JP7020791B2 - Color filters and display devices - Google Patents

Description

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

In recent years, liquid crystal display devices have been developed to widen the color reproduction range that can be displayed, and as a part of this, color filters are required to have darker colors.
Examples of the method of darkening the color filter include a method of increasing the colorant concentration in the color filter. However, if the concentration of the colorant is increased, the performance of the color-curable resin composition deteriorates, such as deterioration of the pattern shape. On the other hand, by using a colorant having a high coloring power, it is possible to produce a pattern of a dark color filter. However, when a colorant having high coloring power is used, the brightness may decrease. Another method is to obtain a dark color filter by making the color filter a thick film. However, if the film is thickened, color mixing of light will occur between the adjacent pixels when applied to a liquid crystal display device.

Japanese Patent Application Laid-Open No. 2012-123302 (Patent Document 1) contains at least a cyan-colored material and a yellow-colored material as a green coloring composition capable of obtaining high-intensity green light, and has a peak wavelength in the range of 520 nm to 540 nm. We have proposed a green coloring composition having spectral characteristics such that the transmittance at a wavelength of 510 nm is 40% or less and the transmittance at a wavelength of 560 nm is 40% or less when the transmittance at a peak wavelength is 70%.

Japanese Unexamined Patent Publication No. 2012-123302

In recent years, the recommendation Rec. Which defines the video format of Super Hi-Vision (SHV). ITU-R BT. 2020 has been published, further expanding the color reproduction range, thereby Rec. ITU-R BT. There is a demand for a color filter having a high inclusion rate of the color gamut of 2020 (the ratio of the color gamut that can be expressed in the color gamut to the color reproduction range of Rec. ITU-R BT. 2020).

In the present invention, Rec. ITU-R BT. A color filter having a high inclusion rate in the color gamut of 2020 can be formed, and a color curable resin composition having good patterning property, a color filter formed from the color curable resin composition, and the color filter can be used. The purpose is to provide a display device including.

The present invention provides a color curable resin composition, a color filter and a display device shown below.
[1] Contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).
The colorant (A) is C.I. I. Contains Pigment Blue 16 and yellow colorant, no green colorant,
C. I. The content of Pigment Blue 16 is 26% by mass or more in 100% by mass of the colorant (A).
A colored curable resin composition in which the polymerization initiator (D) contains an oxime compound.
[2] The color-curable resin composition according to [1], wherein the yellow colorant contains a compound having an isoindoline skeleton.
[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].

Rec. ITU-R BT. A color filter having a high inclusion rate in the color gamut of 2020 can be formed, and a color curable resin composition having good patterning property, a color filter formed from the color curable resin composition, and the color filter can be used. A display device including can be provided.

<Coloring curable resin composition>
The color-curable resin composition according to the present invention contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the colorant (A) is C.I. I. Pigment Blue 16 and a yellow colorant are included, no green colorant is contained, and the polymerization initiator (D) contains an oxime compound.
According to the color curable resin composition, good patterning property can be exhibited, and the displayable color reproduction range is expanded (and Rec. ITU-R by this) even though the colorant concentration is appropriate. It is possible to improve the inclusion rate of the color gamut of BT.2020).
Unless otherwise specified, the compounds exemplified as each component in the present specification may be used alone or in combination of two or more.

[1] Colorant (A)
The colorant (A) is C.I. I. Contains Pigment Blue 16 and yellow colorant, but does not contain green colorant.
Examples of the yellow colorant include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and the like can be mentioned.
The colorant (A) may contain two or more kinds of yellow colorants.
Among them, the yellow colorant preferably contains a compound having an isoindoline skeleton, and is composed of a compound having an isoindoline skeleton, because the lightness can be further increased in comparison with the same color filter thickness and colorant concentration. Is more preferable.
Examples of the yellow colorant, which is a compound having an isoindoline skeleton, include C.I. I. Pigment Yellow 139, 185 and the like.
The content of the compound having an isoindolin skeleton in the yellow colorant is preferably 50% by mass in 100% by mass of the yellow colorant, because the lightness can be higher in comparison with the thickness of the same color filter and the colorant concentration. % Or more, more preferably 80% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.

C. I. The content of Pigment Blue 16 is usually 10% by mass or more in 100% by mass of the colorant (A), and is preferably 26% by mass or more, more preferably 26% by mass, from the viewpoint of expanding the displayable color reproduction range. It is 35% by mass or more, more preferably 50% by mass or more.
C. I. From the viewpoint of improving the brightness, the content of Pigment Blue 16 is preferably 90% by mass or less, and more preferably 80% by mass or less in 100% by mass of the colorant (A).

The content of the yellow colorant is usually 10% by mass or more in 100% by mass of the colorant (A), and is preferably 20% by mass or more from the viewpoint of expanding the displayable color reproduction range and improving the brightness. Yes, more preferably 30% by mass or more, still more preferably 35% by mass or more.
From the viewpoint of developability, the content of the yellow colorant is preferably 74% by mass or less, more preferably 65% by mass or less, and 50% by mass or less in 100% by mass of the colorant (A). It is more preferable to have.

C.I. in the colorant (A). I. The total content of Pigment Blue 16 and the yellow colorant is usually 20% by mass or more in 100% by mass of the colorant (A), and is preferably 30% by mass or more from the viewpoint of expanding the displayable color reproduction range. It is more preferably 30% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. The total content may be 100% by mass in 100% by mass of the colorant (A).
From the viewpoint of expanding the displayable color reproduction range, the colorant (A) is substantially C.I. I. It is preferably composed of Pigment Blue 16 and a yellow colorant. "Substantially composed of CI Pigment Blue 16 and a yellow colorant" means that C.I. I. It means that the total content of Pigment Blue 16 and the yellow colorant is 98% by mass or more in 100% by mass of the colorant (A).
As will be described later, the colorant (A) is C.I. I. Pigment Blue 16 and other colorants other than the yellow pigment can be included. In this case, the total content may be 90% by mass or less, 80% by mass or less, or 70% by mass or less in 100% by mass of the colorant (A).

C.I. in the colorant (A). I. The content ratio of Pigment Blue 16 to the yellow colorant (CI Pigment Blue 16 / yellow colorant) is usually 0.1 to 10 on a mass basis, from the viewpoint of expanding the displayable color reproduction range. Therefore, it is preferably 0.1 to 8, more preferably 0.2 to 6.

The colorant (A) is C.I. I. Pigment Blue 16, yellow colorants and other colorants other than green colorants can be included.
The other colorant may be a pigment, a dye, or both.
As the other colorants, only one kind may be used, or two or more kinds may be used in combination.
Other pigments include organic pigments, inorganic pigments, and compounds classified as pigments in the Color Index (published by The Society of Dyers and Colorists).

As the dye, a known dye can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes.
Examples of the dye include compounds classified by the Color Index (published by The Society of Dyers and Colorists) as having a hue other than pigments, and known dyes described in dyeing notes (color dyeing company).
According to the chemical structure, the dyes include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acrydin dyes, and styryl dyes. , Cmarin dyes, quinoline dyes, nitro dyes and the like. Of these, organic solvent-soluble dyes are preferred.

The colorant (A) is C.I. I. Other blue colorants (blue pigments and / or blue dyes) other than Pigment Blue 16 can be included. Other blue pigments include C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and the like can be exemplified.

As a blue dye,
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, C.I. of 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139 and the like. I. Solvent blue dye;
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 and the like. I. Acid blue dye;
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 and the like. I. Direct blue dye;
C. I. Disperse Blue 1, 14, 56, 60, etc. I. Disperse blue dye;
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 and the like C.I. I. Basic blue dye;
C. I. Modant Blue 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43 , 44, 48, 49, 53, 61, 74, 77, 83, 84C. I. Mordant blue dye;
And so on.

From the viewpoint of expanding the displayable color reproduction range, C.I. I. The content of Pigment Blue 16 is preferably high. Specifically, C.I. I. The content of Pigment Blue 16 is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass in 100% by mass of the blue colorant. % Or more, most preferably 100% by mass.

The total content of the colorant (A) in the color-curable resin composition is usually 10 to 50% by mass in 100% by mass of the solid content of the color-curable resin composition, but the displayable color reproduction range is expanded. From the viewpoint of the above, it is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more.
From the viewpoint of ease of forming a resist pattern, the total content is preferably 45% by mass or less in 100% by mass of the solid content of the colored curable resin composition.
In addition, in this specification, "solid content of a color curable resin composition" means all components other than a solvent (E) among the components contained in a color curable resin composition. The total amount of the solid content and the content of each component relative to the solid content can be measured by a known analytical means such as liquid chromatography and gas chromatography.

The various pigments in the color-curable resin composition are preferably in the state of a dispersion liquid uniformly dispersed in a solvent. Further, the pigment preferably has a uniform particle size. The dispersion liquid can be obtained by mixing a pigment and a solvent. If necessary, a pigment dispersant may be mixed. By containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solvent can be obtained.

As the pigment dispersant, a commercially available surfactant can be used, and silicone-based, fluorine-based, ester-based (including polyester-based), cationic-based, anionic-based, nonionic-based, amphoteric, polyester-based, and polyamine-based. Examples include acrylic-based surfactants. Specific examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid-modified polyester, tertiary amine-modified polyurethane, polyethylene imine, and the like, as well as KP (trade name). Shinetsu Chemical Industry Co., Ltd.), Floren (Kyoeisha Chemical Co., Ltd.), Solsorbus (Zeneca Co., Ltd.), EFKA (BASF Japan Co., Ltd.), Azisper (registered trademark) (Ajinomoto Fine Techno Co., Ltd.) ), Disperbyk (manufactured by Big Chemie) and the like. As the pigment dispersant, only one kind may be used, or two or more kinds may be used in combination.

When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, it tends to be easy to obtain a pigment dispersion liquid in a uniformly dispersed state.

The solvent constituting the pigment dispersion is not particularly limited, and examples thereof include the same solvents as the solvent (E) described later that can be contained in the color-curable resin composition. The solvent is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1. -Butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl and the like are preferable. It is preferably acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like.

The amount of the solvent used is not particularly limited, but the concentration of the solid content in the pigment dispersion is preferably 3 to 20% by mass, more preferably 5 to 18% by mass.

Various pigments in the color-curable resin composition are, if necessary, treated with a rosin, surface-treated with a pigment derivative having an acidic group or a basic group introduced, a pigment dispersant, etc., and applied to the pigment surface with a polymer compound or the like. , A pulverization treatment by a sulfuric acid atomization method or the like, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment by an ion exchange method of ionic impurities or the like may be performed.

[2] Resin (B)
The colored curable resin composition of the present invention contains one kind or two or more kinds of resins (B). The resin (B) is preferably an alkali-soluble resin. Alkali-soluble refers to the property of being soluble in a developing solution, which is an aqueous solution of an alkaline compound. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (a) [hereinafter, may be referred to as "(a)". ], And a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter, may be referred to as “(b)”. ] And a copolymer.
Resin [K2]: (a) and (b) and the monomer (c) copolymerizable with (a) (however, different from (a) and (b)) [hereinafter "(c)" There is that. ] And a copolymer.
Resin [K3]: A copolymer of (a) and (c).
Resin [K4]: A resin obtained by reacting (b) with a copolymer of (a) and (c).
Resin [K5]: A resin obtained by reacting (a) with a copolymer of (b) and (c).
Resin [K6]: A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.

As (a), specifically,
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, 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, 1,4-cyclohexendicarboxylic 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 [2.2.1] A bicyclounsaturated compound containing a carboxy group such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalates. ;
Examples thereof include unsaturated (meth) acrylic acid containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) (meth) acrylic acid.
Above all, from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution, (a) is preferably (meth) acrylic acid, maleic anhydride or the like.

In addition, in this specification, "(meth) acrylic" means at least one selected from the group consisting of acrylic and methacrylic. The same applies to the notations such as "(meth) acryloyl" and "(meth) acrylate".

(B) is a polymerization having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring (oxolan ring)) and an ethylenically unsaturated bond. Refers to a sex compound. Reference numeral (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
As (b), a monomer (b1) having an oxylanyl group and an ethylenically unsaturated bond [hereinafter, may be referred to as “(b1)”. ], Monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, may be referred to as “(b2)”. ], Monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter, may be referred to as “(b3)”. ] Etc. can be mentioned.

As (b1), there is a monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized [hereinafter, referred to as “(b1-1)”. ], Monomer having an epoxidized structure of unsaturated alicyclic hydrocarbon (b1-2) [hereinafter, may be referred to as "(b1-2)". ] Can be mentioned.

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

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy4-vinylcyclohexane (for example, seroxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), and 3,4-epoxycyclohexylmethyl acrylate (for example, cyclomer). A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the formula (I), formula (II). Examples thereof include compounds represented by.

[In the formulas (I) and (II), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. It may be replaced with. X ¹ and X ² independently represent a single bond, * -R ^{c-, * -R c-O-, * -R c-S-, or * -R c - NH- .} R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like.
The alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group and the like.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.
The alkanediyl group constituting R ^c includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-. Examples thereof include a diyl group and a hexane-1,6-diyl group.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, a * -CH ₂ -O- (* represents a bond with O) group, and a * -CH ₂ CH ₂ -O- group. , More preferably a single bond, * -CH ₂ CH ₂ -O- group.
Specific examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15), preferably formulas (I-1) and (I-3). ), Formula (I-5), Formula (I-7), Formula (I-9), Formulas (I-11) to Formulas (I-15), and more preferably the formula (I-15). Examples thereof include compounds represented by I-1), formula (I-7), formula (I-9), and formula (I-15).

Specific examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15), preferably formulas (II-1) and (II-). Examples thereof include compounds represented by 3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), and more preferably the formula. Examples thereof include compounds represented by (II-1), formula (II-7), formula (II-9), and formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When two or more kinds are used in combination, the mixing ratio is the formula (I): formula (II) [molar ratio], preferably 5:95 to 95: 5, more preferably 20:80 to 80:20, and further. It is preferably 50:50 to 80:20.
The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.
Preferred examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethyloxetane, and the like. Examples thereof include 3-ethyl-3- (meth) acryloyloxyethyl oxetane.
The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Preferred examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscort V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

As a specific example of (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 ] Decane-8- Il (meth) acrylate [In the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate". It may also be called "tricyclodecyl (meth) acrylate". ], Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate [In the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate". ], Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (Meta) acrylic acid esters such as (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, 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- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] Bicyclounsaturated compounds such as hept-2-ene;
Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, Examples thereof include isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among them, from the viewpoint of copolymerization reactivity and heat resistance, (c) includes benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide. Bicyclo [2.2.1] hepto-2-ene and the like are preferable. Further, benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferable as (c) because they are excellent in developability at the time of pattern formation.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural units derived from (a), particularly structural units derived from (b1); 50-98 mol% (more preferably 55-90 mol%),.
Structural unit derived from (b); 2-50 mol% (more preferably 10-45 mol%).
When the ratio of the structural units of the resin [K1] is within the above range, the storage stability, developability, and solvent resistance of the obtained pattern tend to be excellent.
The resin [K1] is described in the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Kagaku-Dojin Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the document. It can be manufactured with reference to the cited references.
Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and the mixture is stirred. Examples include heating and heat retention. The polymerization initiator, solvent, and the like used here are not particularly limited, and any of those usually used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Be done. The solvent may be any one that dissolves each monomer, and the solvent (E) described later can be used as the solvent of the colored curable resin composition.
As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. You may use it. In particular, by using the solvent (E) described later as the solvent in this polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 4 to 45 mol% (more preferably 10 to 30 mol%),
Structural units derived from (b), particularly structural units derived from (b1); 2 to 95 mol% (more preferably 5 to 80 mol%),.
Structural unit derived from (c); 1-65 mol% (more preferably 5-60 mol%).
When the ratio of the structural units of the resin [K2] is within the above range, the storage stability, developability, solvent resistance of the obtained pattern, heat resistance and mechanical strength tend to be excellent.
The resin [K2] can be produced in the same manner as described as the method for producing the resin [K1]. Specifically, predetermined amounts of (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent are charged in the reaction vessel, and the mixture is stirred, heated and kept warm in a deoxidized atmosphere. There is a way to do it. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. You may use it.

In the resin [K3], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K3].
Structural unit derived from (a); 2-55 mol% (more preferably 10-50 mol%),
Structural unit derived from (c); 45-98 mol% (more preferably 50-90 mol%).
The resin [K3] can be produced in the same manner as described as the method for producing the resin [K1].

The resin [K4] obtains a copolymer of (a) and (c), and (a) has a cyclic ether structure having 2 to 4 carbon atoms of (b), particularly an oxylane ring of (b1). It can be produced by adding it to a carboxylic acid and / or a carboxylic acid anhydride having it. Specifically, first, the copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
Structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%),
Structural unit derived from (c); 50-95 mol% (more preferably 55-90 mol%).

Next, a part of the carboxylic acid and / or the carboxylic acid anhydride derived from (a) in the copolymer has a cyclic ether structure having 2 to 4 carbon atoms of (b), particularly (b1). React the oxirane ring. Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced from nitrogen to air, and (b) (particularly (b1)), a carboxylic acid or a carboxylic acid anhydride was used. A reaction catalyst (eg, tris (dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) with the cyclic ether structure are placed in a flask and reacted at 60 to 130 ° C. for 1 to 10 hours. , Resin [K4] can be obtained.
The amount of (b) used, particularly the amount of (b1) used, is preferably 5 to 80 mol, more preferably 10 to 75 mol, with respect to 100 mol of (a). Within this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good. Since the cyclic ether structure is highly reactive and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) (particularly (b1)) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the calorific value due to the polymerization and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value due to the polymerization, and the like.

As the first step, the resin [K5] obtains a copolymer of (b) (particularly (b1)) and (c) in the same manner as in the above-mentioned method for producing the resin [K1]. In the same manner as above, the obtained copolymer may be a solution after the reaction as it is, a concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation. You may use the one taken out as.
(B) The ratio of the structural units derived from (particularly (b1)) and (c) is preferably in the following range with respect to the total number of moles of all the structural units constituting the above-mentioned copolymer.
Structural units derived from (b), particularly structural units derived from (b1); 5 to 95 mol% (more preferably 10 to 90 mol%),.
Structural unit derived from (c); 5 to 95 mol% (more preferably 10 to 90 mol%).

Further, under the same conditions as the method for producing the resin [K4], (a) is added to the cyclic ether structure derived from (b) of the copolymer of (b) (particularly (b1)) and (c). The resin [K5] can be obtained by reacting the carboxylic acid or the carboxylic acid anhydride having. The amount of (a) used to react with the above-mentioned copolymer is preferably 5 to 80 mol with respect to 100 mol of (b) (particularly (b1)). Since the cyclic ether structure is highly reactive and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K5], and (b1-1) is more preferable.

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction between the cyclic ether structure and the carboxylic acid or the carboxylic acid anhydride.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, 1 , 2,3,6-Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymicic acid anhydride) and the like. Be done.

Among the resins [K1] to [K6], the preferred resin as the resin (B) is [K1] or [K2]. The resin (B) may be made of one kind of resin or may contain two or more kinds of resins.

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30, It is 000. When the weight average molecular weight (Mw) is in the above range, the unexposed portion tends to have high solubility in a developing solution, and the residual film ratio and hardness of the obtained pattern tend to be high. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
The solution acid value of the resin (B) is preferably 5 to 180 mg-KOH / g, more preferably 10 to 100 mg-KOH / g, and even more preferably 12 to 50 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.
The content of the resin (B) is preferably 5 to 50% by mass, more preferably 15 to 45% by mass, and further preferably 25 to 40% of the solid content of the colored curable resin composition in 100% by mass. It is mass%. When the content of the resin (B) is in the above range, the unexposed portion tends to have high solubility in the developing solution.

[3] Polymerizable compound (C)
The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical or the like generated from the polymerization initiator (D) by light irradiation or the like, and is a compound having a polymerizable ethylenically unsaturated bond or the like. Can be mentioned. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.
Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and is preferably a trimethylolpropanetri (meth) acrylate, a pentaerythritol tri (meth) acrylate, and a pentaerythritol. Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate , Tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified Examples thereof include pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Of these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable.
The colored curable resin composition of the present invention can contain one kind or two or more kinds of polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, and more preferably 40 to 70 parts by mass with respect to 100 parts by mass of the resin (B) in the colored curable resin composition. ..

[4] Polymerization initiator (D)
The polymerization initiator (D) is a compound capable of initiating polymerization by generating active radicals, acids and the like by the action of light and heat.
The polymerization initiator (D) contains an oxime-based compound. As a result, even with an appropriate colorant concentration, Rec. ITU-R BT. A color filter having a high inclusion rate in the color gamut of 2020 can be formed, and a colored curable resin composition having good patterning property can be obtained.
Two or more kinds of the polymerization initiator (D) may be used in combination in consideration of sensitivity, patterning property, formability of a precise pattern shape, and the like.

Examples of the oxime compound include an O-acyloxime compound and the like.
The O-acyloxime compound is a compound having a structure represented by the formula (d). Hereinafter, * represents a bond.

Examples of such O-acyloxym compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-on-2-imine, N-acetyloxy-1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetyloxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-) 2,4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetyloxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazole-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3- Cyclopentylpropane-1-on-2-imine, N-acetyloxy-1- [9- (2-ethylhexyl) -6- (2,4,6-trimethylbenzoyl) -9H-benzo [i] carbazole-3-3 Il] -3- [1- (2,2,3,3-tetrafluoropropyloxy) phenyl] methaneimine and the like.
Commercially available products such as Irgacure OXE01, OXE02, OXE03 (all manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may be used. With these O-acyloxime compounds, there is a tendency to obtain a color filter having excellent photolithography performance.

The polymerization initiator (D) can contain other polymerization initiators other than the oxime-based compound. Examples of other polymerization initiators include alkylphenone compounds, biimidazole compounds, triazine compounds, acylphosphine oxide compounds and the like.

The alkylphenone compound is a compound having a structure represented by the formula (d4) or a structure represented by the formula (d5). * Represents a bond. In these structures, the benzene ring may have a substituent.

Examples of the compound having a structure represented by the formula (d4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl). ) -2-Benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one, etc. Be done. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF Corporation) may be used.
Examples of the compound having a structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy). ) Phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d4).

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-Tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5'-Tetraphenyl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-2'-bis) Chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) Biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), imidazole in which the phenyl group at the 4,4', 5,5'-position is substituted with a carboalkoxy group. Examples thereof include compounds (see, for example, Japanese Patent Application Laid-Open No. 7-10913) and the like.
Of these, a compound represented by the following formula or a mixture thereof is preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-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- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like can be mentioned. ..

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of the polymerization initiator (D) other than the above include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, o-benzoylmethyl benzoate, 4-phenylbenzophenone, and the like. Benzoyl compounds such as 4-benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-fe. Kinon compounds such as nanthrenquinone, 2-ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, titanosen compounds and the like.

From the viewpoint of patterning property and expansion of the displayable color reproduction range, it is preferable that the content of the oxime compound in the polymerization initiator (D) is high. Specifically, the content of the oxime compound in the polymerization initiator (D) is preferably 50% by mass or more, more preferably 80% by mass or more, based on 100% by mass of the polymerization initiator (D). It is more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.

The content of the polymerization initiator (D) is preferably 0.03 to 0.25 parts by mass, more preferably 0, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 0.05 to 0.15 parts by mass, more preferably 0.07 to 0.10 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter tends to be improved.

[5] Polymerization initiation aid (D1)
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Of these, the thioxanthone compound is preferable. Two or more kinds of polymerization initiation aids (D1) may be used in combination.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-. 2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( Examples thereof include ethylmethylamino) benzophenone, and among them, 4,4'-bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, and N. -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

The content of the polymerization initiation aid (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a department. When the content of the polymerization initiation aid (D1) is within the above range, a pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

[6] Solvent (E)
The color-curable resin composition preferably contains one kind or two or more kinds of solvents (E). Examples of the solvent (E) include an ester solvent (solvent containing -COO-), an ether solvent other than the ester solvent (solvent containing -O-), an ether ester solvent (solvent containing -COO- and -O-), and the like. Examples thereof include a ketone solvent (solvent containing −CO—) other than the ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, 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.
Examples of the ether solvent include 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, and propylene glycol monoethyl ether. , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol, methyl anisol and the like.

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

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

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

The solvent (E) preferably contains an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm from the viewpoint of coatability and drying property. Among them, the solvent (E) is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3 It preferably contains at least one selected from the group consisting of -methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide, preferably containing propylene glycol monomethyl ether acetate, propylene glycol monomethyl. It is more preferable to contain at least one selected from the group consisting of ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate.

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

[7] Leveling agent (F)
The colored curable resin composition of the present invention may contain one or more leveling agents (F). Examples of the leveling agent (F) include a silicone-based surfactant (without a fluorine atom), a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324. , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK), etc. Can be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554. R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

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 Megafuck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

The content of the leveling agent (F) is usually 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, in the colored curable resin composition. It is preferably 0.004% by mass or more and 0.05% by mass or less. The content of the pigment dispersant is not included in this content.

[8] Other Ingredients The color curable resin composition of the present invention contains, if necessary, a filler, a polymer compound other than the resin (B), an antioxidant, an adhesion accelerator, an ultraviolet absorber, and an anti-aggregation agent. It can contain one or more additives such as agents.

<Manufacturing method of colored curable resin composition>
The color-curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and if necessary, a solvent (E) and a leveling agent ( It can be prepared by mixing F), a polymerization initiator (D1), and other components.

<Color filter and its manufacturing method>
The color curable resin composition of the present invention is useful as a material for a color filter, particularly a green color filter.
The color filter may be formed of a molded product of the cured product of the colored curable resin composition, or may be formed as a cured product (coating film) of the colored curable resin composition applied on the substrate. It may be a cured product (pattern) of a colored curable resin composition formed in a pattern on a substrate.
The color filter according to the present invention is typically used as a green pixel.
Examples of the method for producing a cured product of the colored curable resin composition in a pattern include a photolithography method, an inkjet method, a printing method and the like, and a photolithography method is preferable. The photolithography method is a method in which a colored curable resin composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed and developed through a photomask. In the photolithography method, the cured product of the composition layer can be formed as a coating film by not using a photomask at the time of exposure and / or not developing the photomask.

The substrate includes a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or on the above substrate. Aluminum, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit and the like may be formed on these substrates.

The formation of the coating film or the pattern by the photolithography method can be performed by known or conventional equipment and conditions, and can be produced, for example, as follows. First, a colored curable resin composition is applied onto a substrate and dried by heating and drying (pre-baking) and / or under reduced pressure to remove volatile components such as a solvent to obtain a smooth composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature for heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When drying under reduced pressure, it is preferable to carry out drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C. The film thickness of the composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.
The composition layer is then exposed via a photomask when forming the desired pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. It is not necessary to use a photomask when forming the coating film. As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp and the like.
For exposure, since it is possible to uniformly irradiate the entire exposed surface with parallel rays and accurately align the photomask with the substrate on which the composition layer is formed, an exposure device such as a mask aligner or a stepper can be used. It is preferable to use.
A pattern is formed on the substrate by bringing the exposed composition layer into contact with a developing solution for development. By development, the unexposed portion of the composition layer is dissolved in a developer and removed.
The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
Further, it is preferable to post-bake the obtained pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.
The film thickness of the coating film and the pattern after post-baking is generally preferably 3 μm or less, and more preferably 2.8 μm or less.
The lower limit of the film thickness of the coating film and the pattern is not particularly limited, but is usually 1 μm or more, and may be 1.5 μm or more. As described above, according to the present invention, it is possible to expand the displayable color gamut (and to improve the inclusion rate of the color gamut of Rec. ITU-R BT. 2020) even with a thin film. Is.

<Display device>
The color filter according to the present invention is useful as a color filter used in a display device (liquid crystal display device, organic EL device, electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples. In the examples,% and parts representing the content or the amount used are based on mass unless otherwise specified.

<Synthesis Example 1: Preparation of Resin (B)>
An appropriate amount of nitrogen was poured into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace it with a nitrogen atmosphere, and 371 parts by mass of 1-methoxy-2-propyl acetate was added and heated to 85 ° C. with stirring. .. Then, 54 parts by mass of acrylic acid, 225 parts by mass of a mixture of 3,4-epoxytricyclo [5.2.1.02,6] decane-8 and / and 9-yl acrylate, vinyl toluene (isomer mixture) 81. A mixed solution of 80 parts by mass of 1-methoxy-2-propyl acetate was added dropwise over 4 hours. On the other hand, a solution prepared by dissolving 30 parts by mass of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts by mass of 1-methoxy-2-propylacetylate was added dropwise over 5 hours. After the dropping of the initiator solution is completed, the mixture is kept at the same temperature for 4 hours and then cooled to room temperature to have a B-type viscosity (23 ° C.) of 246 mPas, a solid content of 37.5% by mass, and a solution acid value of 43 mg-KOH / g. A polymer was obtained. The weight average molecular weight Mw of the produced copolymer was 10600 and the dispersity was 2.01.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin (B) were measured by using the GPC method under the following conditions. The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained under the following conditions was defined as the molecular weight distribution.

Equipment; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40 ° C
Solvent; THF
Flow velocity; 1.0 mL / min
Test solution solid content concentration; 0.001 to 0.01% by mass
Injection volume; 50 μL
Detector; RI
Calibration standard; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Made by Tosoh Corporation)

<Synthesis Example 2: Preparation of Pigment Dispersion Liquid (A1)>
C. I. Pigment Blue 16 6.8 copies C.I. I. Pigment Yellow 139 5.2 parts Acrylic pigment dispersant 4.5 parts Propylene glycol monomethyl ether acetate 83.5 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A1). rice field.

<Synthesis Example 3: Preparation of Pigment Dispersion Liquid (A2)>
C. I. Pigment Blue 16 4.8 copies C.I. I. Pigment Yellow 185 7.2 parts Acrylic pigment dispersant 5.5 parts Propylene glycol monomethyl ether acetate 82.5 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A2). rice field.

<Synthesis Example 4: Preparation of Pigment Dispersion Liquid (A3)>
C. I. Pigment Blue 16 3.0 copies C. I. Pigment Yellow 150 9.0 parts Acrylic pigment dispersant 5.3 parts Propylene glycol monomethyl ether acetate 82.7 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A3). rice field.

<Synthesis Example 5: Preparation of Pigment Dispersion Liquid (A4)>
C. I. Pigment Blue 16 4.8 copies C.I. I. Pigment Yellow 139 1.0 copies C.I. I. Pigment Yellow 150 6.3 parts Acrylic pigment dispersant 5.1 parts Propylene glycol monomethyl ether acetate 82.8 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A4). rice field.

<Synthesis Example 6: Preparation of Pigment Dispersion Liquid (A5)>
C. I. Pigment Blue 16 5.2 Part C. I. Pigment Yellow 139 2.6 copies C.I. I. Pigment Yellow 138 4.3 parts Acrylic pigment dispersant 4.3 parts Propylene glycol monomethyl ether acetate 83.6 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A5). rice field.

<Synthesis Example 7: Preparation of Pigment Dispersion Liquid (A6)>
C. I. Pigment Blue 16 5.3 Part C. I. Pigment Yellow 139 0.2 copies C. I. Pigment Yellow 129 7.2 parts Acrylic pigment dispersant 5.1 parts Propylene glycol monomethyl ether acetate 82.2 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A6). rice field.

<Examples 1 to 6 and Comparative Example 1>
(1) Preparation of Coloring Curable Resin Composition Each component shown in Table 1 was mixed so as to have the blending amount shown in Table 1 to obtain a coloring curable resin composition. In each Example and Comparative Example, the PWC (pigment volume concentration) is 40%. The unit of the blending amount of each component in Table 1 is "part by mass", and the blending amount is in terms of solid content.
The polymerizable compound (C), the polymerization initiator (D-1), the polymerization initiator (D-2), and the leveling agent (F) are as follows.
Polymerizable compound (C): dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "A-9550")
Polymerization Initiator (D-1): Compound represented by the following formula (manufactured by BASF Corporation, trade name "Irgacure OXE03")

Polymerization Initiator (D-2): 2,2', 4-Tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4,5-diphenyl-1,1'-CHEMBRIDGE INTERNATIONAL Product name "TCDM" made by CORPORATION)
Leveling agent (F): Fluorine-containing group / lipophilic group-containing oligomer (manufactured by DIC Corporation, trade name "Megafuck F-554")

(2) Preparation of Coating Film A colored curable resin composition was applied on a 2-inch square glass substrate (“Eagle XG” manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes. After cooling, the substrate coated with this colored curable resin composition was exposed to an exposure amount of 80 mJ / cm ² (based on 365 nm) under an atmospheric atmosphere using an exposure machine (“TME-150RSK” manufactured by Topcon Corporation). It was irradiated with light. Then, it was post-baked in an oven at 230 ° C. for 30 minutes to obtain a coating film.

(3) Film thickness measurement With respect to the obtained coating film, the film thickness was measured using a film thickness measuring device (“DEKTAK3” manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.

(4) Measurement of chromaticity The obtained coating film is spectrally measured using a colorimeter (“OSP-SP-200” manufactured by Olympus Co., Ltd.), and the characteristic function of the C light source is used to measure the CIE. The xy chromaticity coordinates (x, y) and the lightness Y in the XYZ color system were measured. The results are shown in Table 2.

(5) Measurement of chromaticity A color curable resin composition was applied on a 2-inch square glass substrate (“Eagle XG” manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes.
After cooling, the distance between the substrate on which the composition layer was formed and the quartz glass photomask was set to 150 μm, and an exposure machine (“TME-150RSK” manufactured by Topcon Corporation) was used to create an atmosphere of 50 mJ / cm. Light was irradiated with an exposure amount of ² (based on 365 nm). As the photomask, a photomask having a 100 μm line and space pattern formed was used.
The composition layer after light irradiation was developed by immersing it in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, and according to the following evaluation criteria. The patterning property was evaluated. The results are shown in Table 2.
◯: A pattern having a predetermined line width is formed.
X: There is a portion where a pattern having a predetermined line width is not formed and is not dissolved and removed by the developer.

In Examples 1 to 6, the chromaticity coordinates (x, y) are unified to one of the target green chromaticity coordinates (0.170, 0.760). In addition, Rec. ITU-R BT. The chromaticity coordinates (x, y) of 2020 are (0.170, 0.797).
Comparative Example 1 had poor patterning properties. On the other hand, in Examples 1 to 6, Rec. ITU-R BT. It showed good patterning while achieving a high inclusion rate of the 2020 color gamut. In particular, in Examples 1, 2, 4, and 5, Rec. ITU-R BT. It showed good patterning while achieving a high inclusion rate of the 2020 color gamut.

Claims (3)

A color filter formed from a color curable resin composition .
The color curable resin composition contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).
The colorant (A) is C.I. I. Contains Pigment Blue 16 and yellow colorant, no green colorant,
C. I. The content of Pigment Blue 16 is 25% by mass or more in 100% by mass of the colorant (A).
A color filter in which the polymerization initiator (D) contains an oxime compound . The color filter according to claim 1, wherein the yellow colorant contains a compound having an isoindoline skeleton. A display device comprising the color filter according to claim 1 or 2 .