Red coloring composition, color filter, and display device

Abstract

To provide a red coloring composition capable of forming a color filter further improved in luminance (brightness).SOLUTION: The red coloring composition contains a red colorant and a yellow colorant. The red colorant contains a diketopyrrolopyrrole pigment and a quinacridone pigment having a halogen atom. The yellow colorant contains at least one selected from the group consisting of an azo dye containing a metal and a quinophthalone pigment.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a red coloring composition, a color filter, and a display device. [Background technology]

[0002] Color filters used in display devices such as liquid crystal displays, electroluminescent displays, and plasma displays, as well as solid-state image sensors such as CCDs and CMOS sensors, are manufactured using coloring compositions. Various colorants are used as coloring compositions for forming these color filters, and examples of using diketopyrrolopyrrole pigment and CI pigment red 177 as colorants in coloring compositions are known (Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2016-176058 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, colored compositions containing the above-mentioned colorants sometimes failed to achieve sufficiently satisfactory brightness (luminosity). Therefore, the present invention aims to provide a red colored composition capable of forming a color filter with even greater brightness (luminosity). [Means for solving the problem]

[0005] In other words, the gist of this invention is as follows: [1] A red coloring composition comprising a red coloring agent and a yellow coloring agent, wherein the red coloring agent comprises a diketopyrrolopyrrole pigment and a quinacridone pigment having a halogen atom, and the yellow coloring agent comprises at least one selected from the group consisting of azo dyes containing metals and quinophthalone pigments. [2] The red coloring composition according to [1], wherein the content of the quinacridone pigment having the halogen atom is 1% by mass or more and 50% by mass or less based on 100% by mass of the total coloring agent. [3] The red coloring composition according to [1] or [2], wherein the diketopyrrolopyrrole pigment has a halogen atom, and the content of the diketopyrrolopyrrole pigment is 40% by mass or more and 95% by mass or less based on 100% by mass of the total coloring agent. [4] The red coloring composition according to any one of [1] to [3], wherein the yellow coloring agent comprises at least one selected from the group consisting of CI Pigment Yellow 150 and CI Pigment Yellow 138, and the content of the yellow coloring agent is 3% by mass or more and 47% by mass or less based on 100% by mass of the total coloring agent. [5] A red coloring composition according to any one of [1] to [4], comprising a resin (B), a polymerizable compound (C), and a polymerization initiator (D). A color filter formed from the red coloring composition described in [6] [5]. A display device including the color filter described in [7] [6]. [Effects of the Invention]

[0006] According to the present invention, a color filter with further improved brightness (luminosity) can be provided. [Modes for carrying out the invention]

[0007] The red coloring composition of the present invention includes a red coloring agent and a yellow coloring agent as coloring agents (hereinafter sometimes referred to as coloring agent (A)). The red coloring composition of the present invention may contain a resin (hereinafter sometimes referred to as resin (B)), a polymerizable compound (hereinafter sometimes referred to as polymerizable compound (C)), and a polymerization initiator (hereinafter sometimes referred to as polymerization initiator (D)). The red coloring composition of the present invention may further contain a solvent (hereinafter sometimes referred to as solvent (E)). The red coloring composition of the present invention may further contain a polymerization initiator (hereinafter sometimes referred to as polymerization initiator (D1)). The red coloring composition of the present invention may further contain a leveling agent (hereinafter sometimes referred to as leveling agent (F)). In the present specification, the compounds exemplified as each component can be used alone or in combination of two or more unless otherwise specified.

[0008] The red coloring composition of the present invention is a red coloring composition containing a red coloring agent and a yellow coloring agent, wherein the red coloring agent includes a diketopyrrolopyrrole pigment and a quinacridone pigment having a halogen atom, and the yellow coloring agent includes at least one selected from the group consisting of an azo dye containing a metal and a quinophthalone pigment.

[0009] The red coloring composition of the present invention contains a red coloring agent as a main component in the coloring agent, and the red color is represented as having a maximum wavelength in the range of 380 to 600 nm.

[0010] The diketopyrrolopyrrole pigment preferably has a halogen atom (fluorine atom, bromine atom, chlorine atom, iodine atom), more preferably has one or both of a bromine atom and a chlorine atom, and even more preferably has a bromine atom. The number of halogen atoms in the diketopyrrolopyrrole pigment is preferably 1 or more, more preferably 2 or more, and even more preferably 2. The substitution position of the halogen atom in the diketopyrrolopyrrole pigment is preferably the para position of the phenyl group of the diketopyrrolopyrrole pigment. The diketopyrrolopyrrole pigment may be one kind or two or more kinds in the red coloring composition.

[0011] Examples of the diketopyrrolopyrrole pigment include C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Red 272, C.I. Pigment Red 291, etc. Among them, the diketopyrrolopyrrole pigment is particularly preferably C.I. Pigment Red 291.

[0012] The content of the diketopyrrolopyrrole pigment is preferably 40% by mass or more and 95% by mass or less, more preferably 45% by mass or more and 90% by mass or less, even more preferably 50% by mass or more, and even more preferably 55% by mass or more, based on 100% by mass of the total colorant.

[0013] The content of the diketopyrrolopyrrole pigment is preferably 40% by mass or more and 99% by mass or less, more preferably 49% by mass or more and 99% by mass or less, even more preferably 75% by mass or more and 99% by mass or less, even more preferably 80% by mass or more and 98% by mass or less, and even more preferably 85% by mass or more and 96% by mass or less, based on 100% by mass of the red coloring agent. When the content of the diketopyrrolopyrrole pigment is low within the above range, the brightness tends to be higher.

[0014] The content of the diketopyrrolopyrrole pigment is preferably 15% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less, and even more preferably 25% by mass or more and 40% by mass or less, based on 100% by mass of the solid content of the red coloring composition.

[0015] The quinacridone pigment contains halogen atoms (fluorine atoms, bromine atoms, chlorine atoms, iodine atoms), preferably containing one or both of bromine and chlorine atoms, and more preferably containing chlorine atoms. The number of halogen atoms in the quinacridone pigment is preferably one or more, more preferably two or more, and even more preferably two. The substitution positions of halogen atoms in quinacridone pigments are preferably at least one of the 1-4 positions and at least one of the 8-11 positions, more preferably a combination of the 2 and 9 positions, or the 3 and 10 positions, and even more preferably a combination of the 2 and 9 positions. The quinacridone pigment having a halogen atom may be present in one or more types in the red coloring composition.

[0016] Examples of quinacridone pigments containing halogen atoms include CI Pigment Red 202, CI Pigment Red 207, and CI Pigment Red 209. Among these, the quinacridone pigment having a halogen atom is particularly preferably CI Pigment Red 202 and CI Pigment Red 209, with CI Pigment Red 202 being the most preferred.

[0017] The content of the quinacridone pigment having the halogen atom is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 42% by mass or less, even more preferably 2% by mass or more and 25% by mass or less, even more preferably 3% by mass or more and 20% by mass or less, and even more preferably 4% by mass or more and 15% by mass or less, based on 100% by mass of the total colorant. A higher content of quinacridone pigment within the above range tends to result in higher brightness.

[0018] The content of the quinacridone pigment having the halogen atom is preferably 1% by mass or more and 70% by mass or less, more preferably 1% by mass or more and 50% by mass or less, even more preferably 1% by mass or more and 25% by mass or less, even more preferably 2% by mass or more and 20% by mass or less, and even more preferably 4% by mass or more and 15% by mass or less, based on 100% by mass of the red coloring agent.

[0019] The content of the quinacridone pigment having the halogen atom is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, even more preferably 0.1% by mass or more and 10% by mass or less, even more preferably 0.2% by mass or more and 8% by mass or less, and even more preferably 0.5% by mass or more and 5% by mass or less, based on 100% by mass of the solid content of the red coloring composition.

[0020] The content of diketopyrrolopyrrole pigment and quinacridone pigment having halogen atoms is preferably 90% by mass or more, more preferably 92% by mass or more, even more preferably 94% by mass or more, even more preferably 96% by mass or more, particularly preferably 98% by mass or more, and most preferably 100% by mass, based on 100% by mass of the red coloring agent.

[0021] The content of diketopyrrolopyrrole pigment and quinacridone pigment having halogen atoms is preferably 15% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less, and even more preferably 25% by mass or more and 40% by mass or less, based on 100% by mass of the solid content of the red coloring composition.

[0022] The yellow coloring agent is at least one selected from the group consisting of metal-containing azo dyes and quinophthalone pigments. The metal contained in the azo dye may be copper, nickel, cobalt, zinc, etc., but nickel is preferred. In the azo dye, it is preferable that the metal forms a complex with the organic dye through coordination bonds. Examples of azo dyes containing metals include CI Pigment Yellow 150.

[0023] Quinophthalone pigments preferably contain halogen atoms (fluorine atoms, bromine atoms, chlorine atoms, iodine atoms), more preferably contain one or both bromine atoms and chlorine atoms, and even more preferably contain chlorine atoms. The number of halogen atoms in the quinophthalone pigment is preferably 1 to 15, more preferably 2 to 13, even more preferably 3 to 11, and even more preferably 4 to 9. Examples of quinophthalone pigments include CI Pigment Yellow 138, CI Pigment Yellow 231, and CI Pigment Yellow 233.

[0024] The yellow coloring agent preferably contains at least one selected from the group consisting of CI Pigment Yellow 150 and CI Pigment Yellow 138, and more preferably contains CI Pigment Yellow 150 or CI Pigment Yellow 138.

[0025] The content of the yellow coloring agent is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 49% by mass or less, even more preferably 3% by mass or more and 48% by mass or less, even more preferably 3% by mass or more and 47% by mass or less, even more preferably 4% by mass or more and 40% by mass or less, and particularly preferably 5% by mass or more and 35% by mass or less, based on 100% by mass of the total coloring agent.

[0026] The content of the yellow coloring agent is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 18% by mass or less, and even more preferably 3% by mass or more and 16% by mass or less, based on 100% by mass of the solid content of the red coloring composition.

[0027] The content of CI Pigment Yellow 150 and / or CI Pigment Yellow 138 is preferably 95% by mass or more, more preferably 97% by mass or more, even more preferably 99% by mass or more, and even more preferably 100% by mass, of 100% by mass of the yellow coloring agent.

[0028] The content of the red coloring agent and the yellow coloring agent is preferably 95% by mass or more, more preferably 97% by mass or more, even more preferably 99% by mass or more, and even more preferably 100% by mass, out of 100% by mass of the total coloring agent.

[0029] The colorant (A), which contains a red colorant and a yellow colorant, may be subjected to rosin treatment, surface treatment using derivatives into which acidic or basic groups have been introduced, graft treatment of the surface of the colorant (A) with polymer compounds, atomization treatment by sulfuric acid atomization method, washing treatment with organic solvents or water to remove impurities, removal treatment of ionic impurities by ion exchange method, etc. The particle size of the colorant (A) is preferably substantially uniform.

[0030] If the red coloring composition contains a solvent (E), a coloring agent-containing solution containing the coloring agent (A) and solvent (E) may be prepared in advance, and then the red coloring composition may be prepared using the coloring agent-containing solution. If the coloring agent (A) does not dissolve in solvent (E), the coloring agent-containing solution can be prepared by dispersing the coloring agent (A) in solvent (E) and mixing them. The coloring agent-containing solution may contain some or all of the solvent (E) contained in the red coloring composition.

[0031] The solid content in the coloring agent-containing liquid is preferably 0.01% by mass or more and 99.99% by mass or less, more preferably 0.1% by mass or more and 99.9% by mass or less, even more preferably 0.1% by mass or more and 99% by mass or less, even more preferably 0.5% by mass or more and 90% by mass or less, and particularly preferably 1% by mass or more and 50% by mass or less, relative to the total amount of the coloring agent-containing liquid.

[0032] The coloring agent (A) can be uniformly dispersed in solution by dispersing it with a dispersant. When using two or more coloring agents (A) in combination, each may be dispersed individually, or multiple types may be mixed and dispersed together.

[0033] Examples of dispersants include surfactants, which may be cationic, anionic, nonionic, or amphoteric. Specifically, examples include polyester-based, polyamine-based, and acrylic-based surfactants. These dispersants may be used alone or in combination of two or more. Examples of dispersants, by trade name, include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solspers® (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA® (registered trademark) (manufactured by BASF Ltd.), Azisper® (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), and Disperbyk® (registered trademark) (manufactured by BIC Chemie Co., Ltd.), BYK® (registered trademark) (manufactured by BIC Chemie Co., Ltd.). A resin (B) described later may also be used as a dispersant.

[0034] When a dispersant is used, the amount of dispersant (solid content) used is usually 1 to 10,000 parts by mass, preferably 5 to 5,000 parts by mass, more preferably 10 to 1,000 parts by mass, and even more preferably 15 to 800 parts by mass, per 100 parts by mass of colorant (A). When the amount of dispersant used is within the above range, a colorant-containing liquid with a more uniform dispersion state tends to be obtained.

[0035] The content of the coloring agent (A) is preferably 16% to 50% by mass, more preferably 22% to 49% by mass, and even more preferably 28% to 48% by mass, based on the total amount of solids in the red colored composition. When the content of the coloring agent (A) is within the above range, the color density when used as a color filter is sufficient, and the required amount of resin (B) can be included in the composition, so it is preferable that a pattern with sufficient mechanical strength can be formed. Herein, "total amount of solids" as used herein refers to the amount obtained by subtracting the solvent content from the total amount of the coloring composition. The total amount of solids and the content of each component therein can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0036] <Resin (B)> Resin (B) is an alkali-soluble resin, and preferably an alkali-soluble resin containing a carboxylic acid.

[0037] Examples of resin (B) include the following resins [K1] to [K6]. Resin [K1]; a copolymer having structural units derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)") and structural units derived from a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); Resin [K2]; a copolymer having structural units derived from (a) and structural units derived from (b) and a monomer (c) copolymerizable with (a) (however different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); Resin [K3]; a copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]; a copolymer having structural units derived from (a) to which (b) is added and structural units derived from (c); Resin [K5]; a copolymer having structural units derived from (b) to which (a) is added and structural units derived from (c); A copolymer having a structural unit obtained by adding (a) to a resin [K6] and further adding a carboxylic acid anhydride, and a structural unit obtained by adding (c).

[0038] Examples of monomers (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as 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, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; Bicyclounsaturated compounds containing carboxyl groups, such as 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-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; Carboxylic acid anhydrides such as the anhydrides of the above unsaturated dicarboxylic acids, excluding fumaric acid and mesaconic acid; Unsaturated mono(meth)acryloyloxyalkyl) esters of divalent or higher polycarboxylic acids such as mono(2-(meth)acryloyloxyethyl) succinate and mono(2-(meth)acryloyloxyethyl) phthalate; Examples include unsaturated acrylates containing both a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid. Of these, acrylic acid, methacrylic acid, and maleic anhydride are preferred in terms of copolymerization reactivity and the solubility of the resulting resin in alkaline aqueous solutions. In this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0039] Monomer (b) refers to a polymerizable compound having a cyclic ether structure with 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. Preferably, monomer (b) is a monomer having a cyclic ether with 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0040] Examples of monomer (b) include monomers having an oxyranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b1)"), monomers having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b2)"), and monomers having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b3)").

[0041] Examples of monomers (b1) include monomers having a structure in which unsaturated aliphatic hydrocarbons are epoxidized (hereinafter sometimes referred to as "monomer (b1-1)") and monomers having a structure in which unsaturated alicyclic hydrocarbons are epoxidized (hereinafter sometimes referred to as "monomer (b1-2)").

[0042] As monomer (b1-1), monomers having a glycidyl group and an ethylenically unsaturated bond are preferred. Specifically as monomer (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis( Examples include 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, and 2,4,6-tris(glycidyloxymethyl)styrene.

[0043] Examples of monomers (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celoxide® 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer® A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer® M100; manufactured by Daicel Corporation), compounds represented by formula (BI), and compounds represented by formula (BII).

[0044] [ka]

[0045] [In formulas (BI) and (BII), R a and R bEach independently represents 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 hydroxy group. X a and X b Each independently represents a single bond, *-R c -, *-R c -O-, *-R c -S- or *-R c -NH-. R c represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond with O.

[0046] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and the like.

[0047] Examples of the alkyl group in which the hydrogen atom is 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, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, and the like.

[0048] R a and R b Preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, and more preferably include a hydrogen atom, a methyl group.

[0049] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, and the like.

[0050] X a and X bPreferably, the bonds include single bonds, methylene groups, ethylene groups, *-CH2-O- (* represents a bond with O) groups, and *-CH2CH2-O- groups, and more preferably, single bonds and *-CH2CH2-O- groups (* represents a bond with O).

[0051] Compounds represented by formula (BI) include those represented by any of formulas (BI-1) to (BI-15). Among these, compounds represented by formulas (BI-1), (BI-3), (BI-5), (BI-7), (BI-9), and (BI-11) to (BI-15) are preferred, and compounds represented by formulas (BI-1), (BI-7), (BI-9), and (BI-15) are more preferred.

[0052] [ka]

[0053] Compounds represented by formula (BII) include compounds represented by any of formulas (BII-1) to (BII-15), among which compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9), and (BII-11) to (BII-15) are preferred, and compounds represented by formulas (BII-1), (BII-7), (BII-9), and (BII-15) are more preferred.

[0054] [ka]

[0055] The compound represented by formula (BI) and the compound represented by formula (BII) may be used individually, or the compound represented by formula (BI) and the compound represented by formula (BII) may be used in combination. When used in combination, the content ratio of the compound represented by formula (BI) and the compound represented by formula (BII) is preferably 5:95 to 95:5 on a molar basis, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.

[0056] As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferred. Examples of monomer (b2) include 3-methyl-3-(meth)acryloyloxymethyl oxetane, 3-ethyl-3-(meth)acryloyloxymethyl oxetane, 3-methyl-3-(meth)acryloyloxyethyl oxetane, and 3-ethyl-3-(meth)acryloyloxyethyl oxetane.

[0057] As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferred. Examples of monomer (b3) include tetrahydrofuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofuryl methacrylate.

[0058] Examples of monomers (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] Decane-8-yl(meth)acrylate (in the relevant technical field, it is commonly called "dicyclopentanyl(meth)acrylate". It is also sometimes called "tricyclodecyl(meth)acrylate"), tricyclo[5.2.1.0 2,6 Decane-9-yl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] Decen-8-yl(meth)acrylate (commonly known as "dicyclopentenyl(meth)acrylate" in the relevant art), tricyclo[5.2.1.02,6 (meth)acrylic acid esters such as decen-9-yl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; 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-methoxybic Chlo[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 Bicyclounsaturated compounds such as -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, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide; Examples include vinyl group-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; vinyl group-containing nitriles such as (meth)acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-containing amides such as (meth)acrylamide; esters such as vinyl acetate; and dienes such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. Of these, styrene, vinyltoluene, and tricyclotoluene were selected based on their copolymerization reactivity and heat resistance. [5.2.1.0 2,6 Decane-8-yl(meth)acrylate, tricyclo[5.2.1.0 2,6 Decane-9-yl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] Decen-8-yl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] Decen-9-yl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hepto-2-ene and benzyl(meth)acrylate are preferred, and tricyclo[5.2.1.0 2,6 ] Decen-8-yl (meth)acrylate, tricyclo[5.2.1.0 2,6 Decen-9-yl (meth)acrylate and N-cyclohexyl maleimide are more preferred.

[0059] In resin [K1], the ratio of structural units derived from each is, among all structural units constituting resin [K1], (a) Structural units derived from (a); 2-60 mol% (b) Structural units derived from (b); 40-98 mol% It is preferable that this be the case. (a) Structural units derived from (a); 10-50 mol% (b) Structural units derived from (b); 50-90 mol% It is preferable that it be so. When the ratio of structural units of resin [K1] is within the above range, the storage stability of the red colored composition, the developability when forming the colored pattern, and the solvent resistance of the resulting optical filter tend to be excellent.

[0060] The resin [K1] can be manufactured, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the cited literature.

[0061] Specifically, a method involves placing predetermined amounts of (a) and (b), a polymerization initiator, and a solvent into a reaction vessel, creating a deoxygenated atmosphere by, for example, replacing oxygen with nitrogen, and heating and maintaining the temperature while stirring. The polymerization initiator and solvent used here are not particularly limited and can be those commonly used in the field. For example, examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.), and the solvent can be any solvent that dissolves each monomer. Examples of solvents include those described later as solvent (E) of the colored composition of the present invention.

[0062] The resulting copolymer may be used as is after the reaction, or after being concentrated or diluted, or after being extracted as a solid (powder) by methods such as reprecipitation. In particular, by using the solvent contained in the red coloring composition of the present invention as the solvent during polymerization, the solution after the reaction can be used directly in the preparation of the red coloring composition of the present invention, thereby simplifying the manufacturing process of the red coloring composition of the present invention.

[0063] In resin [K2], the ratio of structural units derived from each is, among all structural units constituting resin [K2], (a) Structural units derived from (a); 2-45 mol% (b) Structural units derived from (b); 2-95 mol% (c) Structural units derived from (c); 1-65 mol% It is preferable that this be the case. (a) Structural units derived from (a); 5-40 mol% (b) Structural units derived from (b); 5-80 mol% (c) Structural units derived from (c); 5-60 mol% It is preferable that it be so. When the ratio of structural units of resin [K2] is within the above range, the storage stability of the red colored composition, the developability when forming the colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the resulting optical filter tend to be excellent.

[0064] Resin [K2] can be manufactured, for example, in the same manner as described as the method for manufacturing resin [K1].

[0065] In resin [K3], the ratio of structural units derived from each is, out of the total structural units constituting resin [K3], (a) Structural units derived from (a); 2-60 mol% (c) Structural units derived from (c); 40-98 mol% It is preferable that this be the case. (a) Structural units derived from (a); 10-50 mol% (c) Structural units derived from (c); 50-90 mol% It is preferable that it be so. Resin [K3] can be manufactured, for example, in the same manner as described as the method for manufacturing resin [K1].

[0066] The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid and / or carboxylic acid anhydride of (a). First, a copolymer of (a) and (c) is produced in the same manner as described for the production of resin [K1]. In this case, it is preferable that the ratio of structural units derived from each is the same as that given for resin [K3].

[0067] Next, a portion of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms that (b) possesses. Following the production of the copolymer of (a) and (c), the atmosphere inside the flask is replaced from nitrogen to air, and (b), a reaction catalyst for the reaction between a carboxylic acid or carboxylic acid anhydride and a cyclic ether (e.g., tris(dimethylaminomethyl)phenol) and a polymerization inhibitor (e.g., hydroquinone) are added to the flask and the mixture is reacted at, for example, 60 to 130°C for 1 to 10 hours to produce resin [K4]. The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). This range tends to result in a good balance of storage stability of the red coloring composition, developability when forming patterns, and solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting patterns. Since the cyclic ether is highly reactive and unreacted (b) is less likely to remain, (b1) is preferred as the (b) used in the resin [K4], and (b1-1) is even more preferred. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b), and (c). The reaction conditions, such as the preparation method, reaction temperature, and time, can be adjusted as appropriate, taking into account the manufacturing equipment and the amount of heat generated by polymerization. Similarly, the preparation method and reaction temperature can be adjusted as appropriate, taking into account the manufacturing equipment and the amount of heat generated by polymerization.

[0068] As a first step, resin [K5] is produced in the same manner as the production method for resin [K1] described above to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used as is after the reaction, or a concentrated or diluted solution may be used, or it may be used after being extracted as a solid (powder) by methods such as reprecipitation. The ratios of structural units derived from (b) and (c) are, in relation to the total number of moles of all structural units constituting the copolymer, respectively: (b) Structural units derived from (b); 5-95 mol% (c) Structural units derived from (c); 5-95 mol% It is preferable that this be the case. (b) Structural units derived from (b); 10-90 mol% (c) Structural units derived from (c); 10-90 mol% It is preferable that it be so.

[0069] Furthermore, resin [K5] can be obtained by reacting the cyclic ether derived from (b) in the copolymer of (b) and (c) with the carboxylic acid or carboxylic acid anhydride of (a) under the same conditions as for the production of resin [K4]. The amount of (a) used to react with the copolymer is preferably 5 to 80 moles per 100 moles of (b). Since the cyclic ether is highly reactive and unreacted (b) is less likely to remain, (b1) is preferred as the (b) used in the resin [K5], and (b1-1) is even more preferred.

[0070] Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic acid anhydride. The hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or carboxylic acid anhydride is reacted with the carboxylic acid anhydride. Examples of carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride. The amount of carboxylic acid anhydride used is preferably 0.5 to 1 mole per mole of (a).

[0071] Specific resins (B) include 3,4-epoxycyclohexylmethyl(meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Resins such as decyl acrylate / (meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.02,6 Decyl acrylate / (meth)acrylic acid / N-cyclohexyl maleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 Decyl acrylate / (meth)acrylic acid / N-cyclohexyl maleimide / 2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 Decyl acrylate / (meth)acrylic acid / N-cyclohexyl maleimide / tricyclo[5.2.1.0 2,6 ] Resins such as decen-8-yl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyl oxetane / (meth)acrylic acid / styrene copolymer [K2]; resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer [K3]; resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, tricyclodecyl (meth)acrylate / benzyl (meth) Examples of resins include those obtained by adding glycidyl (meth)acrylate to an acrylate / (meth)acrylic acid copolymer [K4]; resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate [K5]; and resins obtained by reacting tetrahydrophthalic anhydride with a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate [K6].

[0072] The resin (B) is more preferably resin [K1] and resin [K2], and is particularly preferably resin [K2].

[0073] The weight-average molecular weight (Mw) of resin (B) in terms of polystyrene is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 3,000 to 30,000. When the weight-average molecular weight is within the above range, the solubility of the unexposed areas in the developer is high, and the residual film rate and hardness of the resulting pattern tend to be high. The degree of dispersion of resin (B) [weight-average molecular weight (Mw) / number-average molecular weight (Mn)] is preferably 1 or more and 6 or less, more preferably 1.001 or more and 4 or less, and even more preferably 1.01 or more and 4 or less.

[0074] The acid value (solid content equivalent) of resin (B) is preferably 10 mg-KOH / g or more and 300 mg-KOH / g or less, more preferably 20 mg-KOH / g or more and 250 mg-KOH / g or less, even more preferably 25 mg-KOH / g or more and 200 mg-KOH / g or less, even more preferably 30 mg-KOH / g or more and 150 mg-KOH / g or less, and particularly preferably 60 mg-KOH / g or more and 135 mg-KOH / g or less. Here, the acid value is measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0075] The content of resin (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, based on 100% by mass of the solid content of the red coloring composition. When the content of resin (B) is within the above range, the solubility of the unexposed areas in the developer tends to be high.

[0076] <Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), and examples include compounds having polymerizable ethylenically unsaturated bonds, and is preferably a (meth)acrylic acid ester compound.

[0077] Examples of polymerizable compounds having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and monomers (a), (b), and (c) mentioned above.

[0078] Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.

[0079] In particular, polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, and ethylene glycol-modified pentaerythritol tetra(meth)acrylate. Examples include ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate, preferably dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and trimethylolpropane tri(meth)acrylate, more preferably trimethylolpropane tri(meth)acrylate.

[0080] The weight-average molecular weight of the polymerizable compound (C) is preferably 50 to 4,000, more preferably 70 to 3,500, even more preferably 100 to 3,000, even more preferably 150 to 2,900, and particularly preferably 250 to 1,500.

[0081] The content of polymerizable compound (C) may be, for example, 1% by mass or more and 50% by mass or less, preferably 5% by mass or more and 45% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 15% by mass or more and 35% by mass or less, based on the total amount of solids of the red colored composition.

[0082] <Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that generates active radicals, acids, etc., upon the action of light or heat and can initiate polymerization; any known polymerization initiator can be used.

[0083] Examples of polymerization initiators (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

[0084] Examples of O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, N-acetoxy-1-[ Examples include 9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine. Furthermore, commercially available O-acyloxime compounds such as Irgacure® OXE01, OXE02, OXE03 (all manufactured by BASF) and N-1919 (manufactured by ADEKA Corporation) may be used. Among these, at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine is preferred as the O-acyloxime compound, with N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine being more preferred.

[0085] Examples of alkylphenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercial alkylphenone compounds such as Irgacure® 369, 907, and 379 (all manufactured by BASF) may also be used. Examples of alkylphenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal.

[0086] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Publication No. 6-75372, Japanese Patent Publication No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, and 2,2'-bis(2-chloro Examples include phenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), and biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Publication No. 7-10913, etc.).

[0087] Examples of triazine compounds 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, and 2,4-bis(trichloromethyl)-6-[2-( Examples include 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, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0088] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure® 819 (manufactured by BASF) may also be used.

[0089] Furthermore, examples of polymerization initiators (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; and 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with polymerization initiators (D1) (especially amines) as described later.

[0090] The polymerization initiator (D) is preferably a polymerization initiator comprising at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds, and more preferably a polymerization initiator comprising an O-acyloxime compound.

[0091] The content of the polymerization initiator (D) is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 1 part by mass to 20 parts by mass, based on 100 parts by mass of the total amount of resin (B) and polymerizable compound (C) contained in the red coloring composition. When the content of the polymerization initiator (D) is within the above range, sensitivity tends to increase and exposure time tends to be shortened, thus improving the productivity of color filters.

[0092] <Polymerization initiator (D1)> A polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of a polymerizable compound (C) whose polymerization has been initiated by a polymerization initiator (D). When a polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

[0093] Examples of polymerization initiators (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0094] Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michla's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, with 4,4'-bis(diethylamino)benzophenone being preferred. Alternatively, commercially available amine compounds such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

[0095] Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0096] Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0097] Examples of carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0098] When these polymerization initiators (D1) are used, their content is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total amount of the total resin (B) and polymerizable compound (C) contained in the red coloring composition.

[0099] <Solvent (E)> The solvent (E) is not particularly limited, and any solvent commonly used in the art may be used. Examples of solvent (E) include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing both -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxides, etc. Two or more of these solvents may be used in combination.

[0100] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0101] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, 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, phenethole, and methylanisole.

[0102] 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, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxy-2-methylpropionate Examples include ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

[0103] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0104] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0105] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0106] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0107] As solvent (E), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and cyclohexanone are preferred, with propylene glycol monomethyl ether acetate being more preferred.

[0108] When solvent (E) is included, the content of solvent (E) is usually 99.99% by mass or less, preferably 40% to 99% by mass, more preferably 50% to 95% by mass, even more preferably 70% to 95% by mass, and even more preferably 75% to 90% by mass, relative to the total amount of the red coloring composition. In other words, the total amount of solids in the red coloring composition is usually 0.01% by mass or more, preferably 1% to 60% by mass, more preferably 5% to 50% by mass, even more preferably 5% to 30% by mass, and even more preferably 10% to 25% by mass. When the content of solvent (E) is within the above range, the flatness during application is good, and the display characteristics tend to be good because the color density is not insufficient when a color filter is formed.

[0109] <Leveling agent (F)> Examples of leveling agents (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants containing fluorine atoms. These may have polymerizable groups in their side chains.

[0110] Examples of silicone-based surfactants include surfactants that have siloxane bonds in their molecules. Specifically, examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (product 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, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

[0111] Examples of fluorine-based surfactants include surfactants having fluorocarbon chains in their molecules. Specifically, these include Florard® FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac® F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), F-Top® EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon® S381, S382, SC101, SC105 (manufactured by AGC Inc.), and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).

[0112] Examples of silicone-based surfactants containing fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in their molecules. Specifically, examples include Megafac® R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0113] When a leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.0005% by mass or more and 1% by mass or less, more preferably 0.001% by mass or more and 0.5% by mass or less, and even more preferably 0.005% by mass or more and 0.1% by mass or less, relative to the total amount of the red coloring composition. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0114] <Other ingredients> The red coloring composition may optionally contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, quenchers, antioxidants, light stabilizers, and chain transfer agents.

[0115] <Method for producing a red colored composition> A red colored composition can be prepared by mixing a colorant (A), a resin (B) used as needed, a polymerizable compound (C), a polymerization initiator (D), a solvent (E), a leveling agent (F), and other components. Mixing can be carried out using known or conventional apparatus and conditions. The coloring agent (A) may be used in a dispersed state after being mixed with part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle size is about 0.2 μm or less. It is preferable to use it in a dispersed state. In this case, part or all of the dispersant and resin (B) may be added as needed. Alternatively, the coloring agent (A) may be used after being dissolved in part or all of the solvent (E) in advance. The desired red coloring composition can be prepared by mixing the remaining components to the coloring agent-containing liquid obtained in this way to a predetermined concentration.

[0116] <How to manufacture color filters> A color filter, which may also be a color conversion layer, can be formed from a red coloring composition. Methods for forming the coloring pattern include photolithography, inkjet printing, and printing. Among these, photolithography is preferred. Photolithography is a method in which the coloring composition is applied to a substrate, dried to form a coloring composition layer, and then exposed to light through a photomask for development. In photolithography, by not using a photomask during exposure and / or by not developing, a colored coating film, which is a cured product of the coloring composition layer, can be formed. The coloring pattern or colored coating film formed in this way is the color filter of the present invention.

[0117] The film thickness of the color filter to be manufactured is not particularly limited and can be adjusted as appropriate depending on the purpose and application. For example, it is 0.1 μm or more and 30 μm or less, preferably 0.1 μm or more and 20 μm or less, and more preferably 0.5 μm or more and 6 μm or less.

[0118] As substrates, glass plates such as quartz glass, borosilicate glass, aluminasilate glass, and soda-lime glass with a silica coating on the surface are used; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used; silicon plates are used; and aluminum, silver, silver / copper / palladium alloy thin films are formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

[0119] The formation of each color pixel by photolithography can be carried out using known or conventional equipment and conditions. For example, it can be manufactured as follows. First, the colored composition is applied to the substrate, and volatile components such as solvents are removed by heat drying (pre-baking) and / or vacuum drying, and then dried to obtain a smooth colored composition layer. Coating methods include spin coating, slit coating, and slit and spin coating. When performing heat drying, the temperature is preferably between 30°C and 120°C, and more preferably between 50°C and 110°C. The heating time is preferably between 10 seconds and 60 minutes, and more preferably between 30 seconds and 30 minutes. When performing vacuum drying, it is preferable to do so under a pressure of 50 Pa to 150 Pa and at a temperature range of 20°C to 25°C. The thickness of the colored composition layer is not particularly limited and can be appropriately selected according to the desired thickness of the color filter.

[0120] Next, the colored composition layer is exposed via a photomask to form the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern appropriate to the intended application is used. Furthermore, it is preferable to use an exposure apparatus such as a mask aligner and a stepper, as this allows for uniform irradiation of the entire exposure surface with parallel light rays and precise alignment between the photomask and the substrate on which the colored composition layer is formed.

[0121] For exposure, a light source that generates light with a wavelength between 250 nm and 450 nm is preferred. For example, light below 350 nm can be filtered out using a filter that cuts out this wavelength range, or light around 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

[0122] A colored pattern is formed on the substrate by developing the red colored composition layer after exposure by contacting it with a developer. During development, the unexposed parts of the red colored composition layer are dissolved and removed by the developer. As the developer, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.03% by mass or more and 5% by mass or less. Furthermore, the developer may also contain a surfactant. The development method can be any of the following: paddle method, dipping method, or spray method. Furthermore, the substrate may be tilted to any angle during development. It is preferable to wash the substrate with water after development.

[0123] Furthermore, it is preferable to perform post-baking on the obtained coloring pattern. The post-baking temperature is preferably 150°C to 250°C, and more preferably 160°C to 240°C. The post-baking time is preferably 1 minute to 120 minutes, and more preferably 10 minutes to 60 minutes.

[0124] <Display device> The aforementioned color filter is useful as a color filter for display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors, and is particularly useful as a color filter for organic EL devices. [Examples]

[0125] The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the following examples, and it is certainly possible to implement it with appropriate modifications within the scope that is consistent with the spirit of the preceding and following descriptions, and all such modifications are included within the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass".

[0126] Synthesis Example 1 Preparation of resin (B) A flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was subjected to a nitrogen atmosphere by flowing nitrogen at 0.02 L / min. 268 parts of ethyl lactate were added, and the mixture was heated to 70°C while stirring. Then, 55 parts of acrylic acid, 81 parts of N-cyclohexylmaleimide, and 3,4-epoxytricyclo[5.2.1.0 2,6 224 parts of decyl acrylate (a mixture of the compound represented by formula (I-1) and the compound represented by formula (II-1) in a molar ratio of 50:50), and tricyclo[5.2.1.0 2,6A solution was prepared by dissolving 7 parts of decene-8-yl acrylate (a mixture of the compound represented by formula (c-1) and the compound represented by formula (c-2) in a molar ratio of 50:50) in 140 parts of ethyl lactate. This solution was then added dropwise to a flask kept at 70°C over 4 hours using a dropping funnel. Meanwhile, a solution of 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 225 parts of ethyl lactate was added dropwise to the flask over 4 hours using another dropping funnel. After the addition of the polymerization initiator solution was complete, the flask was kept at 70°C for 4 hours, and then cooled to room temperature. The weight-average molecular weight Mw was 11.2 × 10⁻⁶. 3 A copolymer (B1-1) solution with a solid content of 36.7% and a solution acid value of 44 mg-KOH / g was obtained. The solid content acid value was calculated from the above solid content and solution acid value to be 119 mg-KOH / g.

[0127] [ka]

[0128] [ka]

[0129] Examples 1-5 and Comparative Examples 1-4 (1) Preparation of red coloring composition Red colored compositions 1-5 and comparative red colored compositions 1-4 were prepared using the components and quantities shown in Tables 1 and 2. Note that the amounts of colorants (A), acrylic pigment dispersants, resins (B), polymerizable compounds (C), polymerization initiators (D), and leveling agents (F) in Tables 1 and 2 are calculated on a solid content basis.

[0130] [Table 1]

[0131] [Table 2]

[0132] In Tables 1 and 2, R202, R177, R291, Y150, and Y138 in colorant (A) were used after being mixed with the acrylic pigment dispersant in Tables 1 and 2 and the amount of propylene glycol monomethyl ether acetate indicated in "(E-1) (Note 2)" in Tables 1 and 2, and pre-dispersed. "(E-1)(Note 1)" includes the amount of "(E-1)(Note 2)" used to disperse the coloring agent (A), and represents the total amount of solvent (E) contained in the red coloring composition.

[0133] In Tables 1 and 2, the components are as follows: Coloring agent (A) [R202]: CI Pigment Red 202 (pigment) Coloring agent (A) [R177]: CI Pigment Red 177 (pigment) Coloring agent (A) [R291]: CI Pigment Red 291 (pigment) Coloring agent (A) [Y150]: CI Pigment Yellow 150 (pigment) Coloring agent (A) [Y138]: CI Pigment Yellow 138 (pigment) Resin (B): Copolymer (B1-1) Polymerizable compound (C-1): NK ester A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Polymerization initiator (D-1): Compound represented by the following formula (manufactured by BASF Corporation, trade name "Irgacure OXE03")

[0134] [ka] Solvent (E-1): Propylene glycol monomethyl ether acetate Leveling agent (F): Oligomer containing fluorine-containing and lipophilic groups (manufactured by DIC Corporation, product name "Megafac F-554")

[0135] (2) Preparation of coating film A red coloring composition was applied to a 2-inch square glass substrate (Eagle XG; Corning Corporation) by spin coating, and then pre-baked in a clean oven at 100°C for 3 minutes. After cooling, the substrate was exposed to 80 mJ / cm² under an atmospheric atmosphere using an exposure unit (Topcon Corporation's "TME-150RSK"). 2 The sample was irradiated with light at an exposure level of 365 nm. Afterward, post-baking was performed in an oven at 230°C for 30 minutes to obtain the coating.

[0136] (3) Film thickness measurement The film thickness of the obtained coating was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Tables 1 and 2.

[0137] (4) Measurement of chromaticity The obtained coating film was subjected to spectral analysis using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) and lightness Y in the CIE XYZ color system were measured using the characteristic function of the C light source. The results are shown in Tables 1 and 2. In Table 1, △Y indicates the degree of improvement in lightness Y for each example 1 to 3, relative to the lightness Y of each comparative example 1 to 3. In Table 2, △Y indicates the degree of improvement in lightness Y for examples 4 and 5, relative to the lightness Y of comparative example 4.

Claims

1. A red coloring composition comprising a red coloring agent and a yellow coloring agent, wherein the red coloring agent comprises a diketopyrrolopyrrole pigment and a quinacridone pigment having a halogen atom, the diketopyrrolopyrrole pigment being C.I. Pigment Red 291, the quinacridone pigment having a halogen atom being C.I. Pigment Red 202, and the yellow coloring agent comprising at least one selected from the group consisting of azo dyes containing metals and quinophthalone pigments. A red coloring composition in which the azo dye containing the aforementioned metal is C.I. Pigment Yellow 150 and the quinophthalone pigment is C.I. Pigment Yellow 138.

2. The red coloring composition according to claim 1, wherein the content of the quinacridone pigment having the halogen atom is 1% by mass or more and 50% by mass or less, based on 100% by mass of the total coloring agent.

3. The red coloring composition according to claim 1 or 2, wherein the diketopyrrolopyrrole pigment has a halogen atom, and the content of the diketopyrrolopyrrole pigment is 40% by mass or more and 95% by mass or less based on 100% by mass of the total coloring agent.

4. The red coloring composition according to claim 1 or 2, wherein the content of the yellow coloring agent is 3% by mass or more and 47% by mass or less, based on 100% by mass of the total coloring agent.

5. A red coloring composition according to claim 1 or 2, comprising a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

6. A color filter formed from the red coloring composition described in claim 5.

7. A display device including the color filter described in claim 6.

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