JP6704337B2 - Colored photosensitive resin composition, color filter and display device including the same - Google Patents

Description

The present invention relates to a colored photosensitive resin composition, a color filter and a display device including the same.

In recent years, liquid crystal display devices have been under development for expanding the displayable color reproduction range, and as a part thereof, darker color filters are required. As a method for darkening the color of the color filter, there is a method of increasing the colorant concentration in the color filter. However, when the colorant concentration is increased, the performance as a colored photosensitive resin composition is deteriorated such as the deterioration of the pattern shape. Resulting in. On the other hand, by using a coloring agent having a high coloring power, it is possible to form a pattern of a dark color filter, but the lightness is lowered. There is also a method of expressing a dark color by using a thick film as a color filter. However, if the film is made thick, color mixture of light occurs between adjacent pixels when applied to a liquid crystal display device.

Japanese Patent No. 5604968 (Patent Document 1) discloses C.I. as a colorant composition capable of realizing a green color filter having a high color purity with a thin film. I. Pigment Blue 16 and C.I. I. Pigment Green 58 and C.I. I. Pigment Yellow 129 and C.I. I. Pigment Yellow 150, and C.I. I. Pigment Blue 16 is proposed as a green colorant composition having a content of 5 to 40% by mass.

Japanese Patent No. 5604968

The colorant composition described in Patent Document 1 aims to bring the NTSC standard ratio close to 100% (paragraphs [0003], [0044] to [0046], etc.) and has a displayable color reproduction range. It has not been possible to satisfy the recent demand for further expansion. In recent years, Recommendation Rec. which defines a video format of Super Hi-Vision (SHV). ITU-R BT. 2020 has been issued, and the color reproduction range is further expanded. ITU-R BT. There is a demand for a color filter having a high coverage of the color gamut of 2020 (the ratio of the color gamut that can be expressed in the color gamut to the color gamut of Rec. ITU-R BT.2020).

Therefore, the present invention can exhibit good brightness even with a thin film and an appropriate colorant concentration, and at the same time, Rec. ITU-R BT. An object is to provide a colored photosensitive resin composition capable of forming a color filter having a high coverage of the color gamut of 2020, a color filter formed from the colored photosensitive resin composition, and a display device including the color filter. And

The present invention provides the following colored photosensitive resin composition, color filter, and display device.

[1] contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
The colorant (A) is C.I. I. Pigment Blue 16 and C.I. I. Pigment Green 59, a colored photosensitive resin composition.

[2] The colored photosensitive resin composition according to [1], wherein the colorant (A) further contains a yellow pigment.

[3] The yellow pigment is C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 150, or the colored photosensitive resin composition according to [2].

[4] The yellow pigment is C.I. I. Pigment Yellow 185, the colored photosensitive resin composition according to [2] or [3].

[5] The colored photosensitive resin composition according to any one of [1] to [4], wherein the polymerization initiator (D) contains an oxime compound.

[6] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [5].

[7] A display device including the color filter according to [6].

According to the colored photosensitive resin composition of the present invention, good brightness can be exhibited even with a thin film and an appropriate colorant concentration, and Rec. ITU-R BT. A color filter having a high coverage of the color gamut of 2020 and a display device including the color filter can be provided.

3 is a spectrum of a light source used for chromaticity evaluation in Examples and Comparative Examples.

<Colored photosensitive resin composition>
The colored photosensitive 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 C.I. I. Pigment Green 59 is included. C. I. Pigment Blue 16 and C.I. I. Pigment Green 59, which contains a specific combination of pigment green 59, has a good lightness and an expandable color gamut even though it is a thin film and has an appropriate concentration of the coloring agent (and thus Rec. ITU). -Improvement of the coverage of the color gamut of RBT.2020).

The compounds exemplified as each component in the present specification can be used alone or in combination of two or more kinds, unless otherwise specified.

[1] Colorant (A)
In the colored photosensitive resin composition according to the present invention, the colorant (A) is C.I. I. Pigment Blue 16 and C.I. I. Pigment Green 59 is included.
C. in the colorant (A). I. Pigment Blue 16 and C.I. I. The content ratio with CI Pigment Green 59 (CI Pigment Blue 16/CI Pigment Green 59) is usually 0.1 to 60 on a weight basis, and has good brightness and displayable color reproduction range. From the viewpoint of effectively coexisting with expansion of 0.1, it is preferably 0.1 to 20, more preferably 0.1 to 10, still more preferably 0.4 to 6, and still more preferably 0.45 to 3, Particularly preferably, it is 0.45 to 2.

In the colorant (A), C.I. I. Pigment Green 59 is C.I. I. Pigment Blue 16 and C.I. I. Pigment Green 59 is preferably 10 to 70% by weight, and more preferably 40 to 70% by weight.

C. in the colorant (A). I. Pigment Blue 16 and C.I. I. Pigment Green 59, the total content is usually 10% by weight or more in 100% by weight of the colorant (A), from the viewpoint of effectively achieving both good brightness and expansion of the displayable color gamut. It is preferably at least 20% by weight, more preferably at least 30% by weight, further preferably at least 45% by weight, particularly preferably at least 50% by weight. The total content may be 100% by weight in 100% by weight of the colorant (A).
As described below, the colorant (A) is C.I. I. Pigment Blue 16 and C.I. I. Pigment Green 59 may be included in other colorants. In this case, the total content may be 90% by weight or less, 80% by weight or less, or 70% by weight or less in 100% by weight of the colorant (A).

C. I. Pigment Blue 16 and C.I. I. When a colorant other than Pigment Green 59 is included, the total content may be 30% by weight or more, or 35% by weight or more in 100% by weight of the colorant (A).

C. in the colorant (A). I. The content of Pigment Blue 16 is, for example, 1 to 99% by weight in 100% by weight of the colorant (A), which is preferable from the viewpoint of effectively achieving both good lightness and expansion of the displayable color reproduction range. Is 10 to 80% by weight, more preferably 25 to 40% by weight.

C. in the colorant (A). I. The content of Pigment Green 59 is, for example, 1 to 99% by weight in 100% by weight of the colorant (A), which is preferable from the viewpoint of effectively achieving both good lightness and expansion of the displayable color reproduction range. Is 2 to 60% by weight, more preferably 5 to 60% by weight, still more preferably 15 to 50% by weight.

The colorant (A) is C.I. I. Pigment Blue 16 and C.I. I. Pigment Green 59 may be included in other colorants.
Other colorants include Pigment Blue 16 and C.I. I. Pigment Green 59 may be a pigment other than Pigment Green 59, a dye, or both of them.
Other colorants may be used alone or in combination of two or more. Other pigments include organic pigments and inorganic pigments, and compounds that are classified as pigments by the Color Index (published by The Society of Dyers and Colorists).

Known dyes can be used as the dye, 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 those having a hue other than pigment, and known dyes described in Dyeing Note (Shikiso Co., Ltd.).
Further, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin. Examples include 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 pigment and/or blue dye) other than Pigment Blue 16 may be included. Other blue pigments include C.I. I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and the like.

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. 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, C. 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293 and the like. I. Direct blue dye;
C. I. C. such as Disperse Blue 1, 14, 56, 60 and the like. 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. 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. Modant blue dye;
Etc.

However, from the viewpoint of effectively achieving both good lightness and expansion of the displayable color reproduction range, C.I. I. It is preferable that the content of Pigment Blue 16 is high. Specifically, C.I. I. The content of Pigment Blue 16 is preferably 50% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and particularly preferably 95% by weight in 100% by weight of the blue colorant. % Or more, and most preferably 100% by weight.

The colorant (A) is C.I. I. In addition to Pigment Green 59, other green colorants (green pigment and/or green dye) can be included. Other green pigments include C.I. I. Pigment Green 7, 36, 58 and the like can be exemplified.

However, from the viewpoint of effectively achieving both good brightness and expansion of the displayable color reproduction range, C.I. I. It is preferable that the content of Pigment Green 59 is high. Specifically, C.I. I. The content of Pigment Green 59 in 100% by weight of the green colorant is preferably 50% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and particularly preferably 95% by weight. % Or more, and most preferably 100% by weight.

The colorant (A) is C.I. I. Pigment Blue 16 and C.I. I. As the colorant other than Pigment Green 59, a colorant (pigment and/or dye) other than the blue colorant and the green colorant can be included.
The other colorants may be used alone or in combination of two or more. As other colorants other than the blue colorant and the green colorant,
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, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like violet color pigments;
Etc.

Above all, the colorants other than the blue colorant and the green colorant are preferably yellow pigments. Examples of the yellow pigment include C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 150 is preferred. Among the yellow pigments, when compared with the same color filter thickness and the same colorant concentration, C.I. I. Pigment Blue 16 and C.I. I. Pigment Green 59 provides better lightness, so that C.I. I. Pigment Yellow 139, 185 and the like, a colorant having an isoindoline skeleton (isoindoline yellow pigment) is preferably contained, and particularly C.I. I. Pigment Yellow 185 is more preferable. The colorant (A) may contain two or more types of yellow pigments. The combination of yellow pigments is not particularly limited, and C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 150, and the like.

The content of other colorants (yellow pigment, etc.) other than the blue colorant and the green colorant is C.I. I. Pigment Green 59 100 parts by weight, preferably 1 to 1000 parts by weight, more preferably 5 to 800 parts by weight, and further preferably 50 to 300 parts by weight.

The total content of the colorant (A) in the colored photosensitive resin composition is usually 20 to 50% by weight in 100% by weight of the solid content of the colored photosensitive resin composition, but the displayable color reproduction range is expanded. From the viewpoint of, it is preferably 30% by weight or more, and more preferably 35% by weight or more.
Further, from the viewpoint of easy formation of the resist pattern, the total content is preferably 45% by weight or less in 100% by weight of the solid content of the colored photosensitive resin composition.
According to the present invention, by setting the total content of the colorant (A) to an appropriate amount, good brightness can be exhibited while suppressing deterioration of the pattern shape and the like. ITU-R BT. A color filter having a high coverage of the 2020 color gamut can be formed.
In addition, in this specification, "solid content of a colored photosensitive resin composition" refers to all components other than a solvent (E) among the components contained in a colored photosensitive resin composition. The total amount of solid content and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography and gas chromatography.

The various pigments in the colored photosensitive resin composition are preferably in a state of a dispersion liquid in which they are uniformly dispersed in a solvent. The pigment preferably has a uniform particle size. The dispersion liquid can be obtained by mixing a pigment and a solvent. You may mix a pigment dispersant as needed. By performing the dispersion treatment by adding the pigment dispersant, it is possible to obtain a pigment dispersion liquid in which the pigment is uniformly dispersed in the solvent.

As the pigment dispersant, commercially available surfactants can be used, including silicone-based, fluorine-based, ester-based (including polyester-based), cation-based, anion-based, nonionic, amphoteric, polyester-based, polyamine-based, Acrylic-based surfactants may be mentioned. Specific examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid-modified polyester, tertiary amine-modified polyurethane, polyethyleneimine, and KP (trade name). Shin-Etsu Chemical Co., Ltd.), Floren (Kyoeisha Chemical Co., Ltd.), Sols Perth (Zeneca Co., Ltd.), EFKA (BASF Japan Co., Ltd.), Addisper (registered trademark) (Ajinomoto Fine Techno Co., Ltd.) Manufactured by Big Chemie) and the like. The pigment dispersants may be used alone or in combination of two or more.

When a pigment dispersant is used, the amount thereof is preferably 100 parts by weight or less, more preferably 5 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniform dispersed state tends to be easily obtained.

The solvent that constitutes the pigment dispersion is not particularly limited, and examples thereof include the same solvents as the below-mentioned solvent (E) that may be contained in the colored photosensitive 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. It is preferably acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate or the like.

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

Various pigments in the colored photosensitive resin composition, if necessary, rosin treatment, surface treatment using a pigment derivative or a pigment dispersant having an acidic group or a basic group introduced, to the pigment surface with a polymer compound, etc. Grafting treatment, atomization treatment by sulfuric acid atomization method, etc., cleaning treatment by organic solvent or water for removing impurities, removal treatment of ionic impurities by ion exchange method, etc. may be performed.

[2] Resin (B)
The colored photosensitive resin composition of the present invention contains one kind or two or more kinds of resin (B). The resin (B) is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: at least one kind (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides [hereinafter, sometimes 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)”. ) With a copolymer.

Resin [K2]: (a) and (b), and a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) [hereinafter "(c)". There is a thing. ) With a copolymer.

Resin [K3]: a copolymer of (a) and (c).
Resin [K4]: Resin obtained by reacting (b) with the copolymer of (a) and (c).

Resin [K5]: Resin obtained by reacting (a) with the copolymer of (b) and (c).
Resin [K6]: A resin obtained by reacting the 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-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride);
Unsaturated mono[(meth)acryloyloxyalkyl]esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl]succinate and mono[2-(meth)acryloyloxyethyl]phthalate. ;
Examples include α-(hydroxymethyl)(meth)acrylic acid and unsaturated (meth)acrylic acid containing a hydroxy group and a carboxy group in the same molecule.

Among them, (a) is preferably (meth)acrylic acid, maleic anhydride or the like, from the viewpoint of copolymerization reactivity and the solubility in an alkaline aqueous solution.

In addition, in this specification, "(meth)acryl" represents at least 1 sort(s) selected from the group which consists of acryl and methacryl. The same applies to expressions 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 oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. Refers to a sex compound. (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

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

Examples of (b1) include a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter, referred to as “(b1-1)”. ], and a monomer (b1-2) having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon [hereinafter, may be referred to as “(b1-2)”. ] Is 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 (Glycidyloxymethyl) styrene etc. are mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, , Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd., 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by the following formula (I). Examples thereof include compounds and compounds represented by the following formula (II).

In formulas (I) and (II), R ^a and R ^b each 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. May be replaced with. X ¹ and X ² are, independently of one another, a single ^{bond, * - R c -, *} - R c -O -, * - R c -S-, or * represents a -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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Examples of the alkyl group having a hydrogen atom substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. Examples thereof include a 1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.

R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

As the alkanediyl group constituting R ^c , 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-group. 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. There, more preferably a single bond, * - is CH ₂ CH ₂ -O- group.

Specific examples of the compound represented by the formula (I) include compounds represented by the following formula (I-1) to the following formula (I-15), preferably the formula (I-1) and the formula (I-1). I-3), the formula (I-5), the formula (I-7), the formula (I-9), and the compounds represented by the formula (I-11) to the formula (I-15) are mentioned, more preferably. Are compounds represented by formula (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 following formulas (II-1) to (II-15), preferably the formula (II-1) and the formula (II-1). II-3), the formula (II-5), the formula (II-7), the formula (II-9), and the compounds represented by the formula (II-11) to the formula (II-15) are mentioned, more preferably. Are compounds represented by formula (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) can be used alone. They can be mixed in any ratio. When mixing, the mixing ratio is represented by formula (I): formula (II) [molar ratio], preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and further preferably 20:. 80 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. As a preferable example of (b2), 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyl oxetane may be mentioned.

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. Preferable examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat 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- Iyl (meth)acrylate [In the art, it is referred to by its trivial name as "dicyclopentanyl (meth)acrylate". It may also be called "tricyclodecyl (meth)acrylate". ], tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate [known in the art as a trivial name "dicyclopentenyl (meth)acrylate"]. ], dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (Meth)acrylic acid ester such as (meth)acrylate;
Hydroxy group-containing (meth)acrylic acid ester such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and itaconic acid diethyl;
Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]. Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2] .1] hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy -5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2 2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyl) Oxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclo unsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 A dicarbonylimide derivative such as maleimide propionate or N-(9-acridinyl)maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene. , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, (c) is benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo. [2.2.1] Hept-2-ene and the like are preferable. Further, (c) is more preferably benzyl (meth)acrylate or tricyclodecyl (meth)acrylate because of excellent developability during pattern formation.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range in all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol%),
Structural units derived from (b), particularly structural units derived from (b1); 50 to 98 mol% (more preferably 55 to 90 mol%).

When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability, the developability and the solvent resistance of the obtained pattern tend to be excellent.

The resin [K1] is described in the literature “Experimental method for polymer synthesis” (Takayuki Otsu, Kagaku Dojin, 1st edition, 1st edition, published on March 1, 1972) and the literature. It can be manufactured by referring to the cited references.

Specifically, a method of charging a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent and the like into a reaction vessel, and stirring, heating and keeping the temperature in a deoxygenated atmosphere is a method. Can be mentioned. The polymerization initiator, solvent and the like used here are not particularly limited, and any of those commonly 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. As the solvent, any solvent capable of dissolving each monomer may be used, and the solvent (E) described below may be used as the solvent of the colored photosensitive resin composition.

The obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. May be used. In particular, when the solvent (E) described below is used as a solvent in this polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably in the following range in all the structural units constituting the resin [K2].
Structural unit derived from (a): 4-45 mol% (more preferably 10-30 mol%),
Structural unit derived from (b), particularly structural unit derived from (b1); 2-95 mol% (more preferably 5-80 mol%),
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol %).

When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability, the developability, the solvent resistance of the obtained pattern, the heat resistance and the mechanical strength tend to be excellent.

The resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1]. Specifically, the reaction vessel is charged with a predetermined amount of (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. There is a method of doing. The obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural units derived from each is preferably in the following range in 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 to 98 mol% (more preferably 50 to 90 mol%).

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

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

Next, a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the above copolymer has a cyclic ether structure having 2 to 4 carbon atoms, which is contained in (b), particularly (b1). React the oxirane ring. Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with nitrogen from air to produce (b) (particularly (b1)), a carboxylic acid or a carboxylic acid anhydride. By placing a reaction catalyst (eg, tris(dimethylaminomethyl)phenol) and a polymerization inhibitor (eg, hydroquinone) in the flask with a cyclic ether structure and reacting 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, and more preferably 10 to 75 mol, per 100 mol of (a). Within this range, the storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tend to be well balanced. Since the cyclic ether structure has high reactivity and unreacted (b) hardly remains, (b1) is preferable as (b) used in the resin [K4], and (b1-1) is more preferable.

The amount of the reaction catalyst used is preferably 0.001 to 5% by weight based on the total amount of (a), (b) (particularly (b1)) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by weight based on the total amount of (a), (b) and (c).

Reaction conditions such as a charging method, a reaction temperature and a time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by 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 and the amount of heat generated by the polymerization.

As the resin [K5], as a first step, a copolymer of (b) (particularly (b1)) and (c) is obtained in the same manner as in the method for producing the resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation. You may use what was taken out as.

The ratio of the structural units derived from (b) (particularly (b1)) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the above copolymer.
A structural unit derived from (b), particularly a structural unit derived from (b1); 5 to 95 mol% (more preferably 10 to 90 mol%),
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%).

Furthermore, under the same conditions as in the method for producing the resin [K4], the cyclic ether structure derived from (b) in the copolymer of (b) (particularly (b1)) and (c) has (a) The resin [K5] can be obtained by reacting the carboxylic acid or carboxylic acid anhydride that it has. The amount of (a) used to react with the above-mentioned copolymer is preferably 5 to 80 mol per 100 mol of (b) (particularly (b1)). Since the cyclic ether structure has high reactivity and unreacted (b) hardly remains, (b1) is preferable as (b) used in 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 anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic 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 (hymic 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 composed 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, and further preferably 5,000 to 30, It is 000. When the weight average molecular weight is in the above range, the unexposed portion has high solubility in a developing solution, and the residual film rate and hardness of the obtained pattern tend to be high. The dispersity [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The solution acid value of the resin (B) is preferably 5 to 180 mg-KOH/g, more preferably 10 to 100 mg-KOH/g, and further 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, for example, by titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and further preferably 15 to 30% in 100% by weight of the solid content of the colored photosensitive resin composition. % By weight. 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 a compound having a polymerizable ethylenically unsaturated bond and the like. Is mentioned. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.

The polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra( (Meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetra Pentaerythritol 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 Examples thereof include 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 and dipentaerythritol hexa(meth)acrylate are preferable.

The colored photosensitive resin composition of the present invention may 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 weight, and more preferably 80 to 120 parts by weight, based on 100 parts by weight of the resin (B) in the colored photosensitive resin composition. ..

[4] Polymerization initiator (D)
The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate an active radical, an acid or the like by the action of light or heat and initiates polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds. The polymerization initiator (D) may be used in combination of two or more kinds in consideration of sensitivity, formation of precise pattern shape and the like. The polymerization initiator (D) preferably contains an oxime compound such as an O-acyl oxime compound because it is advantageous in precisely forming a pattern shape having sensitivity and a desired line width.

The O-acyl oxime compound is a compound having a structure represented by the following formula (d). Hereinafter, * represents a bond.

The O-acyl oxime compound is, for example, a compound represented by the formula (d1) (hereinafter sometimes referred to as “compound (d1)”) or a compound represented by the formula (d2) (hereinafter, referred to as “compound (d2 )”) and a compound represented by the formula (d3) (hereinafter, sometimes referred to as “compound (d3)”).

[In formulas (d1) to (d3),
R ^d1 has a C6-18 aromatic hydrocarbon group which may have a substituent, a C3-C36 heterocyclic group which may have a substituent, and a substituent. Optionally represents an alkyl group having 1 to 15 carbon atoms, or a combination of an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group, which represents a group which may have a substituent. is, -O - methylene group contained _{(-CH 2) -, - CO} -, - S -, - SO 2 - or -NR ^d5 - may be replaced with.
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.
R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent. group a methylene group contained in the hydrocarbon group (-CH ₂ -) is, -O -, - may be replaced in the CO- or -S-, a methine group (-CH contained in the aliphatic hydrocarbon group < ) May be replaced with —PO ₃ <, and the hydrogen atom contained in the above aliphatic hydrocarbon group may be substituted with an OH group.
R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (—CH ₂ —) contained in the alkyl group may be replaced with —O— or —CO—. ]

The aromatic hydrocarbon group represented by R ^d1 has preferably 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group. A phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

The aromatic hydrocarbon group represented by R ^d1 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, more preferably at the γ-position. As the substituent, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group. And the like, an alkyl group having 1 to 15 carbon atoms; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom;

The alkyl group as the above substituent preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms. The alkyl group as the substituent may be linear, branched, or cyclic, or may be a group in which a chain group and a cyclic group are combined. The methylene group (—CH ₂ —) contained in the alkyl group as the substituent may be replaced with —O— or —S—. The hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, and is preferably substituted with a fluorine atom.

Regarding the aromatic hydrocarbon group represented by R ^d1 , examples of the alkyl group as a substituent thereof include groups represented by the following formula. In the formula, * represents a bond.

Regarding the group represented by R ^d1 , examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulas. In the formula, * represents a bond.

Regarding the group represented by R ^d1 , the aromatic hydrocarbon group which may have a substituent is preferably a group represented by the following formula.

(In the formula, R ^d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and the hydrogen atom contained in R ^d6 may be substituted with a halogen atom. m2 is 1 ~ Represents an integer of 5.)

Examples of the alkyl group represented by R ^d6 include the same groups as the alkyl groups exemplified as the substituent for the aromatic hydrocarbon group represented by R ^d1 . The carbon number of R ^d6 is preferably 2 to 7, and more preferably 2 to 5. The alkyl group represented by R ^d6 may be linear, branched or cyclic, and is preferably linear.

Examples of the halogen atom which may be substituted for the hydrogen atom contained in R ^d6 include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, and fluorine is particularly preferable. It is preferable that 2 or more and 10 or less of hydrogen atoms contained in R ^d6 are substituted with halogen atoms, and it is more preferable that 3 or more and 6 or less of hydrogen atoms are substituted with halogen atoms. The substitution position of the R ^d6 O- group is preferably the ortho position and the para position, and particularly preferably the para position. m2 is preferably 1 to 2, and particularly preferably 1.

The heterocyclic group represented by R ^d1 preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and further preferably 3 to 5 carbon atoms. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group and a carbazolyl group.

The heterocyclic group represented by R ^d1 may have one or two or more substituents. Examples of the substituent include the groups exemplified as the substituent for the aromatic hydrocarbon group represented by R ^d1 .

The alkyl group represented by R ^d1 preferably has 1 to 12 carbon atoms. ^Examples of the alkyl group represented by R ^d1 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples thereof include a tetradecyl group and a pentadecyl group. These alkyl groups may be linear, branched, or cyclic, or may be a combination of a chain and a cyclic group. In the alkyl group represented by R ^d1 , the methylene group (—CH ₂ —) may be replaced with —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 — and is a hydrogen atom. May be substituted with an OH group or an SH group.

R ^d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear (linear or branched) or cyclic, and may be linear, branched, or cyclic, and is a linear group. It may be a group in which a cyclic group and a cyclic group are combined. Moreover, in the alkyl group of R ^d5 , the methylene group (—CH ₂ —) may be replaced with —O— or —CO—.

Specific examples of the alkyl group which may have a substituent and which is represented by R ^d1 include groups represented by the following formulas. * Represents a bond.

The number of carbon atoms of the group represented by R ^d1 in which the aromatic hydrocarbon group and the alkanediyl group derived from the above alkyl group are combined is preferably 7 to 33, more preferably 7 to 18; More preferably, it is 7-12. The combined group may have one or more substituents, and examples of the substituent include the same groups as the substituents that an aromatic hydrocarbon group or an alkyl group may have. Be done. Examples of the group represented by R ^d1 which is a combination of an aromatic hydrocarbon group and an alkanediyl group derived from the above alkyl group include an aralkyl group, and specifically, a group represented by the following formula: Can be mentioned. In the formula, * represents a bond.

Among them, R ^d1 is preferably an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent, and an aromatic hydrocarbon group which may have a substituent. Is more preferable.

The aromatic hydrocarbon group represented by R ^d2 preferably has 6 to 15 carbon atoms, more preferably 6 to 12 and even more preferably 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group.

The heterocyclic group represented by R ^d2 preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and further preferably 3 to 5 carbon atoms. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group and a carbazolyl group.

The alkyl group represented by R ^d2 preferably has 1 to 7 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. The alkyl group may be linear, branched or cyclic, or may be a combination of a chain and a cyclic group.

R ^d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, further preferably a chain alkyl group having 1 to 3 carbon atoms, and a methyl group. Particularly preferred.

The aromatic hydrocarbon group represented by R ^d3 preferably has 6 to 15 carbon atoms, more preferably 6 to 12 and even more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group, and a phenyl group and a naphthyl group are more preferable.

The aromatic hydrocarbon group represented by R ^d3 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group. C1 to C15 alkyl groups such as groups and decyl groups; ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, decenyl and other alkenyl groups having 1 to 15 carbons; etc. Is mentioned.

The aliphatic hydrocarbon group which the aromatic hydrocarbon group represented by R ^d3 may have has preferably 1 to 7 carbon atoms, and the aliphatic hydrocarbon group is linear or branched. It may be either chain-like or cyclic, or may be a group obtained by combining a chain-like group and a cyclic group. A methylene group contained in the aliphatic hydrocarbon group (-CH ₂ -) is, -O -, - may be replaced in the CO- or -S-, a methine group (-CH <) may, -N <in It may be replaced.

Examples of the aliphatic hydrocarbon group which the aromatic hydrocarbon group represented by R ^d3 may have include groups represented by the following formulas. In the formula, * represents a bond.

As R ^d3 , examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulae. In the formula, * represents a bond.

The heterocyclic group represented by R ^d3 preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and further preferably 3 to 5 carbon atoms. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group and a carbazolyl group. The heterocyclic group represented by R ^d3 may have one or two or more substituents, and the substituent may be a substituent which the aromatic hydrocarbon group for R ^d1 may have. Similar groups may be mentioned.

R ^d3 is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms). The number of is preferably 2 or more and 5 or less.

The aromatic hydrocarbon group represented by R ^d4 preferably has 6 to 15 carbon atoms, more preferably 6 to 12 and even more preferably 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group. A phenyl group and a naphthyl group are more preferable, and a phenyl group is still more preferable. The aromatic hydrocarbon group represented by R ^d4 may have one or more substituents. Examples of the substituent include the same groups as the substituents that the aromatic hydrocarbon group for R ^d1 may have.

The aliphatic hydrocarbon group represented by R ^d4 preferably has 1 to 13 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 4 to 9 carbon atoms. Examples of the aliphatic hydrocarbon group represented by R ^d4 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, Alkyl groups such as tridecyl group, tetradecyl group and pentadecyl group; ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, butadecenyl group And alkenyl groups such as pentadecenyl group; and the like. These aliphatic hydrocarbon groups may be linear (linear or branched), cyclic, or a combination of a linear group and a cyclic group. In the aliphatic hydrocarbon group for R ^d4 , the methylene group (—CH ₂ —) may be replaced with —O—, —CO— or —S—, and the methine group (—CH<) is —PO ₃ <may be substituted, and the hydrogen atom contained in the above aliphatic hydrocarbon group may be replaced with an OH group.

Examples of the aliphatic hydrocarbon group which may have a substituent and which is represented by R ^d4 include groups represented by the following formulas. In the formula, * represents a bond.

R ^d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and further preferably a branched chain having no substituent. It is a chain alkyl group.

The compound (d1) is a compound represented by the formula (d1), specifically a compound of the formula (d1) having a combination of substituents described in each of the formulas (d1-1) to (d1-67). Is mentioned. In Tables 1 to 7, * represents a bond.

Among them, compounds having a substituent represented by formula (d1-3) to compounds having a substituent represented by formula (d1-6), compounds having a substituent represented by formula (d1-18) to formula (d1) A compound having a substituent represented by formula (d1-55), a compound having a substituent represented by formula (d1-55), a compound having a substituent represented by formula (d1-56), and a formula (d1-60) A compound having a substituent of, and a compound having a substituent of formula (d1-61) are preferable,
More preferably, the compound having a substituent represented by formula (d1-3) to the compound having a substituent represented by formula (d1-6), the compound having a substituent represented by formula (d1-18) to formula ( a compound having a substituent described in d1-41),
More preferably, it is a compound having a substituent represented by formula (d1-24), a compound having a substituent represented by formula (d1-36) to a compound having a substituent represented by formula (d1-40),
Particularly preferred are compounds having a substituent represented by formula (d1-24).

Compound (d1) can be produced, for example, by the production method described in JP-T-2014-500852.

The compound (d2) is
R ^d1 is an ^optionally substituted alkyl group having 1 to 15 carbon atoms,
R ^d2 is an alkyl group having 1 to 10 carbon atoms,
R ^d3 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent,
A compound in which R ^d4 is an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent is preferable,
More preferably,
R ^d1 represents a methyl group, an ethyl group or a propyl group,
R ^d2 represents a methyl group, an ethyl group or a propyl group,
R ^d3 represents a phenyl group substituted with a methyl group,
A compound in which R ^d4 is a methyl group, an ethyl group or a propyl group,
More preferably,
R ^d1 and R ^d2 are methyl groups, R ^d3 is an o-tolyl group, and R ^d4 is an ethyl group.

The compound (d3) is
R ^d1 is an ^optionally substituted alkyl group having 1 to 15 carbon atoms,
A compound in which R ^d2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms is preferable,
More preferably,
R ^d1 is a hexyl group and R ^d2 is a phenyl group.

Such O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane. -1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-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-carbazole -3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane- 1-on-2-imine and the like can be mentioned. 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-acyl oxime compounds, a color filter having excellent lithographic performance tends to be obtained.

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

Examples of the compound having the structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl). )-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Be done. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF Corp.) may be used.

Examples of the compound having the 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]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomer, α,α-diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by 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 JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5 ,5'-Tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl) -4,4',5,5'-Tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (See JP-B-48-38403, JP-A-62-174204, etc.), and an imidazole compound in which the phenyl group at the 4,4′,5,5′-position is substituted with a carboalkoxy group (Japanese Patent Laid-Open Publication No. 7-10913, etc.) and the like. Of these, compounds represented by the following formulas or mixtures thereof are 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-(furan-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.

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with the below-mentioned polymerization initiation aid (D1) (particularly amines).

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by weight, more preferably 5 to 25 parts by weight based on 100 parts by weight of the total amount of the resin (B) and the polymerizable compound (C). Parts by weight, and more preferably 10 to 20 parts by weight. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time is shortened, so that the productivity of the color filter tends to be improved.

[5] Polymerization initiation aid (D1)
The polymerization initiation aid (D1) is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator. When the polymerization initiator auxiliary agent (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, thioxanthone compounds are preferable. You may use together 2 or more types of polymerization initiation assistants (D1).

As the amine compound, 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 called 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. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

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. Examples thereof include anthracene and 2-ethyl-9,10-dibutoxyanthracene.

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

As the carboxylic acid compound, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, 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 weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight 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 colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

[6] Thiol compound (T)
The colored photosensitive resin composition of the present invention may contain one kind or two or more kinds of thiol compounds (T). The thiol compound (T) is particularly preferably used when the polymerization initiator (D) is an oxime compound such as an O-acyl oxime compound and/or a biimidazole compound. The thiol compound (T) is a compound having at least one sulfanyl group (-SH) in the molecule. The thiol compound (T) is preferably a compound having one sulfanyl group in the molecule.

Examples of the compound having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, and 2-sulfanyl. Pyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridin-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino- 2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6 -Sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propyl Pyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-sulfanylimidazole , 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2-methyl- 4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2 -Amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2 -Yl) methanethiol, 2-sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl -5-methylbenzimidazole, 2-sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro 2-Sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4- Triazole, 4-amino-6-sulfanylpyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine and 4-sulfanyl-1H-pyrazolo[2,4-d]pyrimidine and the like. Is mentioned.

Examples of the compound having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediolbis(3-sulfanylpropionate), butanediolbis(3-sulfanyl). Acetate), ethylene glycol bis(3-sulfanyl acetate), trimethylolpropane tris(3-sulfanyl acetate), butanediol bis(3-sulfanyl propionate), trimethylol propane tris(3-sulfanyl propionate), tri Methylolpropane tris(3-sulfanyl acetate), pentaerythritol tetrakis(3-sulfanyl propionate), pentaerythritol tetrakis(3-sulfanyl acetate), trishydroxyethyl tris(3-sulfanyl propionate), pentaerythritol tetrakis(3) -Sulfanyl butyrate) and 1,4-bis(3-sulfanylbutyloxy)butane.

The content of the thiol compound (T) is preferably 0.5 to 50 parts by weight, more preferably 5 to 45 parts by weight, and further preferably 10 to 40 parts by weight with respect to 100 parts by weight of the polymerization initiator (D). Is. When the content of the thiol compound (T) is within the above range, the sensitivity tends to be high and the developability tends to be good.

[7] Solvent (E)
The colored photosensitive resin composition of the present invention preferably contains one or more solvents (E). As the solvent (E), an ester solvent (a solvent containing -COO-), an ether solvent other than the ester solvent (a solvent containing -O-), an ether ester solvent (a solvent containing -COO- and -O-), A ketone solvent (a solvent containing —CO—) other than the ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, and the like can be given.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

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

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

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Etc.

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

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

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

The solvent (E) preferably contains an organic solvent 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. 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-methoxy. It is preferable to contain at least one selected from the group consisting of -1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide. Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, More preferably, at least one selected from the group consisting of dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate is included.

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

[8] Leveling agent (F)
The colored photosensitive resin composition of the present invention may contain one kind or two or more kinds of leveling agents (F). Examples of the leveling agent (F) include a silicone-based surfactant (however, it does not contain a fluorine atom), a fluorine-based surfactant and a fluorine-containing silicone-based surfactant. These may have a polymerizable group in the side chain.

Examples of the silicone-based surfactant (however, containing no fluorine atom) include a surfactant having a siloxane bond in the molecule. Specifically, Toray 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 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) and the like. Can be mentioned.

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

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

The content of the leveling agent (F) in the colored photosensitive resin composition is usually 0.001% by weight or more and 0.2% by weight or less, preferably 0.002% by weight or more and 0.1% by weight or less, It is preferably 0.005% by weight or more and 0.05% by weight or less. The content of the pigment dispersant is not included in this content.

[9] Antioxidant (G)
From the viewpoint of improving the heat resistance and light resistance of the colorant (A), the colored photosensitive resin composition preferably contains an antioxidant. The antioxidant is not particularly limited as long as it is an industrially commonly used antioxidant, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and the like can be used. You may use 2 or more types of antioxidants.

As the phenolic antioxidant, Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corp.), Irganox 1076. (Irganox 1076: octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Ltd.), Irganox 1330 (Irganox 1330:3,3′,3″,5). , 5′,5″-hexa-t-butyl-a,a′,a″-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Ltd., Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione , BASF Corporation, Irganox 3790 (Irganox 3790: 1,3,5-tris((4-t-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine. -2,4,6(1H,3H,5H)-trione, manufactured by BASF Ltd., Irganox 1035 (Irganox 1035: thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxy). (Phenyl)propionate], manufactured by BASF Ltd., Irganox 1135 (Irganox 1135: benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, BASF). Co., Ltd.), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Ltd.), Irganox 3125 (Irganox 3125, manufactured by BASF Ltd.), Irga Knox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy3′,5′-di-t-butylanilino)-1,3,5-triazine, manufactured by BASF Corporation) Adekastab AO-80 (Adekastab AO-80:3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)- 2,4,8,10-Tetraoxaspiro(5,5)undecane, manufactured by ADEKA Corporation, Sumilizer BH T (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790). , Manufactured by Cytec Co., Ltd., vitamin E (manufactured by Eisai Co., Ltd.) and the like.

Examples of the phosphorus-based antioxidant include Irgafos 168 (Irgafos 168: tris(2,4-di-t-butylphenyl)phosphite, manufactured by BASF Ltd.), Irgafos 12 (Irgafos 12: Tris[2-[[[2 , 4,8,10-Tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, manufactured by BASF Ltd., Irgafos 38 ( Irgafos 38: Bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Ltd., Adekastab 329K (manufactured by ADEKA), Adekastab PEP36 ( ADEKA Co., Ltd., ADEKA STAB PEP-8 (made by ADEKA Co., Ltd.), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE). , Ultranox 626 (Ultranox 626, manufactured by GE) and Sumilizer GP (Sumilizer GP: 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10. -Tetra-t-butyldibenz[d,f][1.3.2]dioxaphosphepin) (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of the sulfur-based antioxidants include dilauryl thiodipropionate, dialkylthiodipropionate compounds such as dimyristyl or distearyl, and β-alkylmercaptopropionate ester compounds of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane. Is mentioned.

[10] Other components In the colored photosensitive resin composition of the present invention, if necessary, a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an anti-aggregation agent, an organic acid. One or more additives such as an organic amine compound and a curing agent may be contained.

Examples of the filler include glass, silica, alumina and the like.

Examples of polymer compounds other than the resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

As the adhesion promoter, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl). -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Examples thereof include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.

Examples of the ultraviolet absorber include benzotriazole compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone. Compounds; benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-(4,6-diphenyl-1,3,5-triazine- 2-yl)-5-hexyloxyphenol and other triazine compounds; and the like.

Examples of the aggregation preventing agent include sodium polyacrylate and the like.

Organic acid is used for adjusting the developability, and specifically,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melophanoic acid and pyromellitic acid; and the like.

As the organic amine compound,
n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine , Monoalkylamines such as n-undecylamine and n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di- dialkylamines such as n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamine such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol and 6-amino-1-hexanol. ;
A monocycloalkanolamine such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
A dicycloalkanolamine such as di(4-cyclohexanol)amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine and tri-n-hexanolamine;
Tricycloalkanolamines such as tri(4-cyclohexanol)amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 , 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol and other aminoalkanediols;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanol such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanol such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol and 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid and 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, p-methyl-N,N-dimethylaniline;
Aminobenzyl alcohol such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
Aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol;
Aminobenzoic acid such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid;

Examples of the curing agent include a compound capable of reacting with a carboxy group in the resin (B) to crosslink the resin (B) when heated, a compound capable of being polymerized alone to cure a colored pattern, and the like. .. Examples of the curing agent include epoxy compounds and oxetane compounds. As the curing agent, only one kind may be used, or two or more kinds may be used in combination.

Examples of the epoxy compound include bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, novolac type epoxy resin, other aromatic epoxy resin, and alicyclic system. Epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, epoxy resins and aliphatics and fats other than the brominated derivatives thereof. Examples include cyclic or aromatic epoxy compounds, epoxides of (co)polymers of butadiene, epoxides of (co)polymers of isoprene, (co)polymers of glycidyl (meth)acrylate, triglycidyl isocyanurate, and the like. Be done. Examples of commercially available epoxy resins include orthocresol novolac type epoxy resin, "Sumiepoxy (registered trademark) ESCN-195XL-80" (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

When the colored photosensitive resin composition of the present invention contains an epoxy compound as a curing agent, an oxetane compound, etc., it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound, the oxetane skeleton of the oxetane compound. Good. Examples of the compound include polycarboxylic acids, polycarboxylic anhydrides, acid generators, and the like.

As the polycarboxylic acid, in addition to the compounds exemplified as the above organic acid,
Aromatic polyvalent carboxylic acids such as 3,4-dimethylphthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid and 3,3′,4,4′-benzophenonetetracarboxylic acid acid;
Aliphatic polycarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid Alicyclic polyvalent carboxylic acid such as 1,2,4,5-cyclohexanetetracarboxylic acid; and the like.

As the polycarboxylic acid anhydride,
Aromatic polyvalent carboxylic acid anhydrides such as phthalic anhydride, pyromellitic dianhydride, trimellitic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride;
Aliphatic polycarboxylic acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride ;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polyvalent carboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic acid anhydride, and nadic acid anhydride;
And ester group-containing carboxylic acid anhydrides such as ethylene glycol bis trimellitate acid and glycerin tris trimellitate anhydride; and the like.
As the carboxylic acid anhydride, one commercially available as an epoxy resin curing agent may be used. As the epoxy resin curing agent, a trade name "ADEKA HARDNER (registered trademark) EH-700" (manufactured by ADEKA), a trade name "RICACID (registered trademark) HH" (manufactured by Shin Nippon Rika Co., Ltd.), a trade name "MH-700" (manufactured by New Japan Rika Co., Ltd.) and the like can be mentioned.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium. Onium salts such as hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, and benzointosylate. Etc.

<Method for producing colored photosensitive resin composition>
The colored photosensitive 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), a thiol compound ( It can be prepared by mixing T), the leveling agent (F), the polymerization initiation aid (D1), the antioxidant (G), and other components.

<Color filter and its manufacturing method, color filter and display device>
The colored photosensitive resin composition of the present invention is useful as a material for a color filter, particularly a green color filter. A color filter formed from the colored photosensitive resin composition of the present invention also falls within the scope of the present invention. The color filter may form a colored pattern.
Examples of the method for producing a colored pattern from the colored photosensitive resin composition of the present invention include a photolithographic method, an inkjet method, a printing method and the like. Among them, the photolithographic method is preferable. The photolithography method is a method of applying a colored photosensitive resin composition to a substrate, drying the colored composition layer to form a colored composition layer, exposing the colored composition layer through a photomask, and developing the colored pattern. Is a method of forming. In the photolithographic method, a coating film which is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and/or not developing. The colored pattern or coating formed from the colored photosensitive resin composition of the present invention is the color filter of the present invention.
The color filter according to the present invention is typically used as a green pixel.

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

The formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions, and can be produced, for example, as follows. First, the colored photosensitive resin composition is applied onto a substrate, and dried by heating (prebaking) and/or vacuum drying to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. The heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When performing drying under reduced pressure, it is preferable to perform drying under a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C. The thickness of the coloring composition layer is not particularly limited and may be appropriately selected according to the intended thickness of the color filter. According to the present invention, it is possible to form a color filter having a dark color while exhibiting good brightness even with a thin film.

Next, the colored composition layer is exposed through a photomask for forming a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. As a light source used for exposure, a light source that emits light having a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You may. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

For the exposure, since it is possible to uniformly illuminate the entire exposed surface with parallel light rays and perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed, exposure of the mask aligner and stepper, etc. Preference is given to using the device.

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

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

Since the film thickness of the obtained coating film affects adjacent pixels, it is preferably as thin as possible. Especially when a thick film is used, light from a light source may leak through pixels of two or more colors when a liquid crystal panel is manufactured. May be lost. The coating film after post-baking is preferably 3 μm or less, more preferably 2.8 μm or less.
The lower limit of the coating film 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, even if it is a thin film, good brightness can be exhibited, and Rec. ITU-R BT. A color filter having a high coverage of the 2020 color gamut can be formed.

The higher the brightness of the coating film is, the more preferable it is, it is preferably 38.5 or more, more preferably 39 or more, and the upper limit is not particularly limited, but it is usually 70 or less.

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

Hereinafter, the present invention will be described more specifically by showing 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 weight unless otherwise specified.

<Synthesis Example 1: Preparation of resin (B)>
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and then 280 parts by weight of propylene glycol monomethyl ether acetate was added and heated to 80° C. with stirring.
Then, 38 parts by weight of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8 and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]. A mixed solution obtained by mixing 289 parts by weight of the mixture of decan-9-yl acrylate and 125 parts by weight of propylene glycol monomethyl ether acetate was added dropwise to the above propylene glycol monomethyl ether acetate over 5 hours. On the other hand, a mixed solution of 33 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts by weight of propylene glycol monomethyl ether acetate was added dropwise to the above propylene glycol monomethyl ether acetate over 6 hours.
After completion of dropping, the mixture was kept at the same temperature for 4 hours, then cooled to room temperature, and had a B-type viscosity (23° C.) of 125 mPas, a solid content of 37.0% by weight, and a solution acid value of 27 mg-KOH/g. Solution (B)] was obtained. The weight average molecular weight Mw of the copolymer was 9200, and the dispersity was 2.08.

The polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin (copolymer) contained in the resin solution (B) were measured under the following conditions using the GPC method.

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

<Synthesis Example 2: Preparation of pigment dispersion liquid (A1)>
C. I. Pigment Blue 16 12.0 parts Acrylic pigment dispersant 5.4 parts Propylene glycol monomethyl ether acetate 82.6 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A1). It was

<Synthesis Example 3: Preparation of pigment dispersion liquid (A2)>
C. I. Pigment Green 59 14.0 parts Acrylic pigment dispersant 1.9 parts Propylene glycol monomethyl ether acetate 84.1 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A2). It was

<Synthesis Example 4: Preparation of pigment dispersion liquid (A3)>
C. I. Pigment Green 58 14.0 parts Acrylic pigment dispersant 1.9 parts Propylene glycol monomethyl ether acetate 84.1 parts are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid (A3). It was

<Synthesis Example 5: Preparation of pigment dispersion liquid (A4)>
C. I. Pigment Yellow 185 12.0 parts Acrylic pigment dispersant 6.0 parts Propylene glycol monomethyl ether acetate 82.0 parts are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A4). It was

<Synthesis Example 6: Preparation of pigment dispersion liquid (A5)>
C. I. Pigment Yellow 150 12.0 parts Acrylic pigment dispersant 3.6 parts Propylene glycol monomethyl ether acetate 84.4 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A5). It was

<Synthesis Example 7: Preparation of pigment dispersion liquid (A6)>
C. I. Pigment Yellow 129 13.0 parts Acrylic pigment dispersant 5.2 parts Propylene glycol monomethyl ether acetate 81.8 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A6). It was

<Synthesis Example 8: Preparation of pigment dispersion liquid (A7)>
C. I. Pigment Yellow 139 12.0 parts Acrylic pigment dispersant 4.0 parts Propylene glycol monomethyl ether acetate 84.0 parts are mixed and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (A7). It was

<Examples 1 to 8 and Comparative Examples 1 to 5>
(1) Preparation of colored photosensitive resin composition By mixing the components shown in Table 8, a colored photosensitive resin composition was obtained. In preparing the colored photosensitive resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored photosensitive resin composition was 20% by weight. The unit of the blending amount of each component in Table 8 is "part by weight". The following compounds were used as the polymerizable compound (C), the polymerization initiator (D) and the leveling agent (F).

Polymerizable compound (C); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.),
Polymerization initiator (D); the following formula:

A compound represented by
Leveling agent (F); polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.).

(2) Preparation of Pattern A colored photosensitive resin composition was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100° C. for 3 minutes. After cooling, the substrate coated with the colored photosensitive resin composition was exposed to light with an exposure amount (365 nm standard) of 80 mJ/cm ² using an exposure machine (TME-150RSK; manufactured by Topcon Corp.) in an air atmosphere. Irradiated. After that, post-baking was performed in an oven at 230° C. for 30 minutes to obtain a coating film.

(3) Film Thickness Measurement The film thickness (μm) of the obtained coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 9.

(4) Chromaticity Evaluation The obtained coating film was subjected to spectroscopic measurement using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and a characteristic function of a light source having a spectroscopic spectrum shown in FIG. Was used to measure xy chromaticity coordinates (x, y), lightness (Y), and spectral peak top (maximum peak maximum wavelength (nm)) in the CIE XYZ color system. The results are shown in Table 9.

In Examples 1 to 8 and Comparative Examples 1 to 5, the chromaticity coordinates (x, y) are unified to (0.170, 0.760), which is one of the target green chromaticity coordinates. Note that Rec. ITU-R BT. The chromaticity coordinate (x, y) of green of 2020 is (0.170, 0.797).
In Examples 1 to 8 and Comparative Examples 1 to 5, the film thickness was further made equal (2.7 μm, Comparative Example 3 was 2.8 μm).

In Examples 1 to 8, it was possible to realize color filters having a higher lightness Y than in Comparative Examples 1 to 5. In Comparative Example 4, it was necessary to increase the film thickness to realize the chromaticity coordinates (0.170, 0.760), and it was not possible to obtain a sufficient brightness Y.
In Comparative Example 5, the film thickness was the same as in Examples 1 to 8, and although the brightness Y was high, the chromaticity coordinates (0.170, 0.760) could not be achieved.

Claims (7)

Contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
The colorant (A) is C.I. I. Pigment Blue 16 and C.I. I. Pigment Green 59, a colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the colorant (A) further contains a yellow pigment. The yellow pigment is C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 150, The colored photosensitive resin composition of Claim 2 containing either or both. The yellow pigment is C.I. I. Pigment Yellow 185, The colored photosensitive resin composition according to claim 2 or 3. The colored photosensitive resin composition according to claim 1, wherein the polymerization initiator (D) contains an oxime compound. A color filter formed from the colored photosensitive resin composition according to claim 1. A display device comprising the color filter according to claim 6.