KR102355406B1 - Colored curable resin composition, color filter and display device - Google Patents

Abstract

a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant is C.I. Pigment Blue 16 and yellow colorant, free of green colorant, C.I. The colored curable resin composition in which content of the pigment blue 16 is 26 mass % or more in 100 mass % of coloring agents, and a polymerization initiator contains an oxime type compound, a color filter, and a display apparatus using the are provided.

Description

Colored curable resin composition, a color filter, and a display device TECHNICAL FIELD

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

In recent years, development of a liquid crystal display device to widen a displayable color gamut is progressing, and as a part of the development, a color filter with a more intense color is required.

For example, in Rec.ITU-R BT.2020, which stipulates the video format of Super Hi-Vision (SHV), the color gamut is further expanded. Accordingly, a color with a high coverage ratio of the color gamut of Rec.ITU-R BT.2020 (ratio of the color gamut that can be expressed within the color gamut of Rec.ITU-R BT.2020) A filter is required.

As a method of thickening a color filter, the method of raising the coloring agent density|concentration in a color filter is mentioned. However, when a coloring agent density|concentration is made high, the performance as colored curable resin composition, such as deterioration of a pattern shape, will deteriorate. Moreover, the method of producing a color filter with the coloring curable resin composition containing a coloring agent with high coloring power is also mentioned as a method of producing the color filter of a hyperchromic color. However, when using a coloring agent with high coloring power, brightness may become low. Moreover, the method of obtaining the color filter of deep color by making a color filter into a thick film is also mentioned. However, in a thick-film color filter, when it is applied to a liquid crystal display device, the color mixture of light may generate|occur|produce between adjacent pixels.

Japanese Patent Application Laid-Open No. 2012-123302 discloses, as a green coloring composition from which green light of high luminance is obtained, contains at least a cyan colorant and a yellow colorant, a peak wavelength is in the range of 520 nm to 540 nm, and transmittance of the peak wavelength The green coloring composition which has the transmittance|permeability of 40 % or less at a wavelength of 510 nm when it is set as 70 % and the transmittance|permeability of 560 nm of wavelength becomes 40 % or less is proposed.

This application provides the invention shown below.

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

The colorant is C.I. Contains Pigment Blue 16 and yellow colorant, no green colorant;

C.I. The content of Pigment Blue 16 is 26% by mass or more in 100% by mass of the colorant,

The colored curable resin composition in which a polymerization initiator contains an oxime type compound.

[2] The colored curable resin composition according to [1], wherein the yellow colorant contains a compound having an isoindoline skeleton.

[3] A color filter formed of the colored curable resin composition according to [1] or [2].

[4] A display device comprising the color filter according to [3].

<Colored Curable Resin Composition>

The colored curable resin composition according to the present invention contains a colorant, a resin, a polymerizable compound and a polymerization initiator, and the colorant contains C.I. It contains Pigment Blue 16 and a yellow colorant, does not contain a green pigment, and the polymerization initiator contains an oxime-based compound.

Hereinafter, the coloring agent, resin, a polymeric compound, and a polymerization initiator in this invention are called a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D), respectively.

According to the colored curable resin composition, good patterning properties can be exhibited, and a color filter with a high color gamut coverage of Rec.ITU-R BT.2020 is produced with a wide displayable color reproduction gamut with an appropriate colorant concentration. it becomes possible to

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

[1] Colorant (A)

Colorant (A) is C.I. Contains Pigment Blue 16 and yellow colorant, no green colorant.

As a yellow colorant, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, and 214 yellow pigments.

The coloring agent (A) may contain 2 or more types of yellow coloring agents.

Especially, from the point which can make brightness higher, it is preferable that a yellow coloring agent contains the compound which has an isoindoline skeleton, and it is more preferable that it consists of a compound which has an isoindoline skeleton.

As a yellow colorant, which is a compound having an isoindoline skeleton, C.I. Pigment Yellow 139, 185, etc. are mentioned.

In this invention, a coloring agent (A) does not contain a green pigment. In this specification, a "green dye" means the generic name of a green dye compound and a green pigment.

Since the brightness can be made higher, the content of the compound having an isoindoline skeleton in the yellow colorant is preferably 50 mass% or more, more preferably 80 mass% or more, in 100 mass% of the yellow colorant, , More preferably, it is 90 mass % or more, Especially preferably, it is 95 mass % or more, Most preferably, it is 100 mass %.

C.I. The content of Pigment Blue 16 is 26% by mass or more in 100% by mass of the colorant (A), and preferably 30% by mass or more from the viewpoint of producing a color filter with a wide displayable color gamut, more preferably It is 35 mass % or more, More preferably, it is 50 mass % or more.

C.I. It is preferable that it is 90 mass % or less in 100 mass % of coloring agents (A) from a viewpoint of a brightness improvement, and, as for content of the pigment blue 16, it is more preferable that it is 80 mass % or less.

The content of the yellow colorant is usually 10% by mass or more in 100% by mass of the colorant (A), and from the viewpoint of producing a color filter with a wide displayable color gamut and from the viewpoint of improving the brightness, it is preferably 20% by mass or more, More preferably, it is 30 mass % or more, More preferably, it is 35 mass % or more.

Content of a yellow colorant is 74 mass % or less normally in 100 mass % of coloring agents (A) from a developable viewpoint, Preferably it is 70 mass % or less, More preferably, it is 65 mass % or less, More preferably, it is 50 mass %. mass% or less.

As will be described later, the colorant (A) does not contain a green pigment, but additionally C.I. other colorants than Pigment Blue 16 and yellow colorants. In this case, C.I. 90 mass % or less may be sufficient, 80 mass % or less, and 70 mass % or less may be sufficient as total content of the pigment blue 16 and a yellow coloring agent in 100 mass % of coloring agents (A).

C.I. in the colorant (A). The total content of the pigment blue 16 and the yellow colorant is preferably 30 mass% or more, more preferably 50 mass% or more, from the viewpoint of producing a color filter having a wide displayable color gamut in 100 mass% of the colorant (A). It is mass % or more, More preferably, it is 60 mass % or more. 100 mass % may be sufficient as the said total content in 100 mass % of coloring agents (A).

From the viewpoint of producing a color filter with a wide displayable color gamut, the colorant (A) is substantially C.I. Preferably, it consists of a blue colorant including Pigment Blue 16 and a yellow colorant, and substantially C.I. It is more preferable to consist of pigment blue 16 and a yellow colorant. "It substantially consists of a blue coloring agent and a yellow coloring agent" means that the total content of the blue coloring agent and yellow coloring agent in the coloring agent (A) is 98 mass % or more in 100 mass % of coloring agents (A), "substantially C.I. It consists of pigment blue 16 and a yellow coloring agent" means C.I. in the coloring agent (A). Pigment blue 16 and the total content of the yellow coloring agent say 98% by mass or more in 100% by mass of the coloring agent (A).

C.I. in the colorant (A). The content ratio of the pigment blue 16 to the yellow colorant (CI Pigment Blue 16/yellow colorant) is usually 0.1 to 10 on a mass basis, from the viewpoint of producing a color filter with a wide displayable color gamut, preferably 0.1 to 8, more preferably 0.2 to 6, still more preferably 0.3 to 5, particularly preferably 0.5 to 1.5.

The colorant (A) is C.I. pigment blue 16, a yellow colorant, and a colorant other than a green colorant.

A pigment may be sufficient as another coloring agent, dye may be sufficient as them, and these both may be sufficient as them.

Only 1 type may be used for another coloring agent, and may use 2 or more types together.

Examples of other pigments include organic pigments and inorganic pigments, and compounds classified as pigments in the color index (published by The Society of Dyers and Colorists).

A well-known dye can be used as said dye, A solvent dye, an acid dye, a direct dye, a mordant dye, etc. are mentioned.

As a dye, the compound classified as having a color other than a pigment in the color index (published by The Society of Dyers and Colorists), and the well-known dye described in the dyeing notebook (Skisensha) are mentioned.

As the dye, 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 , an acridine dye, a styryl dye, a coumarin dye, a quinoline dye, a nitro dye, etc. are mentioned. Among these, organic solvent-soluble dyes are preferable.

The colorant (A) is, for example, C.I. Blue pigments other than Pigment Blue 16 and blue colorants such as blue dyes may be included. As another blue pigment, C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc. can be illustrated.

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, CIs of 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, etc. 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, CIs such as 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340, etc. 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, CIs such as 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc. direct blue dye;

C.I. Disperse Blue 1, 14, 56, 60, etc. C.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, CIs of 67, 68, 81, 83, 88, 89, etc. basic blue dye;

C.I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84, etc. CIs mordant blue dye; and the like.

From the viewpoint of producing a color filter having a wide displayable color gamut, the C.I. It is preferable that content of the pigment blue 16 is high. Specifically, the C.I. Content of the pigment blue 16 is preferably 50 mass % or more in 100 mass % of blue coloring agents, More preferably, it is 80 mass % or more, More preferably, it is 90 mass % or more, Especially preferably, it is 95 mass %. or more, and most preferably 100% by mass.

The total content of the colorant (A) in the colored curable resin composition is usually 10 to 50 mass% in 100 mass% of the solid content of the colored curable resin composition, but from the viewpoint of producing a color filter with a wide displayable color reproduction area, Preferably it is 20 mass % or more, More preferably, it is 30 mass % or more, More preferably, it is 35 mass % or more.

Moreover, from a viewpoint of the easiness of formation of a resist pattern, Preferably the said total content is 45 mass % or less in 100 mass % of solid content of colored curable resin composition.

In addition, in this specification, "solid content of colored curable resin composition" refers to all components other than a solvent (E) among the components contained in colored curable resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography and gas chromatography.

It is preferable that the various pigments in colored curable resin composition are in the state of the dispersion liquid disperse|distributed uniformly in the solvent. In addition, it is preferable that the pigment has a uniform particle size. The dispersion can be obtained by mixing a pigment and a solvent. You may mix a pigment dispersant as needed. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was uniformly disperse|distributed in the solvent can be obtained.

As the pigment dispersant, commercially available surfactants can be used, and silicone-based, fluorine-based, ester-based (including polyester-based), cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, acrylic-based Surfactants are 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, etc., as well as KP ( Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Azispa (registered trademark) (Ajinomoto) Fine Techno Co., Ltd. product), Disperbyk (made by Big Chemi), etc. are mentioned. A pigment dispersant may use only 1 type, and may use 2 or more types together.

When using a pigment dispersant, Preferably the usage-amount is 100 mass parts or less with respect to 100 mass parts of pigments, More preferably, they are 5 mass parts or more and 50 mass parts or less. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be easy to be obtained.

It does not specifically limit as a solvent which comprises a pigment dispersion, The solvent similar to the below-mentioned solvent (E) which can be contained in colored curable resin composition is mentioned. 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-methyl ether. Toxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc. are preferable, and propylene glycol monomethyl ether acetate and propylene glycol monomethyl are preferable. Ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxypropionate ethyl, etc. are preferable.

Although the usage-amount of a solvent is not specifically limited, The density|concentration of solid content in a pigment dispersion liquid becomes like this. Preferably it is 3-20 mass %, More preferably, it is 5-18 mass %.

Various pigments in the colored curable resin composition may be subjected to rosin treatment, surface treatment using a pigment derivative or pigment dispersant to which acidic or basic groups are introduced, graft treatment to the pigment surface with a high molecular compound, etc., sulfuric acid atomization method, etc. as necessary. atomization treatment, washing treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed.

[2] Resin (B)

The colored curable resin composition of this invention contains 1 type(s) or 2 or more types of resin (B). It is preferable that resin (B) is alkali-soluble resin. Alkali solubility means the property which melt|dissolves in the developing solution which is the aqueous solution of an alkali compound. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (a) [hereinafter, sometimes referred to as “(a)”], and a cyclic having 2 to 4 carbon atoms狀) A copolymer with a monomer (b) [hereinafter, sometimes referred to as “(b)”] having an ether structure and an ethylenically unsaturated bond.

Resin [K2]: (a) and (b), and a monomer copolymerizable with (a) (c) (however, it is different from (a) and (b).) [hereinafter referred to as “(c)” There is.] a copolymer with

Resin [K3]: a copolymer of (a) and (c).

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

Resin [K5]: A resin obtained by reacting (a) with the copolymer of (b) and (c).

Resin [K6]: Resin obtained by making (a) react with the copolymer of (b) and (c), and also making carboxylic acid anhydride react.

As (a), specifically,

unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene , 5-Carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxy group, such as [2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] of polyhydric carboxylic acids with more than divalence, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;

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

Especially, it is preferable that (a) is (meth)acrylic acid, maleic anhydride, etc. from a viewpoint of copolymerization reactivity or a viewpoint of solubility in aqueous alkali solution.

In addition, in this specification, "(meth)acryl" shows at least 1 sort(s) chosen from the group which consists of acryl and methacryl. The same applies to descriptions such as “(meth)acryloyl” and “(meth)acrylate”.

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

As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as “(b1)”], a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter .

As (b1), a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter referred to as "(b1-1)" in some cases]], having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon Monomer (b1-2) [hereinafter, sometimes referred to as “(b1-2)”] is mentioned.

As (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxy) methyl) 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. can

As (b1-2), vinylcyclohexene monoxide, 1,2-epoxy 4-vinylcyclohexane (for example, Celoxide 2000; Daicel Chemical Industry Co., Ltd. product), 3,4-epoxycyclohexylmethyl Acrylates (eg, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (eg, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.) , the compound represented by the formula (I), the compound represented by the formula (II), and the like.

[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 may be substituted with a hydroxyl group . X ¹ and X ² each independently represent a single bond, -R ^c -, *-R ^c -O-, *-R ^c -S-, or *-R ^c -NH-. R ^c represents a C1-C6 alkanediyl group. * indicates a bond with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy- 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

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.

Examples of the alkanediyl group constituting R ^c include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , a hexane-1,6-diyl group, and the like.

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, a *-CH ₂ CH ₂ -O- group, More preferably, it is a single bond, *-CH ₂ CH ₂ -O- group.

Specific examples of the compound represented by formula (I) include compounds represented by formulas (I-1) to (I-15), preferably formulas (I-1) and (I-3) ), formulas (I-5), formulas (I-7), formulas (I-9), and compounds represented by formulas (I-11) to (I-15), more preferably formula (I-1), a compound represented by a formula (I-7), a formula (I-9), and a formula (I-15) is mentioned.

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

The compound represented by Formula (I) and the compound represented by Formula (II) may be used independently, respectively, and may use 2 or more types together. When using 2 or more types together, the mixing ratio is Formula (I):Formula (II) [molar ratio] Preferably 5:95-95:5, More preferably, 20:80-80:20, further Preferably it is 50:50-80:20.

It is preferable that the monomer (b2) which has an oxetanyl group and an ethylenically unsaturated bond is a monomer which has an oxetanyl group and a (meth)acryloyloxy group.

Preferred examples of (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth) ) Acryloyloxyethyloxetane and 3-ethyl-3-(meth)acryloyloxyethyloxetane are mentioned.

It is preferable that the monomer (b3) which has a tetrahydrofuryl group and an ethylenically unsaturated bond is a monomer which has a tetrahydrofuryl group and a (meth)acryloyloxy group.

As a preferable example of (b3), tetrahydrofurfuryl acrylate (For example, Viscoat V#150, Osaka Organic Chemical Co., Ltd. product), tetrahydrofurfuryl methacrylate, etc. are mentioned.

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) acrylic rate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate [In the technical field, it is called "dicyclofentanyl (meth)acrylate" as a common name. Also, it is sometimes called “tricyclodecyl (meth)acrylate.”], tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate [in the technical field, as a common name, “dish Clopentenyl (meth) acrylate”], dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate (meth)acrylic acid esters such as , propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept bicyclo unsaturated compounds such as -2-ene;

Dicarbonyl such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, and N-succinimidyl-4-maleimidebutyrate; mide derivatives;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, (meth)acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, vinyl acetate, 1 and 3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, as (c), benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzyl Maleimide, bicyclo[2.2.1]hept-2-ene, and the like are preferable. Moreover, from the point which is excellent in the developability at the time of pattern formation, as (c), benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable.

In resin [K1], it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise resin [K1].

The structural unit derived from (a), especially the structural unit derived from (b1); 50 to 98 mol% (more preferably 55 to 90 mol%);

the structural unit derived from (b); 2-50 mol% (more preferably 10-45 mol%).

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

For resin [K1], refer to the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki, Publishing House Chemical Dongin, 1st edition, 1st edition, March 1, 1972) and the cited literature described in the document. can be manufactured.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are put in a reaction vessel, for example, by replacing oxygen with nitrogen, a deoxidized atmosphere is created, and heating and keeping warm while stirring how to do it In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, Any of those normally used in the said field|area can be used. Examples of the polymerization initiator include azo compounds (such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide). . As a solvent, what is necessary is just to melt|dissolve each monomer, The solvent (E) etc. which are mentioned later can be used as a solvent of colored curable resin composition.

The obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as a solid (powder) by methods, such as reprecipitation. In particular, by using the below-mentioned solvent (E) as a solvent at the time of this polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

In resin [K2], it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise resin [K2].

The structural unit derived from (a); 4 to 45 mol% (more preferably 10 to 30 mol%);

The structural unit derived from (b), especially the structural unit derived from (b1); 2-95 mol% (more preferably 5-80 mol%);

the 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 within the above range, it tends to be excellent in storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the pattern obtained.

Resin [K2] can be manufactured by carrying out similarly to the method described as a manufacturing method of resin [K1]. Specific examples include a method in which predetermined amounts of (a), (b) (particularly (b1)) and (c), a polymerization initiator, and a solvent are put in a reaction vessel, and stirred, heated, and kept warm in a deoxidized atmosphere. . The obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as a solid (powder) by methods, such as reprecipitation.

In resin [K3], it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise resin [K3].

The structural unit derived from (a); 2-55 mol% (more preferably 10-50 mol%);

the structural unit derived from (c); 45 to 98 mol% (more preferably 50 to 90 mol%).

Resin [K3] can be manufactured by carrying out similarly to the method described as a manufacturing method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (b) has a cyclic ether structure having 2 to 4 carbon atoms, especially (b1) has an oxirane ring, carboxylic acid (a) and/or by adding to carboxylic acid anhydride. Specifically, first, the copolymer of (a) and (c) is produced in the same manner as described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise the copolymer of (a) and (c).

The structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%);

the 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 copolymer is reacted with a cyclic ether structure having 2 to 4 carbon atoms in (b), particularly the oxirane ring in (b1). make it Specifically, following the preparation of the copolymers of (a) and (c), the atmosphere in the flask is substituted with air from nitrogen, and (b) (particularly (b1)), carboxylic acid or carboxylic acid anhydride and a cyclic ether structure A reaction catalyst (for example, tris (dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) with K4] can be obtained.

It is preferable that the usage-amount of (b), especially the usage-amount of (b1) is 5-80 mol with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and a sensitivity to become favorable. Since the reactivity of a cyclic ether structure is high and unreacted (b) hardly remains, as (b) used for resin [K4], (b1) is preferable and (b1-1) is more preferable.

It is preferable that the usage-amount of the said reaction catalyst is 0.001-5 mass % with respect to the total amount of (a), (b) (especially (b1)), and (c). It is preferable that the usage-amount of the said polymerization inhibitor is 0.001-5 mass % with respect to the total amount of (a), (b), and (c).

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

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

It is preferable that the ratio of the structural unit derived from (b) (especially (b1)) and (c) exists in the following range with respect to the total number of moles of all the structural units which comprise the said copolymer.

The structural unit derived from (b), especially the structural unit derived from (b1); 5-95 mol% (more preferably 10-90 mol%);

the structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%).

Further, under the same conditions as in the production method of the resin [K4], the carboxylic acid of (a) in the cyclic ether structure derived from (b) that the copolymer of (b) (particularly (b1)) and (c) has Alternatively, resin [K5] can be obtained by reacting carboxylic acid anhydride. It is preferable that the usage-amount of (a) made to react with said copolymer is 5-80 mol with respect to 100 mol of (b) (particularly (b1)). Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, as (b) used for the resin [K5], (b1) is preferable, and (b1-1) is more preferable.

The resin [K6] is a resin in which a carboxylic acid anhydride is further reacted with the resin [K5]. A carboxylic acid anhydride is reacted with the hydroxyl group generated by the reaction of a cyclic ether structure with carboxylic acid or carboxylic acid anhydride.

As carboxylic acid anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride), etc. are mentioned.

Among the resins [K1] to [K6], preferred resins as the resin (B) are [K1] or [K2]. Resin (B) may consist of 1 type of resin, and may contain 2 or more types of resin.

Preferably the weight average molecular weights (Mw) of polystyrene conversion of resin (B) are 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When a weight average molecular weight (Mw) exists in the said range, the solubility with respect to the developing solution of an unexposed part is high, and there exists a tendency for the residual-film rate and hardness of the pattern obtained to also be high. Preferably the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of resin (B) is 1.1-6, More preferably, it is 1.2-4.

The solution acid value of resin (B) becomes like this. Preferably it is 5-180 mg-KOH/g, More preferably, it is 10-100 mg-KOH/g, More preferably, it is 12-50 mg-KOH/g. An acid value is a value measured as the quantity (mg) of potassium hydroxide required for neutralizing 1 g of resin, for example, can be calculated|required by titrating using potassium hydroxide aqueous solution.

Preferably content of resin (B) is 5-50 mass % in 100 mass % of solid content of colored curable resin composition, More preferably, it is 15-45 mass %, More preferably, it is 25-40 mass %. When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

[3] Polymeric compound (C)

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) by irradiation with light or the like, and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. It is preferable that the weight average molecular weight of a polymeric compound (C) is 3,000 or less.

Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra (meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth)acrylate, tetrapentaerythritol nona (meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified di Pentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified di Pentaerythritol hexa(meth)acrylate etc. are mentioned. Especially, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferable.

The colored curable resin composition of this invention can contain 1 type(s) or 2 or more types of polymeric compound (C). Preferably content of a polymeric compound (C) is 20-150 mass parts with respect to 100 mass parts of resin (B) in colored curable resin composition, More preferably, it is 40-70 mass parts.

[4] polymerization initiator (D)

A polymerization initiator (D) is a compound which generate|occur|produces an active radical, an acid, etc. by the action of light or heat, and can initiate polymerization.

A polymerization initiator (D) contains an oxime type compound. Thereby, even if it is an appropriate coloring agent density|concentration, while being able to form a color filter with high inclusion rate of the color gamut of Rec.ITU-R BT.2020, it can be set as the coloring curable resin composition with favorable patternability.

A polymerization initiator (D) may consider a sensitivity, patterning property, the formation property of a precise|precise pattern shape, etc., and may use 2 or more types together.

As an oxime type compound, an O-acyl oxime compound etc. are mentioned.

An O-acyl oxime compound is a compound which has a structure represented by Formula (d). Hereinafter, * represents a bond.

As such an O-acyloxime compound, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane -1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3) -Dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetyloxy-1-[9-ethyl-6-(2-methyl) Benzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-[9-(2-ethylhexyl)-6-(2,4,6-trimethylbenzoyl)-9H- benzo[i]carbazol-3-yl]-3-[1-(2,2,3,3-tetrafluoropropyloxy)phenyl]methanimine; and the like.

You may use commercial items, such as Irgacure OXE01, OXE02, OXE03 (above, BASF Corporation make), and N-1919 (made by ADEKA Corporation). If it is such an O-acyl oxime compound, there exists a tendency for the color filter excellent in photolithographic performance to be obtained.

The polymerization initiator (D) may contain polymerization initiators other than the oxime-based compound. As another polymerization initiator, an alkylphenone compound, a biimidazole compound, a triazine compound, an acylphosphine oxide compound, etc. are mentioned.

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

Examples of the compound having a structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morph Polynophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1- On and so on. You may use commercial items, such as Irgacure 369, 907, 379 (above, BASF Co., Ltd. product).

Examples of the compound having a structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl) Ethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α -diethoxyacetophenone, benzyl dimethyl ketal, etc. are mentioned.

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, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole (see Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'-bis(2 -Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)bi Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4 ,4',5,5'-tetra(trialkoxyphenyl)biimidazole (refer to Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), 4,4', and imidazole compounds in which the phenyl group at the 5,5'-position is substituted with a carboalkoxy group (refer to Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.

Among them, the compound represented by the following formula or a mixture thereof is preferable.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4- Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl ]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4 -Bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. are mentioned.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as an acylphosphine oxide compound.

As another polymerization initiator (D) other than the above, Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoylbenzoate methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone , benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned.

It is preferable that content of the oxime type compound in a polymerization initiator (D) is high from a viewpoint of producing the color filter with patterning property and the wide displayable color gamut. Specifically, the content of the oxime compound in the polymerization initiator (D) is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably, in 100% by mass of the polymerization initiator (D). is 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.

Preferably content of a polymerization initiator (D) is 0.03-0.25 mass part with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), More preferably, it is 0.05-0.15 mass part, More preferably Usually, it is 0.07-0.10 parts by mass. When content of a polymerization initiator (D) exists in the said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, there exists a tendency for productivity of a color filter to improve.

[5] Auxiliary for polymerization initiation (D1)

A polymerization initiation adjuvant (D1) is a compound used in order to accelerate|stimulate superposition|polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator, or a sensitizer. When a polymerization initiator auxiliary (D1) is included, it is used in combination with a polymerization initiator (D).

Examples of the polymerization initiation auxiliary (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound. Especially, a thioxanthone compound is preferable. You may use together 2 or more types of polymerization initiation adjuvant (D1).

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoic acid 2 -Ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'- Bis(ethylmethylamino)benzophenone etc. are mentioned, Especially, 4,4'-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry 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. anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythiok. Santon etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, and chlorophenylsulfanylacetic acid. Panylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

To [ content of a polymerization start adjuvant (D1) / 100 mass parts of total amounts of resin (B) and a polymeric compound (C)), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. When content of a polymerization initiation auxiliary|assistant (D1) exists in the said range, a pattern can be formed more highly sensitively, and there exists a tendency for productivity of a color filter to improve.

[6] Solvent (E)

It is preferable that colored curable resin composition contains 1 type(s) or 2 or more types of solvent (E). As the solvent (E), an ester solvent (a solvent containing -COO-), an ether solvent other than an ester solvent (a solvent containing -O-), an ether ester solvent (a solvent containing -COO- and -O-); Ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. are mentioned.

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

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 ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methyl anisole, etc. can be heard

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

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone Non, cyclohexanone, isophorone, etc. are mentioned.

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-dimethylacetoamide, and N-methylpyrrolidone.

It is preferable that a solvent (E) contains the organic solvent whose boiling points in 1 atm are 120 degreeC or more and 180 degrees C or less from the point of applicability|paintability and drying property. Among them, the solvent (E) is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N- containing at least one selected from the group consisting of dimethylformamide propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and 3-ethoxypropionate ethyl It is more preferable to include at least 1 sort(s) selected from the group which consists of.

Preferably content of a solvent (E) is 70-95 mass % in colored curable resin composition, More preferably, it is 75-92 mass %. In other words, solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When content of a solvent (E) exists in the said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

[7] Leveling agent (F)

The colored curable resin composition of this invention can contain the 1 type(s) or 2 or more types of leveling agents (F). As a leveling agent (F), a silicone type surfactant (which does not have a fluorine atom), a fluorine type surfactant, and the silicone type surfactant which has a fluorine atom, etc. are mentioned. These may have a polymerizable group in a side chain.

Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicon DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: 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 Joint Stock Company) and the like.

As a fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain|strand in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, dong FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapac (registered trademark) F142D, dong F171, dong F172, dong F173, dong F177, dong F183, dong F554, dong R30, RS-718-K (manufactured by DIC Corporation), EFTO (registered trademark) EF301, EF303, copper EF351, copper EF352 (manufactured by Mitsubishi Material Electronics, Kasei Co., Ltd.), Surflon (registered trademark) S381 , copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Labs), and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megapac (trademark) R08, Dong BL20, Dong F475, Dong F477, Dong F443 (DIC Co., Ltd. product), etc. are mentioned.

Content of a leveling agent (F) is 0.001 mass % or more and 0.2 mass % or less normally in colored curable resin composition, Preferably they are 0.002 mass % or more and 0.1 mass % or less, More preferably, they are 0.004 mass % or more and 0.05 mass % or less. . In addition, content of the said pigment dispersant is not contained in this content.

[8] Other ingredients

The colored curable resin composition of the present invention may contain, if necessary, one or two or more kinds of additives such as fillers, polymers other than the resin (B), antioxidants, adhesion promoters, ultraviolet absorbers, and anti-aggregation agents.

<Method for producing colored curable resin composition>

The colored curable resin composition of this invention is a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D), and if necessary, a solvent (E), a leveling agent (F), a polymerization initiation adjuvant (D1), it can prepare by mixing other components.

<Color filter and its manufacturing method>

The colored curable resin composition of this invention is useful as a material of a color filter, especially a green color filter.

The color filter may be formed as a molded product of the cured product of the colored curable resin composition, may be formed as a cured product (coat film) of the colored curable resin composition applied on the substrate, or the colored curable resin composition formed in a pattern shape on the substrate may be a cured product (pattern) of

The color filter according to the present invention is typically used as a green pixel.

As a method of manufacturing the hardened|cured material of colored curable resin composition in pattern shape, the photolithography method, the inkjet method, the printing method, etc. are mentioned, Preferably the photolithography method is mentioned. The photolithography method is a method of apply|coating colored curable resin composition to a board|substrate, drying it, forming a composition layer, exposing the said composition layer through a photomask, and developing. In the photolithography method, the cured product of the composition layer can be formed as a coating film by not using and/or not developing a photomask at the time of exposure.

Examples of the substrate include a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass with a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, or on the substrate. What formed the thin film of aluminum, silver, silver/copper/palladium alloy, etc. is used. Another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed on such a board|substrate.

Formation of the coating film or pattern by the photolithographic method can be performed by a well-known or customary apparatus and conditions, For example, it can produce as follows. First, a colored curable resin composition is apply|coated on a board|substrate, volatile components, such as a solvent, are removed and dried by heat-drying (pre-baking) and/or drying under reduced pressure, and a smooth composition layer is obtained. Examples of the coating method include a spin coating method, a slit coating method, and a slit-and-spin coating method.

As temperature in the case of heat-drying, 30-120 degreeC is preferable and 50-110 degreeC is more preferable. Moreover, as heating time, 10 second - 5 minutes are preferable, and 30 second - 3 minutes are more preferable. When drying under reduced pressure, it is preferable to carry out under a pressure of 50 to 150 Pa at a temperature range of 20 to 25°C. The film thickness of the composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the target color filter.

Next, the composition layer is exposed through a photomask when forming the target pattern. The pattern on the said photomask is not specifically limited, The pattern according to the intended use is used. It is not necessary to use a photomask when forming a coating film. As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250-450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength region, or a band-pass filter that cuts out light in the vicinity of 436 nm, 408 nm, or 365 nm is used in this wavelength region. may be selectively cut. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

For exposure, it is preferable to use an exposure apparatus such as a mask aligner or a stepper, since it is possible to uniformly irradiate parallel rays to the entire exposure surface and to accurately position the photomask and the substrate on which the composition layer is formed. .

By bringing the composition layer after exposure into contact with a developer and developing it, a pattern is formed on the substrate. By development, the unexposed portion of the composition layer is dissolved in the developer and removed.

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

The developing method may be any of a paddle method, a dipping method, and a spray method. Moreover, you may incline a board|substrate at an arbitrary angle at the time of development. It is preferable to wash with water after image development.

Moreover, it is preferable to post-baking to the obtained pattern. As post-baking temperature, 150-250 degreeC is preferable and 160-235 degreeC is more preferable. As post-baking time, 1 to 120 minutes are preferable, and 10 to 60 minutes are more preferable.

Generally, it is preferable that it is 3 micrometers or less, and, as for the film thickness of the coating film and pattern after a post-baking, it is more preferable that it is 2.8 micrometers or less.

Although the lower limit of the film thickness of a coating film and a pattern is not specifically limited, Usually, it is 1 micrometer or more, and 1.5 micrometer or more may be sufficient. As described above, according to the present invention, even with a thin film, it is possible to produce a color filter having a wide displayable color gamut and a high rate of coverage of the color gamut of Rec.ITU-R BT.2020.

<Display device>

The color filter which concerns on this invention is useful as a color filter used for display apparatus (liquid crystal display apparatus, organic electroluminescent apparatus, electronic paper, etc.) and a solid-state image sensor.

(Example)

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

<Synthesis Example 1: Preparation of Resin (B)>

In a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed and replaced with a nitrogen atmosphere, 371 parts by mass of 1-methoxy-2-propyl acetate was put, and the mixture was heated to 85° C. while stirring. Subsequently, 54 parts by mass of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl The mixed solution of 225 mass parts of mixtures of acrylates, 81 parts of vinyltoluene (isomer mixture), and 80 mass parts of 1-methoxy-2- propyl acetate was dripped over 4 hours. On the other hand, the solution which melt|dissolved 30 mass parts of polymerization initiator 2, 2- azobis (2, 4- dimethylvaleronitrile) in 160 mass parts of 1-methoxy-2- propyl acetate was dripped over 5 hours. After completion|finish of dripping of an initiator solution, after hold|maintaining at the same temperature for 4 hours, it cooled to room temperature, and obtained the B-type viscosity (23 degreeC) 246 mPas, and the copolymer of 37.5 mass % of solid content. The produced copolymer had a weight average molecular weight (Mw) of 10600, a dispersion degree of 2.01, and a solid content acid value of 115 mg-KOH/g.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of obtained resin (B) was performed on condition of the following using GPC method. Ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight (Mw) and number average molecular weight (Mn) obtained on the following conditions was made into molecular weight distribution.

Device ; HLC-8120GPC (manufactured by Toso Co., Ltd.)

column ; TSK-GELG2000HXL

column temperature; 40℃

solvent; tetrahydrofuran [THF]

flow rate ; 1.0mL/min

Test solution solid content concentration; 0.001 to 0.01 mass %

injection volume ; 50 μL

detector ; RI

standard for calibration; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500 (manufactured by Toso Corporation)

<Production Example 2: Preparation of pigment dispersion (A1)>

C.I. Pigment Blue 16 6.8 parts

C.I. Pigment Yellow 139 Part 5.2

4.5 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 83.5 parts

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A1).

<Production Example 3: Preparation of pigment dispersion (A2)>

C.I. Pigment Blue 16 4.8 parts

C.I. Pigment Yellow 185 7.2 parts

5.5 parts of acrylic pigment dispersant

82.5 parts of propylene glycol monomethyl ether acetate

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A2).

<Production Example 4: Preparation of pigment dispersion (A3)>

C.I. Pigment Blue 16 3.0 parts

C.I. Pigment Yellow 150 9.0 parts

5.3 parts of acrylic pigment dispersant

82.7 parts of propylene glycol monomethyl ether acetate

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A3).

<Production Example 5: Preparation of pigment dispersion (A4)>

C.I. Pigment Blue 16 4.8 parts

C.I. Pigment Yellow 139 1.0

C.I. Pigment Yellow 150 Part 6.3

5.1 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 82.8 parts

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A4).

<Production Example 6: Preparation of pigment dispersion (A5)>

C.I. Pigment Blue 16 Part 5.2

C.I. Pigment Yellow 139 2.6 copies

C.I. Pigment Yellow 138 4.3 parts

4.3 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 83.6 parts

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A5).

<Production Example 7: Preparation of pigment dispersion (A6)>

C.I. Pigment Blue 16 Part 5.3

C.I. Pigment Yellow 139 0.2 parts

C.I. Pigment Yellow 129 7.2 parts

5.1 parts of acrylic pigment dispersant

82.2 parts of propylene glycol monomethyl ether acetate

was mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A6).

<Examples 1 to 6 and Comparative Example 1>

(1) Preparation of colored curable resin composition

Each component of Table 1 was mixed so that it might become the compounding quantity of Table 1, and the colored curable resin composition was obtained. Moreover, preparation of colored curable resin composition WHEREIN: Propylene glycol monomethyl ether acetate was mixed so that solid content of colored curable resin composition might be 15 weight%. The unit of the compounding quantity of each component in Table 1 is "part by mass", pigment dispersions (A1) - (A6), resin (B), polymerizable compound (C), polymerization initiator (D-1), polymerization initiator (D-2) and each compounding quantity of a leveling agent (F) is conversion of solid content.

The polymerizable compound (C), the polymerization initiator (D-1), the polymerization initiator (D-2), and the leveling agent (F) are as follows.

Polymeric compound (C): dipentaerythritol hexaacrylate dipentaerythritol pentaacrylate (Shin-Nakamura Chemical Industry Co., Ltd. product, brand name "A-9550")

Polymerization initiator (D-1): a compound represented by the following formula (BASF Co., Ltd. product, trade name "Irgacure OXE03")

Polymerization initiator (D-2): 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole (brand name "Chemcure-TCDM" manufactured by CHEMBRIDGE INTERNATIONAL CORPORATION)

Leveling agent (F): an oligomer containing a fluorine-containing group and a lipophilic group (manufactured by DIC Co., Ltd., trade name “Megapac F-554”)

(2) Preparation of coating film

After apply|coating the colored curable resin composition by the spin coating method on the glass substrate ("Eagle XG" made by Corning Corporation) of 2 inches in width, it prebaked at 100 degreeC for 3 minute(s). After cooling, the substrate coated with this colored curable resin composition was irradiated with light at an exposure dose (365 nm standard) of 80 mJ/cm 2 in an atmospheric atmosphere using an exposure machine (“TME-150RSK” manufactured by Topcon Co., Ltd.). . Then, it post-baked at 230 degreeC for 30 minute(s) in oven, and obtained the coating film.

(3) Film thickness measurement

About the obtained coating film, the film thickness was measured using the film thickness measuring apparatus ("DEKTAK3" by Nippon Vacuum Technology Co., Ltd. product). A result is shown in Table 2.

(4) Measurement of chromaticity

About the obtained coating film, spectroscopy was measured using a colorimeter ("OSP-SP-200" manufactured by Olympus Co., Ltd.), and xy chromaticity coordinates (x, y) and brightness (Y) were measured. In addition, as said brightness (Y), the brightness in the coating film which shows green chromaticity coordinates (0.170, 0.760) corresponding to Rec.ITU-R BT.2020 was measured. A result is shown in Table 2.

(5) Evaluation of patternability

After apply|coating the colored curable resin composition by the spin coating method on the 2 inch horizontal glass substrate ("Eagle XG" by a Corning company), it prebaked at 100 degreeC for 3 minute(s).

After cooling, the interval between the substrate on which the composition layer was formed and the quartz glass photomask was set to 150 µm, and an exposure machine (“TME-150RSK” manufactured by Topcon Co., Ltd.) was used in an atmospheric atmosphere at an exposure dose of 50 mJ/cm 2 ( 365 nm standard) to prepare a coating film having chromaticity coordinates (x, y) of (0.170, 0.760). As a photomask, the photomask in which the 100 micrometers line and space pattern was formed was used.

The obtained coating film was developed by immersing in the aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 degreeC for 60 second, and the following evaluation criteria evaluated patternability. A result is shown in Table 2.

○: A pattern having a predetermined line width is formed.

x: The pattern of a predetermined line|wire width is not formed, but there exists a location which has not been dissolved and removed with a developing solution.

Comparative Example 1 had poor patternability. On the other hand, the coating films obtained in Examples 1-6 showed favorable patterning property in addition to showing the chromaticity of the said chromaticity coordinates (0.170, 0.760). In particular, Examples 1, 2, 4, 5 and 6 exhibited good patternability while realizing a high inclusion rate of the color gamut of Rec.ITU-R BT.2020 with a thinner film thickness.

Claims (4)

a colorant, a resin, a polymerizable compound, and a polymerization initiator;
the colorant contains CI Pigment Blue 16 and yellow colorant, no green colorant;
Total content of a coloring agent is 10-50 mass % in 100 mass % of solid content of colored curable resin composition,
Content of CI Pigment Blue 16 is 26 mass % or more in 100 mass % of colorants,
The colored curable resin composition in which a polymerization initiator contains an oxime type compound. The method of claim 1,
Colored curable resin composition in which the said yellow colorant contains the compound which has isoindoline skeleton. The color filter formed from the colored curable resin composition of Claim 1 or 2. A display device comprising the color filter according to claim 3 .