KR20210126630A - Colored curable resin composition - Google Patents

Abstract

An object of this invention is to provide the colored curable resin composition which can form the color filter excellent in heat resistance. The present invention includes a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant is a colorant containing a squarylium dye, and the resin is derived from fluoroalkyl (meth)acrylate. It is related with the colored curable resin composition which is resin containing a structural unit.

Description

Colored curable resin composition

[0001] The present invention relates to a colored curable resin composition.

[0002] A color filter used in a display device such as a liquid crystal display device, an electroluminescent display device, and a plasma display, or a solid-state imaging device such as a CCD or CMOS sensor, is manufactured from a colored resin composition. As a coloring agent used for such a colored resin composition, squarylium dye is known (patent documents 1, 2 etc.).

[0003] 1. Japanese Patent Laid-Open No. 2015-86379 2. Japanese Patent Laid-Open No. 2015-86380

However, conventionally known color filters formed from colored curable resin compositions using squarylium dyes may not sufficiently satisfy heat resistance (preferably heat resistance and absorbance retention, or heat resistance and brightness). Therefore, this invention makes it a subject to provide the colored curable resin composition which can form the color filter excellent in heat resistance (preferably heat resistance and absorbance retention, or heat resistance and brightness).

The gist of the present invention is as follows.

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

The colorant is a colorant containing a squarylium dye,

The colored curable resin composition in which the said resin is resin containing the structural unit derived from (meth)acrylic-acid fluoroalkyl.

[2] The colored curable resin composition according to [1], wherein the squarylium dye is a compound represented by formula (I).

[In 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 hydroxyl 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 formula (i).

[In formula (i),

R ¹² represents 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 may be the same or different, respectively. * represents a bond loss with a 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 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].

[0006] According to the colored curable resin composition of the present invention, a color filter excellent in heat resistance (preferably heat resistance and absorbance retention, or heat resistance and brightness) can be provided.

[0007] The colored curable resin composition of the present invention includes a colorant (hereinafter, may be referred to as a colorant (A)), a resin (hereinafter may be referred to as a resin (B)), a polymerizable compound (hereinafter, may be referred to as a polymerizable compound) compound (C)), and a polymerization initiator (hereinafter, sometimes referred to as polymerization initiator (D)) are included.

The colorant includes a squarylium dye.

Resin contains the structural unit derived from (meth)acrylic-acid fluoroalkyl.

It is preferable that the colored curable resin composition of this invention contains a solvent (it may be hereafter called a solvent (E)) further.

The colored curable resin composition of this invention may also contain a leveling agent (it may call a leveling agent (F) hereafter).

In this specification, the compound illustrated as each component can be used individually or in combination of multiple types, unless otherwise indicated.

[0008] <Colorant (A)>

As for the squarylium dye contained in the coloring agent (A), the compound etc. which were described in Unexamined-Japanese-Patent No. 2013-76926 etc. are illustrated, for example.

It is preferable that a squarylium dye is a compound represented by Formula (I) (Hereinafter, it may be called compound (I)).

Hereinafter, the compound (I) will be described in detail, but in the compound (I), the resonance structure of the formula (I) or each group in the formula (I) is rotated around the bond axis of the single bond. The compound obtained shall also be included.

[0009]

[0010] [In formula (I),

R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl 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 hydroxyl 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 formula (i), preferably a group represented by formula (i).

[In formula (i),

R ¹² represents 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 may be the same or different, respectively. * indicates a bond with a 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 formula (i). An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.]

[0011] In formula (I), examples ^{of the halogen atom in R 1} to R ⁴ include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0012] ^{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, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a linear alkyl group having 1 to 20 carbon atoms, such as a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group and an icosyl group; branched chain alkyl groups having 3 to 20 carbon atoms, such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group and an adamantyl group.

[0013] Examples of the substituent of the saturated hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, and an iodine; hydroxyl group; carboxyl 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); nitro group; an alkoxycarbonyl group having 1 to 10 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group; etc. are mentioned, and as a C1-C20 monovalent saturated hydrocarbon group which has a substituent, the group represented by a following formula is mentioned, for example. In the following formula, * represents a bond.

[0014]

[0015] Examples of the group in which an oxygen atom or a sulfur atom is inserted between carbon atoms constituting these saturated hydrocarbon groups include a group represented by the following formula. In the following formula, * represents a bond.

[0016]

[0017] ^{Examples of the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms in R 12} include, for example, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group. can be heard

[0018] Examples of the substituent of the unsaturated hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, and an iodine; hydroxyl group; carboxyl group; -NR ^c R ^d (R ^c and R ^d are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); nitro group; an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group and an ethoxy group; an alkoxycarbonyl group having 1 to 10 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group; and the like.

[0019] As R ¹ to R ⁴ , a hydrogen atom, a hydroxyl group and an alkyl group having 1 to 4 carbon atoms are preferable, a hydrogen atom, a hydroxyl group and a methyl group are more preferable, and a hydrogen atom is still more preferable.

[0020] It is preferable that at least one of ^{R 5} to R ^{8 is a hydroxyl group.} It is more preferable that at least one of R ⁵ and R ⁶ is a hydroxyl group, and at least one of R ⁷ and R ^{8 is a hydroxyl group.}

[0021] R ⁹ and R ¹⁰ are preferably an alkyl group having 3 to 14 carbon atoms which may have a substituent and a group represented by formula (i), and a straight-chain alkyl group having 3 to 6 carbon atoms which may have a substituent, having a substituent A linear or branched alkyl group having 7 to 14 carbon atoms (eg, octyl group, nonyl group, decyl group, dodecyl group, 2-ethylhexyl group, etc.), which may have 7 to 14 carbon atoms, and the group represented by the formula (i) are more preferable , a linear alkyl group having 3 to 5 carbon atoms having a hydroxyl group at the terminal, a linear alkyl group having 3 to 5 carbon atoms having a carboxy group at the terminal, and 2-ethylhexyl group are more preferable.

As ^{the saturated hydrocarbon group of R 12} , an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group, an ethyl group, and an isopropyl group are more preferable.

As ^{the unsaturated hydrocarbon group for R 12} , an alkenyl group having 2 to 4 carbon atoms is preferable, and a vinyl group or an allyl group is more preferable.

When m is 2 or more, ^{it is preferable that at least one R 12} is a saturated hydrocarbon group. When m is 2 or more, the ^{embodiment in which all R 12} is a saturated hydrocarbon group, or an embodiment in which a part of R ¹² is a saturated hydrocarbon group and a part of R ¹² is an unsaturated hydrocarbon group is more preferable.

[0023] 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 a nitrogen atom.

[0024]

[0025] In formula (I),

[0026]

A group represented by X ¹ ,

[0027]

When the group represented by X ² is defined as ^{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.

[0028]

[0029] Examples of the compound (I) include compounds (AII-1) to (AII-27) shown in Table 1.

[0030] [Table 1]

[0031] Compound (AII-10) to compound (AII-18) are more preferable.

The compound represented by the formula (I) can be produced by reacting the compound represented by the formula (pt1), the compound represented by the formula (pt2), and the compound represented by the formula (pt3). In this reaction, the amount of the compound represented by the formula (pt3) to be used is preferably 0.05 mol or more and 0.8 mol or less with respect to 1 mol of the total of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). and more preferably 0.1 mol or more and 0.6 mol or less.

[0033]

[0034] In the formula, R ¹ to R ¹⁰ , Ar ¹ and Ar ² each have the same meaning as above.

The reaction temperature is preferably 30°C to 180°C, and more preferably 80°C to 140°C. 1 hour - 12 hours are preferable, and, as for reaction time, 3 hours - 8 hours are more preferable.

[0036] The reaction is preferably performed in an organic solvent from the viewpoint of yield. Examples of the organic solvent 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; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone; etc. are mentioned, You may mix and use these. Among them, 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 30 parts by mass to 1 part by mass in total of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). It is more than part and 150 mass parts or less.

The method of extracting compound (I), which is the target compound, from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method of cooling after completion of the reaction and filtering the precipitated crystals is exemplified. It is preferable to wash the crystal|crystallization obtained by filtration with water etc., and to dry then. Moreover, you may further refine|purify according to well-known methods, such as recrystallization, as needed.

[0038] The compound represented by the formula (IV-2) and the compound represented by the formula (IV-3) are reacted to prepare the compound represented by the formula (IV-4), and then the compound represented by the formula (IV-4) is By reacting the compound represented by the compound represented by the formula (IV-5) with the compound represented by the formula (IV-5), the compound represented by the formula (pt1) can be produced.

[0039]

[0040] 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 above.

[0041] 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, such as Eur . J. Org. Chem. 2012, the method described in 3105-3111. is mentioned.

[0042] 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. Polymer Sciene The method described in Science Part A: Polymer Chemistry 2012, 50, 3788-3796 is mentioned.

[0043] The compound represented by formula (pt2) can be prepared by using the same method as above.

[0044] The colorant (A) may contain, in addition to the squarylium dye, a colorant different from the squarylium dye, and the colorant different from the squarylium dye is a dye (hereinafter referred to as dye (A1)). In some cases.), and a pigment (hereinafter, sometimes referred to as a pigment (A2).) may be any, and the coloring agent different from the squarylium dye is one of these dyes (A1) and (A2). Or both may be included.

The dye (A1) is not particularly limited as long as it does not include a squarylium dye, and a known dye may be used, and a solvent dye, an acid dye, a direct dye, a mordant dye, etc. are mentioned. As the dye, for example, a compound classified as having a color other than a pigment in the color index (published by The Society of Dyers and Colorists), or a dyeing note (SHIKISENSHA CO., LTD. and the known dyes that have been described. Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, acridine dyes, and styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferable.

[0046] Specifically, C.I. Solvent Yellow 4 (hereinafter, the description of CI solvent yellow will be omitted and only the numbers will be described.), 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, etc. C.I. solvent dyes,

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, CIs of 104, 105, 106, 109, etc. acid dye,

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. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. direct dye,

C.I. Disperse Yellow 51, 54, 76;

C.I. Disperse Violet 26, 27;

C.I. Disperse Blue 1, 14, 56, 60, etc. C.I. dispers 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. Basic Green 1, etc. C.I. basic dye,

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. Reactive Red 36 and other C.I. reactive dyes,

C.I. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modern Red 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. Mordant 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. Modern 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. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc. C.I. modern dye,

C.I. C.I. of vat green 1 etc. Vat dye etc. are mentioned.

What is necessary is just to select these dyes suitably according to the spectral spectrum of a desired color filter.

[0047] The pigment (A2) is not particularly limited, and a known pigment can be used, for example, a pigment classified as a pigment in the color index (published by The Society of Dyers and Colorists) can be mentioned.

As the pigment, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194, 214 yellow pigments;

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

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 ;

C.I. Blue pigments, such as pigment blue 15:6 and 60;

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

C.I. Green pigments, such as Pigment Green 7, 36, and 58;

C.I. Brown pigments, such as Pigment Brown 23 and 25;

C.I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

[0048] The pigment is, if necessary, rosin treatment, surface treatment using a pigment derivative into which an acidic group or basic group is introduced, graft treatment to the pigment surface with a polymer compound, etc., sulfuric acid atomization method Atomization treatment by such as, washing treatment with an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, etc. may be performed.

The pigment preferably has a uniform particle size. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was uniformly disperse|distributed in the solution can be obtained.

[0049] Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used independently and may be used in combination of 2 or more type. As the pigment dispersant, trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by KYOEISHA CHEMICAL Co., LTD.), Solsperse (manufactured by Zeneca Corporation), EFKA (manufactured by CIBA Corporation). manufacture), Ajispar (manufactured by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (manufactured by BYK-Chemie), and the like.

When using a pigment dispersant, the usage-amount becomes like this with respect to the total amount of a pigment (A2). Preferably they are 1 mass % or more and 100 mass % or less, More preferably, they are 5 mass % or more and 50 mass % or less. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

[0050] 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, and more preferably 0.5% by mass or more and 60% by mass relative to the total amount of solid content. It is mass % or less, More preferably, it is 1 mass % or more and 50 mass % or less. If the content of the colorant (A) is within the above range, the color density when a color filter is used is sufficient, and the resin (B) and the polymerizable compound (C) can be contained in the composition in a required amount, so that the mechanical strength is reduced Sufficient patterns can be formed.

[0051] Here, the "total amount of solid content" in the present specification refers to an amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

[0052] The content of compound (I) is preferably 1% by mass or more, more preferably 3% by mass or more, 100% by mass, or 90% by mass or less, in the total amount of the colorant (A), 60 mass % or less may be sufficient and 40 mass % or less may be sufficient.

[0053] <Resin (B)>

The resin contains a resin containing a structural unit derived from fluoroalkyl (meth)acrylate. In addition, in this specification, "(meth)acrylic acid" shows at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations, such as "(meth)acryloyl" and "(meth)acrylate", also have the same meaning.

[0054] When the colored curable resin composition of the present invention contains the resin, the heat resistance of the color filter is improved.

[0055] The structural unit derived from fluoroalkyl (meth)acrylate is preferably a structural unit represented by the following formula (Bf).

[0056]

[0057] In formula (Bf), R ^f1 represents a hydrogen atom or a methyl group. R ^f2 represents a fluoroalkyl group having 1 to 10 carbon atoms.]

[0058] Examples of the fluoroalkyl group having 1 to 10 carbon atoms include a fluoroalkyl group having 1 carbon atoms, such as a difluoromethyl group and a trifluoromethyl group; a fluoroalkyl group having 2 carbon atoms, such as a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, and a perfluoroethyl group; 1,1,2,2-tetrafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethyl a fluoroalkyl group having 3 carbon atoms, such as a methyl group, perfluoropropyl group, perfluoroisopropyl group, 1-(trifluoromethyl)-2,2,2-trifluoroethyl group, and perfluoropropyl group; 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluoro a fluoroalkyl group having 4 carbon atoms, such as a robutyl group, a perfluorobutyl group, and a perfluorot-butyl group; 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoro Lopentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl group, 1,1-bis(trifluoromethyl)-2, a fluoroalkyl group having 5 carbon atoms, such as a 2,3,3,3-pentafluoropropyl group; 2- (perfluorobutyl) ethyl group, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4, and a fluoroalkyl group having 6 carbon atoms, such as a 4,5,5,6,6-dodecafluorohexyl group, a perfluoropentylmethyl group, and a perfluorohexyl group.

As R ^f2 , it is preferable that it is a C2-C6 fluoroalkyl group, and it is more preferable that it is a C4-C6 fluoroalkyl group.

As the structural unit derived from fluoroalkyl (meth)acrylate, difluoromethyl (meth)acrylate, trifluoromethyl (meth)acrylate, 1,1-difluoroethyl (meth)acrylate , 2,2-difluoroethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, 1,1,2,2-tetra Fluoropropyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl 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-trifluoro Ethyl (meth) acrylate, 1,1,2,2-tetrafluorobutyl (meth) acrylate, 1,1,2,2,3,3-hexafluorobutyl (meth) acrylate, 1,1 ,2,2,3,3,4,4-octafluorobutyl (meth)acrylate, perfluorobutyl (meth)acrylate, perfluorot-butyl (meth)acrylate, 2- (perfluoro Ropropyl) 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)acrylic rate, 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, 1,1,2,2,3,3,4,4,5,5,6 Structural units derived from ,6-dodecafluorohexyl (meth) acrylate, perfluoropentylmethyl (meth) acrylate, perfluorohexyl (meth) acrylate and the like are exemplified.

The resin (B) is preferably an alkali-soluble resin. As resin (B) which shows alkali solubility, the following resins [K1] - [K6], etc. are mentioned.

[0062] Resin [K1]; A structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a ring having 2 to 4 carbon atoms A structural unit derived from a monomer (b) having a shape ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”), and a fluoroalkyl (f) (meth)acrylate (hereinafter referred to as “(f)”) a copolymer composed of structural units derived from ”;

resin [K2]; The structural unit derived from (a), the structural unit derived from (b), the structural unit derived from (f), and a monomer (c) copolymerizable with (a) (provided that (a), (b) and (f) different from (f).) (hereinafter sometimes referred to as “(c)”);

resin [K3]; a copolymer comprising the structural unit derived from (a) and the structural unit derived from (f);

resin [K4]; a copolymer comprising the structural unit derived from (a), the structural unit derived from (f), and the structural unit derived from (c);

resin [K5]; a copolymer comprising a structural unit derived from (a), a structural unit obtained by adding (a) to the structural unit derived from (b), and a structural unit derived from (f);

resin [K6]; A public comprising the structural unit derived from (a) and the structural unit derived from (f), a structural unit obtained by adding (a) to the structural unit derived from (b) and further adding a carboxylic acid anhydride, and (f) coalescence.

[0063] In the structural unit derived from (a), it is preferable that the carboxyl group or carboxylic acid anhydride of (a) remains unreacted. In the resins [K1] and [K2], the structural unit derived from (b) preferably has an unreacted cyclic ether structure having 2 to 4 carbon atoms in (b).

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-cyclohexenedicarboxylic 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-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

Unsaturated mono[(meth)acryl] of polyhydric carboxylic acid of divalent or higher, such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] royloxyalkyl]esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from a viewpoint of copolymerization reactivity or a viewpoint of the solubility with respect to the aqueous alkali solution of resin obtained.

(b) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond Eggplant refers to a polymerizable compound. As for (b), the monomer which has a C2-C4 cyclic ether and a (meth)acryloyloxy group is preferable.

[0066] As (b), for example, 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 (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)”).

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-1)”), an alicyclic and monomers (b1-2) (hereinafter, sometimes referred to as “(b1-2)”) having a structure in which a formula unsaturated hydrocarbon is epoxidized.

As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o -vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl Ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyl) Cydyloxymethyl) 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.

[0069] As (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Seroxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (eg, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by formula (BI) and a formula ( The compound represented by BII), etc. are mentioned.

[0070]

[In 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 may be substituted with a hydroxyl group .

X ^e and X ^f represent a single bond, *-R ^g -, *-R ^g -O-, *-R ^g -S-, or *-R ^g -NH-.

R ^g represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates 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, tert-butyl group, and the like.

Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, and 1-hydroxy group. and a hydroxy-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 , Preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, A hexane-1,6-diyl group etc. are mentioned.

As X ^e and X ^f , Preferably a single bond, a methylene group, an ethylene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O- are mentioned, More preferably, a single bond, *- CH ₂ CH ₂ -O- (* represents a bond with O).

Examples of the compound represented by the formula (BI) include a compound represented by any one of 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) ) is preferable, and a compound represented by a formula (BI-1), a formula (BI-7), a formula (BI-9) or a formula (BI-15) is more preferable.

[0075]

[0076] Examples of the compound represented by the formula (BII) include a compound represented by any one of 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) ) is preferable, and a compound represented by a formula (BII-1), a formula (BII-7), a formula (BII-9) or a formula (BII-15) is more preferable.

[0077]

[0078] 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. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used together, their content ratio [the compound represented by the formula (BI): the compound represented by the formula (BII)] is based on a molar basis, Preferably it is 5:95-95:5, More preferably, it is 20:80-80:20.

As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. are mentioned.

[0080] As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD), tetrahydrofurfuryl methacrylate, and the like.

As (b), it is preferable that it is (b1) from the viewpoint that the reliability of the heat resistance, chemical-resistance, etc. of the obtained color filter can be improved more. Furthermore, (b1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

As (c), 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 ] decan-8-yl (meth) acrylate (in the technical field, as a common name, "dicyclofentanyl (meth) acrylate" Also called "tricyclodecyl (meth) acrylate" in some cases), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the technical field, Commonly called "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylic acid esters such as (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

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 diethyl itaconic acid;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[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-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexylox bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl- dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-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, acetic acid vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

[0083] In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1],

a structural unit derived from (a); 2-55 mol%

a structural unit derived from (b); 2-95 mol%

a structural unit derived from (f); 1-55 mol%

It is preferable that

a structural unit derived from (a); 5-50 mol%

a structural unit derived from (b); 5-80 mol%

a structural unit derived from (f); 5-50 mol%

It is more preferable that

When the ratio of the structural unit of resin [K1] exists in said range, the heat resistance of the color filter obtained from colored curable resin composition can be improved further.

[0084] Resin [K1] is, for example, described in the document "Experimental Methods for Polymer Synthesis" (published by Takayuki Otsu, Kagaku-Dojin Publishing Company, INC. First Edition, First Edition, March 1, 1972) It can be prepared with reference to the method and citations described in the literature.

[0085] Specifically, a predetermined amount of (a), (b) and (f), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, for example, by replacing oxygen with nitrogen, to a deoxygenated atmosphere. and a method of heating and keeping warm while stirring is mentioned. In addition, the polymerization initiator, a solvent, etc. used here are not specifically limited, What is normally used in the said field|area 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.) What is necessary is just to melt|dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (E) of the colored curable resin composition of this invention are mentioned.

In addition, as the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, and a solid (powder) extracted by a method such as re-precipitation is used. also be In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent in the 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. The manufacturing process of colored curable resin composition can be simplified.

[0087] In the resin [K2], the ratio of the structural units derived from each of the total structural units constituting the resin [K2],

a structural unit derived from (a); 2-55 mol%

a structural unit derived from (b); 2-95 mol%

a structural unit derived from (f); 1-55 mol%

a structural unit derived from (c); 1-65 mol%

It is preferable that

a structural unit derived from (a); 5-50 mol%

a structural unit derived from (b); 5-80 mol%

a structural unit derived from (f); 5-50 mol%

a structural unit derived from (c); 5 to 60 mol%

It is more preferable that

When the ratio of the structural unit of resin [K2] exists in said range, the heat resistance of the color filter obtained from colored curable resin composition can be improved further.

[0088] The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0089] In the resin [K3], the ratio of the structural units derived from each of the total structural units constituting the resin [K3],

a structural unit derived from (a); 2~70 mol%

a structural unit derived from (f); 30-98 mol%

It is preferable that

a structural unit derived from (a); 10 to 60 mol%

a structural unit derived from (f); 40-90 mol%

It is more preferable that

The resin [K3] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0090] In the resin [K4], the ratio of the structural units derived from each of the total structural units constituting the resin [K4],

a structural unit derived from (a); 2-55 mol%

a structural unit derived from (f); 1-55 mol%

a structural unit derived from (c); 1-65 mol%

It is preferable that

a structural unit derived from (a); 5-50 mol%

a structural unit derived from (f); 5-50 mol%

a structural unit derived from (c); 5 to 60 mol%

It is more preferable that

[0091] The resin [K4] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0092] The resin [K5] is a first step, in the same manner as in the above-described method for producing the resin [K1], to obtain a copolymer of (a), (b) and (f). As for the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, and the obtained copolymer may use what was extracted as a solid (powder) by methods, such as reprecipitation.

The ratio of the structural units derived from (a), (b) and (f) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer,

a structural unit derived from (a); 2-55 mol%

a structural unit derived from (b); 2-95 mol%

a structural unit derived from (f); 1-55 mol%

It is preferable that

a structural unit derived from (a); 5-50 mol%

a structural unit derived from (b); 5-80 mol%

a structural unit derived from (f); 5-50 mol%

It is more preferable that

[0093] Next, the inside of the flask is made into an air atmosphere, and the copolymer of (a), (b) and (f), (a), a reaction catalyst of a carboxylic acid or carboxylic acid anhydride and a cyclic ether ( For example, tris (dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (such as hydroquinone) are put in a flask, for example, at 60 to 130° C., and reacted for 1 to 10 hours, and (a) and (b) Resin [K5] can be obtained by reacting the cyclic ether derived from (b) which the copolymer of (f) has with the carboxylic acid or carboxylic acid anhydride which has (a).

As for the usage-amount of (a) made to react with said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5].

[0094] 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). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (f).

Reaction conditions, such as the preparation method, reaction temperature, and time, can be suitably adjusted in consideration of manufacturing equipment, the amount of heat generated by polymerization, and the like. In addition, similarly to polymerization conditions, the preparation method and reaction temperature can be adjusted suitably in consideration of manufacturing equipment, the calorific value by polymerization, etc.

[0095] The resin [K6] is a resin in which a carboxylic acid anhydride is further reacted with the resin [K5].

A carboxylic acid anhydride is reacted with the hydroxyl group which arises by reaction of a cyclic ether with carboxylic acid or carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. are mentioned. As for the usage-amount of a carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of the hydroxyl groups which generate|occur|produced by the reaction of the said cyclic ether and carboxylic acid or carboxylic acid anhydride.

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid / 2,2,2-trifluoroethyl (meth) acrylate copolymer, 3 ,4-epoxytricyclo[5.2.1.0 ^2,6 ]decylacrylate/(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} ] a resin [K1] such as decyl acrylate/(meth)acrylic acid/2,2,3,3,4,4,5,5-octafluoropentyl(meth)acrylate copolymer;

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 ]decylacrylate/(meth)acrylic acid/2,2 ,2-trifluoroethyl (meth)acrylate/styrene copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene/2,2,2-trifluoro Ethyl (meth) acrylate copolymer, 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 air Coalesced, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decylacrylate/(meth)acrylic acid/2,2,3,3,4,4,5,5-octafluoropentyl(meth)acryl Late/styrene copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene/2,2,3,3,4,4,5,5-octafluoropentyl Resin [K2], such as a (meth)acrylate copolymer;

2,2,2-trifluoroethyl (meth)acrylate/(meth)acrylic acid copolymer, 2,2,3,3,4,4,5,5-octafluoropentyl(meth)acrylate/( resin [K3] such as meth)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) resin [K4] such as acrylic acid/2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate copolymer;

A resin obtained by reacting (meth)acrylic acid with a copolymer of 2,2,2-trifluoroethyl (meth)acrylate/(meth)acrylic acid/glycidyl (meth)acrylate, 2,2,3,3, resin [K5] such as a resin obtained by reacting (meth)acrylic acid with a copolymer of 4,4,5,5-octafluoropentyl (meth)acrylate/(meth)acrylic acid/glycidyl (meth)acrylate;

2,2,2-trifluoroethyl (meth)acrylate/(meth)acrylic acid/glycidyl (meth)acrylate copolymer is reacted with (meth)acrylic acid, and tetrahydrophthalic anhydride is further reacted (meth)acrylic acid in a copolymer of resin, 2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate / (meth)acrylic acid / glycidyl (meth)acrylate and resin [K6], such as a resin in which tetrahydrophthalic anhydride was further reacted with a resin made to react with the resin [K6].

Especially, as resin (B), resin [K1] - resin [K4] are preferable, and resin [K1] and resin [K2] are more preferable.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. 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 in the developer of the unexposed part is good, and the resolution of the coloring pattern is improved. tends to

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

[0099] The acid value of the resin (B), in terms of solid content, is preferably 40 mg-KOH/g or more, more preferably 50 mg-KOH/g or more, still more preferably 60 mg-KOH/g or more. and preferably 180 mg-KOH/g or less, more preferably 170 mg-KOH/g or less, and still more preferably 160 mg-KOH/g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

[0100] The content of the resin (B) is preferably 7 to 80% by mass, more preferably 13 to 75% by mass, and still more preferably 17 to 65% by mass relative to the total amount of solid content. When the content rate of resin (B) exists in said range, a coloring pattern can be formed and there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

[0101] The content of the resin (B) is preferably 10 parts by mass or more and 95 parts by mass or less, and more preferably 20 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). They are 90 mass parts or more, More preferably, they are 30 mass parts or more and 85 mass parts or less. When content of resin (B) exists in the said range, the heat resistance of the color filter obtained will further improve.

Moreover, content of resin (B) is 55 mass parts or more and 95 mass parts or less with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C), It is also preferable that they are preferably 60 mass parts or more and 90 mass parts or less. do. When content of resin (B) exists in the said range, the heat resistance and absorbance retention of the color filter obtained will improve remarkably.

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 with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), obtained when The heat resistance and brightness of the color filter are improved.

[0102] <Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with active radicals and/or acids generated from the polymerization initiator (D), and examples include compounds having a polymerizable ethylenically unsaturated bond, preferably ( It is a meth)acrylic acid ester compound.

[0103] Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and di Pentaerythritol 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, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth) and acrylates.

Especially, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.

[0104] The content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 55% by mass relative to the total amount of solid content. . When the content rate of a polymeric compound (C) exists in said range, there exists a tendency for the residual-film rate at the time of coloring pattern formation and the chemical-resistance of a color filter to improve.

[0105] <Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat, and a known polymerization initiator can be used.

As a polymerization initiator which generate|occur|produces an active radical, an O-acyl oxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound are mentioned, for example.

[0106] Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfa). Nylphenyl) octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1- O-acyl oxime compounds having a diphenyl sulfide skeleton such as (4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine; N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-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-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2) O-acyloxime compounds having a carbazole skeleton such as -methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine; O-acyloxime compounds having a fluorene skeleton such as 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime; and the like. You may use commercial items, such as Irgacure (trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (made by ADEKA), and DFI-091 (made by DAITO CHEMIX Co., Ltd.). Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, 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-dioxacyclo) Fentanylmethyloxy)benzoyl｝-9H-carbazol-3-yl]ethan-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl] At least one selected from the group consisting of ethanone O-acetyloxime is preferable. If it is these O-acyl oxime compounds, there exists a tendency for the color filter with high brightness to be obtained.

[0107] Examples of the alkylphenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholino). phenyl)-2-benzylbutan-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, an oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal. have. You may use commercial items, such as Irgacure (trademark) 369, 907, 379 (above, BASF Corporation make).

[0108] As the triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 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-methoxystyryl)-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( and trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0109] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. You may use commercial items, such as Irgacure (trademark) 819 (made by BASF).

[0110] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open Nos. H06-75372 and H06-75373), 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-chloro Phenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication Nos. S48-38403 and S62-174204), 4,4 and biimidazole compounds in which the phenyl group at the ',5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Laid-Open No. H07-10913, etc.).

[0111] As the polymerization initiator for generating an acid, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium Onium salts, such as p-toluenesulfonate and diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

[0112] Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned.

[0113] The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds. And the polymerization initiator containing an O- acyl oxime compound is more preferable.

[0114] 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). am. When content of a polymerization initiator (D) exists in said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, productivity of a color filter improves.

[0115] <Solvent (E)>

The solvent (E) is not specifically limited, The solvent normally used in this field|area can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (containing OH in the molecule, -O- , -CO- and -COO--free solvent), an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

[0116] As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, 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, γ-butyrolactone, and the like.

[0117] 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, tetra Hydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and Methylanisole etc. are mentioned.

[0118] As the ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-e Methyl oxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy -2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, 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 ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. are mentioned.

[0119] As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentane on, cyclopentanone, cyclohexanone, isophorone, and the like.

[0120] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

[0121] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

[0122] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

[0123] Among the above solvents, organic solvents having a boiling point of 120°C or more and 180°C or less at 1 atm from the viewpoint of coating properties and drying properties are preferable. As a solvent, Propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy -4-methyl-2-pentanone and N,N-dimethylformamide are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate And 3-ethoxy ethyl propionate is more preferable.

[0124] The content of the solvent (E) is preferably 70 to 95 mass%, more preferably 75 to 92 mass%, based on the total amount of the colored curable resin composition of the present invention. In other words, the total content of solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When the content rate of the solvent (E) is within the above range, flatness at the time of application becomes favorable, and since color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

[0125] <Leveling agent (F)>

As a leveling agent (F), a silicone type surfactant, a fluorine type surfactant, the silicone type surfactant which has a fluorine atom, etc. are mentioned. These may have a polymeric group in a side chain.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, 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), etc. can be heard

[0126] Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Limited), Megapac (registered trademark) F142D, Megapac F171, Megapac F172, Megapac F173, Megapac F177, Megapac F183, Megapac F554, Megapac R30, Megapac RS-718-K (manufactured by DIC CORPORATION), eftop (registered trademark) EF301, eftop EF303, eftop EF351, eftop EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. manufacture), Sufflon (registered trademark) S381, Sufflon S382, Sufflon SC101, Sufflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Genkyusho), and the like.

[0127] Examples of the 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 Megapac (registered trademark) R08, Megapac BL20, Megapac F475, Megapac F477, and Megapac F443 (manufactured by DIC CORPORATION).

The content rate of the leveling agent (F) is preferably 0.001 mass % or more and 0.2 mass % or less, more preferably 0.002 mass % or more and 0.2 mass % or less, further preferably 0.001 mass % or more and 0.2 mass % or less with respect to the total amount of the colored curable resin composition. is 0.005 mass % or more and 0.2 mass % or less. In addition, the content rate of the said dispersing agent is not included in this content rate. When the content rate of a leveling agent (F) exists in said range, the flatness of a color filter can be made favorable.

[0129] <Other ingredients>

The colored curable resin composition of the present invention may contain additives known in the technical field, such as polymerization initiation aids, fillers, other high molecular compounds, adhesion promoters, light stabilizers, and chain transfer agents, as needed.

As the adhesion promoter, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxy Silane, 3-glycidyloxypropylmethyldiethoxysilane, 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-aminopropyl triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane; and the like.

[0130] <Method for producing colored curable resin composition>

The colored curable resin composition of this invention is a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D), and the solvent (E) and leveling agent (F) used as needed, for example, of this invention And it can be prepared by mixing other components.

[0131] <Method for manufacturing color filter>

As a method of manufacturing a colored pattern from the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable. The photolithography method is a method of apply|coating the said colored curable resin composition to a board|substrate, drying it, forming a coloring composition layer, exposing this coloring composition layer through a photomask, and developing. The photolithographic method WHEREIN: The colored coating film which is hardened|cured material of the said coloring composition layer can be formed by not using a photomask at the time of exposure and/or not developing. The colored pattern and colored coating film formed in this way are the color filter of this invention.

The film thickness of the color filter to produce is not specifically limited, According to the objective, a use, etc., it can adjust suitably, For example, 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

[0132] As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass coated with silica, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicone, the substrate Those in which aluminum, silver, silver/copper/palladium alloy thin films, etc. were formed on it are used. On these board|substrates, another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed.

[0133] Formation of each color pixel by the photolithography method can be performed under known or customary apparatus and conditions. For example, it can be produced as follows.

First, a colored curable resin composition is apply|coated on a board|substrate, and volatile components, such as a solvent, are removed and dried by heat-drying (pre-bake) and/or drying under reduced pressure, and a smooth coloring composition layer is obtained.

Examples of the coating method include a spin coating method, a slit coating method, and a slit-and-spin coating method.

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable that they are 10 second - 60 minutes, and it is more preferable that they are 30 second - 30 minutes.

When performing reduced-pressure drying, it is preferable to carry out under the pressure of 50-150 Pa at the temperature range of 20-25 degreeC.

The film thickness of the coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the color filter made into the objective.

[0134] Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on this photomask is not specifically limited, The pattern according to the intended use is used.

As a light source used for exposure, the light source which generate|occur|produces the light which is a wavelength of 250-450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, or 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. do. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper since it is possible to uniformly irradiate parallel rays to the entire exposure surface or to perform accurate alignment between the photomask and the substrate on which the coloring composition layer is formed.

[0135] A colored pattern is formed on the substrate by developing the colored composition layer after exposure in contact with a developer. By image development, the unexposed part of a coloring composition layer melt|dissolves in a developing solution, and is removed.

As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, is preferable, for example. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. Moreover, the developing solution may contain surfactant.

Any of a puddle method, a dipping method, a spray method, etc. may be sufficient as the image development method. Moreover, you may incline a board|substrate at an arbitrary angle at the time of image development.

It is preferable to wash with water after image development.

[0136] Furthermore, it is preferable to post-bake the obtained coloring pattern. 150-250 degreeC is preferable and, as for post-baking temperature, 160-235 degreeC is more preferable. 1 to 120 minutes are preferable and, as for post-baking time, 10 to 60 minutes are more preferable.

Example

[0137] Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not limited by these Examples. In the examples, percentages and parts indicating content or usage are based on mass unless otherwise specified.

In the following synthesis examples, the compounds were identified by NMR (JNM-EX-270; (manufactured by JEOL Ltd.)).

[0138] (Colorant Synthesis Example 1)

10.0 parts of 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 17.0 parts of 2-ethylhexanebromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and tetrabutylammonium bromide (WAKO KAGAKU KOGYO) 44.0 parts of KK) were mixed. The resulting mixture was stirred at 90° C. for 8 hours. After completion of the reaction, 50 parts of 10% sodium bicarbonate water was added, and then 100 parts of ethyl acetate was added to discard the water layer. After repeating the operation of washing with water and 10% hydrochloric acid twice, 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).

[0139]

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ) of the compound represented by formula (a-1)

δ 0.85 (m, 6H), 1.23-1.42 (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)

[0141] 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 parts of palladium acetate, and sodium tert-butoxy (Tokyo 3.2 parts of Chemical Industry Co., Ltd.), 0.055 parts of tritert-butylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 25.6 parts of toluene were mixed and stirred at 100° C. for 15 hours. To the obtained mixture, 30 parts of ethyl acetate and 100 parts of water were added, and the water layer was discarded. After repeating the operation of washing with water twice, the solvent was distilled off. The residue was purified by silica gel chromatography (chloroform/hexane = 1/1), and the obtained oil was dried under reduced pressure at 60° C. for 24 hours, and represented by a compound represented by the following formula (a-2) 1.9 parts of the compound was obtained.

[0142]

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ) of the compound represented by 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)

[0144] 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.) , 90.0 parts of 1-butanol and 60.0 parts of toluene were mixed. The resulting mixture was stirred at 125° C. for 3 hours while removing water generated using a Dean-Stark trap. After completion|finish of reaction, the solvent was distilled off, and after adding 15 parts of acetic acid, it was dripped at 100 parts of 18% saline, and the precipitated solid was filtered and obtained.

The solid obtained by filtration was washed with hexane. The obtained solid was dried under reduced pressure at 60 DEG C for 24 hours to obtain 4.9 parts of a compound represented by the formula (AII-10).

[0145]

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ) of the compound represented by 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)

[0147] In the following, the structure of the compound was confirmed by mass spectrometry (LC; 1200 manufactured by Agilent Technologies, Inc., MASS; LC/MSD manufactured by Agilent Technologies, Inc.).

[0148] (Colorant Synthesis Example 2)

50 parts of 3-bromoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) 36.1 parts of 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene (Kanto Chemical Co., Inc.) (manufactured) 434 parts, dissolved in this solution, 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 1.4 parts of (tri-tert-butylphosphine)palladium (0) (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed. After raising the temperature to 90 degreeC and stirring for 5 hours, the organic layer was acquired by extraction, the solvent was distilled off, and 52.1 parts of crude products were obtained. 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).

[0149] Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] ⁺ 242.3

Exact Mass: +241.2

[0150]

[0151] 33 parts of the compound represented by the formula (a-9), 26.8 parts of 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene (manufactured by Kanto Chemical Co., Inc.) 286 parts were mixed and heated with stirring at 100° C. for 16 hours. 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).

[0152] Identification: (mass spectrometry) ionization mode = ESI +: m/z = [M + H] ⁺ 356.2

Exact Mass: +355.2

[0153] 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. 28.2 parts of boron tribromide (manufactured by FUJIFILM Wako Pure Chemical Corporation) were added dropwise while stirring. After completion of the dropwise addition, the temperature was gradually increased and the mixture was stirred at 10°C for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, a water-organic solvent extraction operation was performed, and the solvent was distilled off to obtain 9.1 parts of a crude product. Among them, the compound represented by the formula (a-11) contained 48% and the compound represented by the formula (a-12) was contained 36%.

[0154]

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

[0155] A solution of 13.2 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 72 parts of methanol (manufactured by Kanto Chemical Co., Inc.) was cooled to 0 ° C. and stirred while stirring, the formula obtained in Synthesis Example 3 9.1 parts of a crude product containing the compound represented by (a-11) and the compound represented by the formula (a-12) were charged. The temperature was raised to room temperature and the reaction was carried out 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). Silica gel column chromatography refine|purified the obtained crude product, and 7.4 parts of compounds represented by Formula (a-11) were obtained.

[0156] Identification: (Mass Spec.) Ionization mode = ESI +: m / z = [M + H] + 342.2

Exact Mass: +341.2

[0157] 2 parts of the compound represented by the formula (a-11), 26.3 parts of a borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Inc.), 18 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.) After mixing at 0°C, the temperature was raised to 10°C and stirred for 5 hours. After completion of the reaction, water was added to quench the mixture, followed by extraction 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).

[0158] Identification: (Mass Spec.) Ionization mode = ESI +: m / z = [M + H] + 300.2

Exact Mass: +299.2

[0159]

[0160] 2.5 parts of the compound represented by the formula (a-13) and 0.55 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by FUJIFILM Wako Pure Chemical Corporation) toluene (Kanto Chemical Co.). , Inc.) and 50 parts of n-butanol (manufactured by Kanto Chemical Co., Inc.) were dissolved in 50 parts, and heated at 110° C. for 6 hours while stirring. After completion of the reaction, the crude product obtained by distilling off the solvent was separated and purified by silica gel column chromatography to obtain 2.7 parts of the compound represented by the formula (AII-18).

[0161] Identification: (mass spectrometry) ionization mode = ESI +: m/z = [M + H] ⁺ 677.4

Exact Mass: +676.4

[0162]

[0163] (Resin Synthesis Example 1)

An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace with a nitrogen atmosphere, 465 parts of propylene glycol monomethyl ether acetate were put, and the mixture was heated to 85°C while stirring. Then, in the flask, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylate rate mixture 75 parts (mixing ratio is 1:1), acrylic acid 75 parts, 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate 150 parts, propylene glycol monomethyl ether acetate The mixed solution of 40 parts was dripped over 5 hours using the dripping pump.

On the other hand, a mixed solution obtained by dissolving 15 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 100 parts of propylene glycol monomethyl ether acetate was dropped into the flask over 5 hours using another dropping pump. . After the dropping of the polymerization initiator was completed, the solution was maintained at the same temperature for 3 hours, then cooled to room temperature, and a copolymer (resin (B-1)) having a type B viscosity (23° C.) of 130 mPas and a solid content of 30.9%. got it The resulting copolymer had a weight average molecular weight (Mw) of 8800, a dispersion degree of 1.76, and an acid value in terms of solid content of 155 mg-KOH/g. Resin (B-1) has the following structural unit.

[0164]

[0165] The polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC method under the following conditions.

Device ; HLC-8120GPC (manufactured by TOSOH CORPORATION)

column ; TSK-GELG2000HXL

column temperature ; 40℃

solvent ; THF

flow rate ; 1.0mL/min

test solution solids concentration; 0.001 to 0.01 mass %

injection volume ; 50 μL

detector ; RI

Calibration standards ; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH CORPORATION)

Ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight and number average molecular weight obtained above was made into dispersion degree.

[0166] (Resin Synthesis Example 2)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed and replaced with a nitrogen atmosphere, 133 parts of propylene glycol monomethyl ether acetate and 69 parts of propylene glycol monomethyl ether were placed, and heated to 85 ° C. while stirring. Then, in the flask, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylate 82 parts of a mixture of rates (the mixing ratio is 1:1), 40 parts of acrylic acid, 30 parts of 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, propylene glycol monomethyl ether acetate The mixed solution of 25 parts was dripped over 5 hours using the dripping pump.

On the other hand, a mixed solution obtained by dissolving 5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) in 100 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours using another dropping pump. After the polymerization initiator was dropped, it was maintained at the same temperature for 3 hours, cooled to room temperature, and a solution of a copolymer (resin (B-2)) having a type B viscosity (23°C) of 160 mPas and a solid content of 31.8% was obtained. got it The resulting copolymer had a weight average molecular weight (Mw) of 12500, a dispersion degree of 2.14, and an acid value in terms of solid content of 154 mg-KOH/g. Resin (B-2) has the same structural unit as resin (B-1).

[0167] (Resin Synthesis Example 3)

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed into the flask, replaced with a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 85°C while stirring. Then, in the flask, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] A solution obtained by dissolving 171 parts of a mixture of decan-9-yl acrylate (mixing ratio 1:1) in 40 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours using a dropping pump.

On the other hand, a solution in which 26 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 120 parts of propylene glycol monomethyl ether acetate was dropped into the flask over about 5 hours using another dropping pump. . After the polymerization initiator was dropped, it 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 weight average molecular weight (Mw) of obtained resin (B-3) was 8000, the dispersion degree was 1.98, and the acid value in conversion of solid content was 53 mg-KOH/g. Resin (B-3) has the following structural unit.

[0168]

[0169] [Examples 1 to 5, Comparative Example 1]

[Preparation of colored curable resin composition]

Each component was mixed so that it might become a composition shown in Table 2, and the colored curable resin composition was obtained.

[0170] [Table 2]

[0171] In Table 2, each component represents the following compounds.

Colorant (A-1): a compound represented by the formula (AII-10)

Colorant (A-2): a compound represented by the formula (AII-18)

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

Resin (B-2): Resin (B-2) (in terms of solid content)

Resin (B-3): Resin (B-3) (in terms of solid content)

Polymeric compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D-1): N-1919 (made by ADEKA; O-acyloxime compound)

Polymerization initiator (D-2): DFI-091 (made by DAITO CHEMIX; O-acyloxime compound)

Polymerization initiator (D-3): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O- acyloxime compounds)

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): polyether-modified silicone oil (“Toray Silicone SH8400” manufactured by Dow Corning Toray Co., Ltd.)

[0172] <Production of colored coating film>

On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated), the colored curable resin composition was applied by spin coating so that the film thickness after post-baking was 2.0 μm, and then freed at 100° C. for 3 minutes. It baked to form the coloring composition layer. After standing to cool, the coloring composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by TOPCON CORPORATION) in an atmospheric atmosphere at ^{an exposure amount of 100 mJ/cm 2 (based on 365 nm).} Then, it post-baked at 230 degreeC for 30 minute(s) in oven, and obtained the colored coating film.

[0173] [Evaluation of fairness]

1. Heat resistance (ΔEab*)

Chromaticity was measured after pre-baking and post-baking, and color difference ΔEab* was calculated from the measured values by the method described in JIS Z 8730:2009 (7. Color difference calculation method). A result is shown in Table 3. ΔEab* means that the smaller the color change, the smaller the color change.

[0174] [Table 3]

[0175] 2. Absorbance retention rate

For the colored coating film formed from the colored curable resin composition of Examples 1 to 2, 4 to 5, and Comparative Example 1, the maximum absorbance was obtained from the spectroscopy measured after pre-baking and after post-baking, and the maximum absorbance was obtained according to the following formula. The retention rate was calculated. A result is shown in Table 4.

Absorbance retention rate (ΔAbs.Max)=Maximum absorbance after post-bake/Maximum absorbance after pre-bake

It means that the suitability in a film|membrane formation process is so high that the absorbance retention rate is high.

[0176] [Table 4]

[0177] 3. Brightness

The chromaticity of the colored coating film formed from the colored curable resin composition of Examples 1, 3, and Comparative Example 1 was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the C light source From the characteristic function of , xy chromaticity in the XYZ color space of CIE was obtained as coordinates (x, y) and Y. A result is shown in Table 5. It indicates that the higher the value of Y, the higher the brightness.

[0178] [Table 5]

Industrial Applicability

[0179] According to the colored resin composition of the present invention, a color filter having excellent heat resistance can be formed.

Claims (4)

a colorant, a resin, a polymerizable compound, and a polymerization initiator;
The colorant is a colorant comprising a squarylium dye,
The colored curable resin composition in which the said resin is resin containing the structural unit derived from (meth)acrylic-acid fluoroalkyl. According to claim 1,
The colored curable resin composition whose squarylium dye is a compound represented by Formula (I).

[In 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 hydroxyl 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 formula (i).

[In formula (i),
R ¹² represents 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 carbon atoms constituting the monovalent saturated hydrocarbon group. When m is 2 or more, a plurality of R ¹² may be the same or different, respectively. * represents a bond loss with a 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 formula (i). An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.] The color filter formed from the colored curable resin composition of Claim 1 or 2. A display device comprising the color filter according to claim 3 .