,3,4,4,5,5-octafluoropentyl(meth)acrylate copolymer, 3,4-epoxytricyclo[5.2] .1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/2,2,3,3,4,4,5,5-octafluoropentyl(meth)acrylate/styrene copolymer, 3-methyl- Resin such as 3-(meth)acryloyloxymethyl oxetane/(meth)acrylic acid/styrene/2,2,3,3,4,4,5,5-octafluoropentyl(meth)acrylate copolymer [K2 ];
2,2,2-Trifluoroethyl (meth)acrylate/(meth)acrylic acid copolymer, 2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate/(meth) Resin [K3] such as acrylic acid copolymer;
Benzyl (meth)acrylate/(meth)acrylic acid/2,2,2-trifluoroethyl(meth)acrylate copolymer, styrene/(meth)acrylic acid/2,2,2-trifluoroethyl(meth)acrylate Copolymer, styrene/(meth)acrylic acid/2,2,3,3,4,4,5,5-octafluoropentyl(meth)acrylate copolymer, benzyl(meth)acrylate/(meth)acrylic acid /2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate copolymer resin [K4];
2,2,2-trifluoroethyl (meth)acrylate/(meth)acrylic acid/glycidyl (meth)acrylate copolymer reacted with (meth)acrylic acid, 2,2,3,3,4 , 4,5,5-octafluoropentyl (meth)acrylate/(meth)acrylic acid/glycidyl (meth)acrylate copolymer [K5] such as resin obtained by reacting (meth)acrylic acid
A copolymer of 2,2,2-trifluoroethyl (meth)acrylate/(meth)acrylic acid/glycidyl (meth)acrylate was reacted with (meth)acrylic acid, and tetrahydrophthalic anhydride was further reacted with the resin. Reactive resin, 2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate/(meth)acrylic acid/glycidyl (meth)acrylate copolymer reacted with (meth)acrylic acid A resin [K6] such as a resin obtained by further reacting tetrahydrophthalic anhydride with the resin thus obtained may be mentioned.
Among them, as the resin (B), resins [K1] to resin [K4] are preferable, and resins [K1] and resin [K2] are more preferable.

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 further preferably 5,000 to 30,000. .. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed area in the developing solution is good, and the resolution of the colored pattern tends to be improved.

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, in terms of solid content, preferably 40 mg-KOH/g or more, more preferably 50 mg-KOH/g or more, still more preferably 60 mg-KOH/g or more, preferably 180 mg-KOH. /G or less, more preferably 170 mg-KOH/g or less, still more preferably 160 mg-KOH/g or less. Here, the acid value is a value measured as an amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by, for example, titration using an aqueous potassium hydroxide solution. ..

The content of the resin (B) is preferably 7 to 80% by mass, more preferably 13 to 75% by mass, and further preferably 17 to 65% by mass, based on the total solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to be improved.

The content of the resin (B) is preferably 10 parts by mass or more and 95 parts by mass or less, more preferably 20 parts by mass or more with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). The amount is 90 parts by mass or less, and more preferably 30 parts by mass or more and 85 parts by mass or less. When the content of the resin (B) is within the above range, the heat resistance of the obtained color filter is further improved.
Further, the content of the resin (B) is 55 parts by mass or more and 95 parts by mass or less, preferably 60 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Is also preferable. When the content of the resin (B) is in the above range, the heat resistance and the absorbance retention of the obtained color filter are remarkably improved.
The content of the resin (B) is 10 parts by mass or more and 60 parts by mass or less, preferably 20 parts by mass or more and 55 parts by mass or less based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). In some cases, the heat resistance and brightness of the resulting color filter are improved.

<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 a compound having a polymerizable ethylenic unsaturated bond, and preferably It is a (meth)acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( (Meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl ) Isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, Examples thereof include caprolactone-modified pentaerythritol tetra(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate.
Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.

The content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, further preferably 10 to 55% by mass, based on the total amount of the solid content. is there. When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of polymerization initiators that generate active radicals include O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.

Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane. 1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl )-3-Cyclohexylpropan-1-one-2-imine and other O-acyl oxime compounds having a diphenyl sulfide skeleton; N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) Benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane Carbazoles such as 1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine O-acyl oxime compound having a skeleton; 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acyl oxime having a fluorene skeleton such as O-acetyloxime Compounds; and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA), and DFI-091 (manufactured by Daito Chemix Co., Ltd.) may be used. Among them, the O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3- Cyclohexylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) Benzoyl}-9H-carbazol-3-yl]ethane-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime At least one selected from the group is preferable. With these O-acyl oxime compounds, a color filter with high brightness tends to be obtained.

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

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-(4- Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy Styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4 -Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-Methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. Are listed.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. A commercially available product such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3-dichlorophenyl)- 4,4′,5,5′-Tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis(2-chlorophenyl)-4 ,4',5,5'-Tetraphenylbiimidazole,2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole,2,2'-bis (2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(tri Alkoxyphenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4′,5,5′-position is substituted with a carboalkoxy group. And the like (see, for example, JP-A-7-10913).

Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate and 4-acetoxy. Onium salts such as phenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate and nitrobenzyl Examples thereof include tosylates and benzoin tosylates.

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds. A polymerization initiator containing a vinyl compound is more preferable.

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

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent commonly used in this field can be used. For example, ester solvents (solvents containing -COO- and not -O- in the molecule), ether solvents (solvents containing -O- and not -COO-), ether ester solvents (intramolecular) A solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule but not -COO-), an alcohol solvent (containing OH in the molecule, -O-,- CO- and -COO--free solvents), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

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

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methylanisole.

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

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

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene and the like.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

Among the above solvents, organic solvents having a boiling point of 120° C. or more and 180° C. or less at 1 atm are preferable from the viewpoints of coating properties and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone And N,N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.

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

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, Examples include KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

Examples of the above-mentioned fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F543. R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).

Examples of the above-mentioned silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megafac (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.02% by mass or less with respect to the total amount of the colored curable resin composition. It is 2% by mass or less, and more preferably 0.005% by mass or more and 0.2% by mass or less. The content of the dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention, if necessary, a polymerization initiation auxiliary agent, a filler, another polymer compound, an adhesion promoter, a light stabilizer, a chain transfer agent, etc., which are known additives in the technical field. An agent may be included.
Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiene. Ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane , 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-( Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxy Examples thereof include silane.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary, It can be prepared by mixing the leveling agent (F) and other components.

<Method of manufacturing color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, a printing method and the like. Among them, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithographic method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and/or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited and may be appropriately adjusted depending on the purpose and application. For example, it is 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5. ˜6 μm.

As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass whose surface is coated with silica, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate Aluminum, silver, silver/copper/palladium alloy thin film, etc. are used. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be manufactured as follows.
First, the colored curable resin composition is applied onto a substrate, and dried by heating (prebaking) and/or vacuum drying to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.
Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.
The temperature for heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferable to perform the drying under a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C.
The thickness of the coloring composition layer is not particularly limited and may be appropriately selected according to the intended thickness of the color filter.

Next, the colored composition layer is exposed through a photomask for forming an intended colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that emits light having a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You may Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.
Use an exposure device such as a mask aligner or stepper because it can irradiate parallel rays uniformly on the entire exposed surface and can perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by bringing the colored composition layer after exposure into contact with a developing solution for development. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developing solution.
As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be a paddle method, a dipping method, a spray method or the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

Furthermore, it is preferable to post-bake the obtained coloring pattern. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples,% and parts indicating the content or the amount used are based on mass unless otherwise specified.
In the following synthesis examples, compounds were identified by NMR (JNM-EX-270; manufactured by JEOL Ltd.).

(Colorant Synthesis Example 1)
2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts, 2-ethylhexane bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 17.0 parts, and tetrabutylammonium bromide (Wako Chemical Industry Co., Ltd.) )) 44.0 parts were mixed. The resulting mixture was stirred at 90°C for 8 hours. After completion of the reaction, 50 parts of 10% aqueous sodium hydrogen carbonate was added, 100 parts of ethyl acetate was added, and the aqueous layer was discarded. After washing twice with water and 10% hydrochloric acid was repeated, the solvent was distilled off. The obtained oil was dried under reduced pressure at 60° C. for 24 hours to obtain 9.3 parts of a compound represented by the following formula (a-1).

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ) of the compound represented by the formula (a-1)
δ 0.85 (m, 6H), 1.23 to 1.42 (br, 8H), 1.59 (br, 1H), 2.04 (s, 3H), 2.12 (s, 3H), 2.91 (d, 2H), 4.37 (br, 1H), 6.38 (d, 1H), 6.75 (s, 1H), 6.77 (d, 1H)

3.0 parts of the compound represented by the formula (a-1) obtained above, 2.2 parts of 3-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.015 part of palladium acetate, tert-butoxy sodium salt 3.2 parts (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.055 parts tri-tert-butylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 25.6 parts toluene were mixed and stirred at 100° C. for 15 hours. .. 30 parts of ethyl acetate and 100 parts of water were added to the obtained mixture, and the aqueous layer was discarded. After the operation of washing with water was repeated twice, the solvent was distilled off. The residue was purified by silica gel chromatography (chloroform/hexane=1/1), the obtained oil was dried under reduced pressure at 60° C. for 24 hours, and the compound represented by the following formula (a-2): 1. 9 parts were obtained.

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ) of the compound represented by the formula (a-2)
δ 0.85 (m, 6H), 1.23-1.42 (br, 8H), 1.55 (br, 1H), 1.94 (s, 3H), 2.27 (s, 3H), 2.90 (d, 2H), 6.37 (d, 1H), 6.75 (s, 1H), 6.76 (d, 1H), 6.92-7.14 (m, 4H), 8 .93 (s, 1H)

4.4 parts of the compound represented by the formula (a-2) obtained above, 0.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 1 -Butanol 90.0 parts and toluene 60.0 parts were mixed. The resulting mixture was stirred at 125° C. for 3 hours while removing the water produced using a Dean-Stark tube. After the reaction was completed, the solvent was distilled off, 15 parts of acetic acid was added, and the mixture was added dropwise to 100 parts of 18% saline, and the precipitated solid was collected by filtration.
The solid collected by filtration was washed with hexane. The obtained solid was dried under reduced pressure at 60° C. for 24 hours to obtain 4.9 parts of a compound represented by the formula (AII-10).

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ) of the compound represented by the formula (AII-10)
δ 0.87 (m, 12H), 1.21-1.57 (m, 16H), 1.72 (br, 2H), 2.05 (s, 6H), 2.36 (s, 6H), 3.37 (br, 2H), 3.78 (br, 2H), 6.00 (br, 4H), 6.97-7.12 (m, 6H), 7.77-7.95 (m, 2H), 11.35 (s, 1H), 12.06 (s, 1H)

In the following, the structure of the compound was confirmed by mass spectrometry (LC: 1200 type manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

(Colorant Synthesis Example 2)
50 parts of 3-bromoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) to 36.1 parts of 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 434 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) Dissolve, 30 parts of potassium hydroxide (manufactured by Kanto Chemical Co., Inc.), 25 parts of water, 2 parts of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), bis(tri-tert-butylphosphine)palladium in this solution. (0) 1.4 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed. After heating to 90° C. and stirring for 5 hours, the organic layer was obtained by extraction, and the solvent was distilled off to obtain 52.1 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 50.2 parts of the compound represented by the formula (a-9).

Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] ⁺ 242.3
Exact Mass: +241.2

33 parts of the compound represented by the formula (a-9), 26.8 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 286 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) are mixed. And heated at 100° C. for 16 hours with stirring. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 30.7 parts of the compound represented by the formula (a-10).

Identification :( mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 356.2
Exact Mass: +355.2

10 parts of the compound represented by the formula (a-10) was dissolved in 95 parts of methylene chloride (manufactured by Kanto Chemical Co., Inc.) and cooled to 0° C. with stirring. With stirring, 28.2 parts of boron tribromide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added dropwise. After the dropping was completed, the temperature was gradually raised and the mixture was stirred at 10° C. for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, water-organic solvent extraction operation was carried out, and the solvent was distilled off to obtain 9.1 parts of a crude product. In this, 48% of the compound represented by the formula (a-11) and 36% of the compound represented by the formula (a-12) were contained.

Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] ⁺ 342.2
Exact Mass: +341.2.

Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] ⁺ 328.1
Exact Mass: +327.2

A solution obtained by dissolving 13.2 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 72 parts of methanol (manufactured by Kanto Kagaku Co., Ltd.) was cooled to 0° C. with stirring, and the formula obtained in Synthesis Example 3 was used. 9.1 parts of a crude product containing the compound represented by (a-11) and the compound represented by formula (a-12) was charged. The temperature was raised to room temperature and the reaction was performed for 16 hours. The solvent was distilled off under reduced pressure to obtain 8.3 parts of a crude product containing the compound represented by the formula (a-11). The obtained crude product was purified by silica gel column chromatography to obtain 7.4 parts of the compound represented by the formula (a-11).

Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] ⁺ 342.2
Exact Mass: +341.2.

2 parts of the compound represented by the formula (a-11), 26.3 parts of borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Inc.) and 18 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) were mixed at 0° C. and 10° C. The temperature was raised to and stirred for 5 hours. After completion of the reaction, water was added to quench the reaction, and the mixture was extracted with an organic solvent. The crude product obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 1.64 parts of the compound represented by the formula (a-13).

Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] ⁺ 300.2
Exact Mass: +299.2

2.5 parts of the compound represented by the formula (a-13) and 0.55 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) are added to toluene (Kanto). It was dissolved in 50 parts of Chemical Co., Ltd. and 50 parts of n-butanol (Kanto Chemical Co., Ltd.) and heated at 110° C. for 6 hours with stirring. After completion of the reaction, the solvent was distilled off and the obtained crude product was separated and purified by silica gel column chromatography to obtain 2.7 parts of a compound represented by the formula (AII-18).

Identification :( mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 677.4
Exact Mass: +676.4

 

(Resin synthesis example 1)
An appropriate amount of nitrogen was flown into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, 465 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85° C. with stirring. Then, in the flask, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^{2, 6} ] 75 parts of a mixture of decan-9-yl acrylate (mixing ratio is 1:1), acrylic acid 75 parts, 2,2,3,3,4,5,5-octafluoropentyl methacrylate 150 parts, propylene A mixed solution of 40 parts of glycol monomethyl ether acetate was added dropwise using a dropping pump over 5 hours.
On the other hand, a mixed solution prepared by dissolving 15 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 100 parts of propylene glycol monomethyl ether acetate was put into the flask for 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 130 mPas and a solid content of 30.9% (resin (B-1 )) was obtained. The produced copolymer had a weight average molecular weight (Mw) of 8,800, a dispersity of 1.76, and an acid value in terms of solid content of 155 mg-KOH/g. The resin (B-1) has the following structural units.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column ；TSK-GELG2000HXL
Column temperature: 40℃
Solvent: THF
Flow rate ；1.0mL/min
Test solution solid content concentration: 0.001 to 0.01 mass%
Injection volume: 50 μL
Detector ；RI
Calibration standard ；TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene equivalent weight average molecular weight and number average molecular weight ratio (Mw/Mn) obtained above was taken as the dispersity.

(Resin synthesis example 2)
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was flushed with an appropriate amount of nitrogen to replace it with a nitrogen atmosphere, 133 parts of propylene glycol monomethyl ether acetate and 69 parts of propylene glycol monomethyl ether were added, and heated to 85° C. with stirring. did. Then, in the flask, 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 mixture 82 parts (mixing ratio 1:1), acrylic acid 40 parts, 2,2,3,3,4,5,5-octafluoropentyl methacrylate 30 parts, propylene A mixed solution of 25 parts of glycol monomethyl ether acetate was added dropwise using a dropping pump over 5 hours.
On the other hand, a mixed solution of 5 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) dissolved in 100 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours using another dropping pump. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 160 mPas and a solid content of 31.8% (resin (B-2 )) was obtained. The produced copolymer had a weight average molecular weight (Mw) of 12,500, a dispersity of 2.14, and an acid value in terms of solid content of 154 mg-KOH/g. The resin (B-2) has the same constitutional unit as the resin (B-1).

(Resin synthesis example 3)
An appropriate amount of nitrogen was flown into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85° C. with stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2. A solution of 171 parts of a mixture of 1.0 ^2,6 ]decane-9-yl acrylate (mixing ratio is 1:1) in 40 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours by using a dropping pump. ..
On the other hand, a solution prepared by dissolving 26 parts of the polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was put into the flask for about 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (B-3)) having a solid content of 43.5%. .. The obtained resin (B-3) had a weight average molecular weight (Mw) of 8,000, a dispersity of 1.98 and an acid value in terms of solid content of 53 mg-KOH/g. The resin (B-3) has the following structural unit.

[Examples 1 to 5 and Comparative Example 1]
[Preparation of colored curable resin composition]
Each component was mixed so as to have the composition shown in Table 2 to obtain a colored curable resin composition.

In Table 2, each component represents the following compound.
Colorant (A-1): Compound represented by Formula (AII-10) Colorant (A-2): Compound represented by Formula (AII-18) Resin (B-1): Resin (B-1) ) (Solid content conversion)
Resin (B-2): Resin (B-2) (solid content conversion)
Resin (B-3): Resin (B-3) (solid content conversion)
Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D-1): N-1919 (manufactured by ADEKA; O-acyl oxime compound)
Polymerization initiator (D-2): DFI-091 (manufactured by Daito Chemix Co.; O-acyl oxime compound)
Polymerization initiator (D-3): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Ltd.; O-acyl oxime Compound)
Solvent (E-1): 4-Hydroxy-4-methyl-2-pentanone Solvent (E-2): Propylene glycol monomethyl ether acetate solvent (E-3): Propylene glycol monomethyl ether leveling agent (F-1): Poly Ether-modified silicone oil ("Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)

<Preparation of colored coating film>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by a spin coating method so that the film thickness after post-baking would be 2.0 μm, and then 3 at 100° C. It was prebaked for a minute to form a colored composition layer. After allowing to cool, the colored composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon Corp.) in an air atmosphere at an exposure dose of 100 mJ/cm ² (365 nm standard). Then, post-baking was performed in an oven at 230° C. for 30 minutes to obtain a colored coating film.

[Processability evaluation]
1. Heat resistance (ΔEab*)
The chromaticity was measured after pre-baking and post-baking, and the color difference ΔEab* was calculated from the measured values by the method described in JIS Z 8730:2009 (7. Calculation method of color difference). The results are shown in Table 3. The smaller ΔEab* means the smaller the color change.

2. Absorbance retention rate Regarding the colored coating films formed from the colored curable resin compositions of Examples 1 to 2, 4 to 5 and Comparative Example 1, the maximum absorbance was determined from the spectra measured after pre-baking and post-baking, and the following values were obtained. The maximum absorbance retention was calculated according to the formula. The results are shown in Table 4.
Absorbance retention rate (ΔAbs.Max)=maximum absorbance after post-baking/maximum absorbance after pre-baking The higher the absorbance retention rate, the higher the suitability in the film forming step.

3. Lightness The chromaticity of the colored coating films formed from the colored curable resin compositions of Examples 1 and 3 and Comparative Example 1 was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). From the obtained spectrum and the characteristic function of the C light source, it was determined as xy chromaticity coordinates (x, y) and Y in the XYZ color system of CIE. The results are shown in Table 5. The larger the value of Y, the higher the brightness.

According to the colored resin composition of the present invention, a color filter having excellent heat resistance can be formed.

Claims (4)

1. Including a colorant, a resin, a polymerizable compound, and a polymerization initiator,
   The colorant is a colorant containing a squarylium dye,
   A colored curable resin composition, wherein the resin is a resin containing a structural unit derived from fluoroalkyl (meth)acrylate.
2. The colored curable resin composition according to claim 1, wherein the squarylium dye is a compound represented by the formula (I).
   

   

   [In the formula (I),
   R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
   R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxy group.
   Ar ¹ and Ar ² each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, or a group represented by the formula (i).
   

   

   [In formula (i),
   R ¹² is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent. And m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. When m is 2 or more, a plurality of R ^12's may be the same or different. * Represents a bond with the nitrogen atom. ]
   R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i). An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. ]
3. A color filter formed from the colored curable resin composition according to claim 1.
4. A display device including the color filter according to claim 3.