WO2024101219A1 - Colored curable resin composition, color filter, display device, and solid-state imaging element - Google Patents

Colored curable resin composition, color filter, display device, and solid-state imaging element Download PDF

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Publication number
WO2024101219A1
WO2024101219A1 PCT/JP2023/039215 JP2023039215W WO2024101219A1 WO 2024101219 A1 WO2024101219 A1 WO 2024101219A1 JP 2023039215 W JP2023039215 W JP 2023039215W WO 2024101219 A1 WO2024101219 A1 WO 2024101219A1
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pigment
structural unit
resin
meth
group
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PCT/JP2023/039215
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French (fr)
Japanese (ja)
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亜矢子 中尾
泰行 桐生
中山 萌黄 宮澤
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住友化学株式会社
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Publication of WO2024101219A1 publication Critical patent/WO2024101219A1/en

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  • the present invention relates to a colored curable resin composition, a color filter, a display device, and a solid-state imaging device.
  • Color filters used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, as well as solid-state imaging devices such as CCD and CMOS sensors, are manufactured from colored curable resin compositions. It is known that a specific polymerization initiator is used in this colored curable resin composition (Patent Document 1).
  • the objective of the present invention is to provide a colored curable resin composition that can form a color filter with improved solvent resistance.
  • the gist of the present invention is as follows. [1] A composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator; The colored curable resin composition, wherein the polymerization initiator comprises a compound represented by formula (I).
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a hydrocarbon group which may have a substituent.
  • n represents an integer of 0 to 4.
  • the --CH 2 -- contained in the hydrocarbon group may be replaced with --O--, --S--, --CO--, or --OCO--.
  • Resin [K1] a copolymer having a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
  • Resin [K2] a copolymer having a structural unit derived from the (a), a structural unit derived from the (b), and a structural unit derived from a monomer (c) copolymerizable with the (a);
  • Resin [K3] a copolymer having a structural unit derived from the (a) and a structural unit derived from the (c);
  • Resin [K4] a copolymer having a structural unit derived from the (a) and a structural unit derived from the (b) by addition, and a structural unit derived from the (c); Res
  • the monomer (c) is at least one selected from the group consisting of (meth)acrylic acid esters having a linear or branched aliphatic unsaturated hydrocarbon group, (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, vinyl monomers having an unsaturated aliphatic hydrocarbon ring, vinyl monomers having an unsaturated heterocycle, and vinyl monomers having an aromatic ring.
  • the colorant includes a green pigment and a yellow pigment, The green pigment includes at least one selected from the group consisting of C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I.
  • the yellow pigment includes at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 231, and C.I. Pigment Yellow 233.
  • the colorant includes a red pigment and a yellow pigment, The red pigment includes at least one selected from the group consisting of C.I. Pigment Red 122, C.I. Pigment Red 177, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I.
  • the yellow pigment includes at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 231, and C.I. Pigment Yellow 233.
  • the colorant includes a blue pigment and a purple pigment, The blue pigment includes at least one selected from the group consisting of C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 16;
  • a display device comprising the color filter according to [11].
  • a solid-state imaging device comprising the color filter according to [11].
  • the present invention makes it possible to provide a colored curable resin composition that can form a color filter with improved solvent resistance.
  • the colored curable resin composition of the present invention contains a colorant (hereinafter, may be referred to as colorant (A)), a resin (hereinafter, may be referred to as resin (B)), a polymerizable compound (hereinafter, may be referred to as polymerizable compound (C)), and a polymerization initiator (hereinafter, may be referred to as polymerization initiator (D)).
  • the colored curable resin composition of the present invention may further contain a solvent (hereinafter, may be referred to as solvent (E)).
  • the colored curable resin composition of the present invention may further contain a polymerization initiation aid (hereinafter, may be referred to as polymerization initiation aid (D1)).
  • the colored curable resin composition of the present invention may further contain a thiol compound (hereinafter, may be referred to as thiol compound (T)).
  • the colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, may be referred to as leveling agent (F)).
  • leveling agent hereinafter, may be referred to as leveling agent (F)
  • the compounds exemplified as each component may be used alone or in combination of two or more kinds, unless otherwise specified.
  • the colorant (A) may be a dye (A1) or a pigment (A2), and the pigment (A2) is preferred. These may be used alone or in combination of two or more.
  • the dye (A1) is not particularly limited, and known dyes can be used, such as solvent dyes, acid dyes, direct dyes, and mordant dyes.
  • dyes include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in Dyeing Notes (Shikisensha).
  • examples of dyes that can be used according to their chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, quinophthalone dyes, and isoindoline dyes.
  • organic solvent-soluble dyes are preferred.
  • dyes having the following Color Index (C.I.) numbers are included.
  • C.I. Color Index
  • Solvent Orange 2 7, 11, 15, 26, 41, 54, 56, 77, 86, 99; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Solvent dyes such as C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; C.I.
  • Acid dyes such as C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109; C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; C.I.
  • Direct dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; C.I. Disperse Yellow 51, 54, 76; C.I. Disperse Violet 26, 27; C.I. Disperse dyes such as C.I. Disperse Blue 1, 14, 56, 6;0, C.I. Basic Red 1, 10; C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; C.I. Basic Violet 2; C.I. Basic Red 9; C.I.
  • Basic dyes such as C.I. Basic Green 1; C.I. Reactive Yellow 2, 76, 116; C.I. Reactive Orange 16; C.I. Reactive dyes such as C.I. Reactive Red 36; C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C.I.
  • These dyes can be selected appropriately to match the spectral spectrum of the desired color filter.
  • Pigments (A2) may be any known pigment, including, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).
  • examples include azo pigments, cyanine pigments, triphenylmethane pigments, xanthene pigments, anthraquinone pigments, naphthoquinone pigments, quinoneimine pigments, methine pigments, azomethine pigments, squarylium pigments, acridine pigments, styryl pigments, coumarin pigments, quinoline pigments, nitro pigments, phthalocyanine pigments, perylene pigments, quinophthalone pigments, and isoindoline pigments. Of these, phthalocyanine pigments, quinophthalone pigments, and isoindoline pigments are preferred.
  • pigments classified as C.I. Pigment include yellow pigments such as 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, 214, and 231; Orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; red pigments such as C.I.
  • These pigments can be selected appropriately to match the spectral spectrum of the desired color filter.
  • the colorant (A) preferably contains at least one selected from the group consisting of a yellow dye and a yellow pigment (hereinafter, these may be collectively referred to as "yellow colorant”), a green dye and a green pigment (hereinafter, these may be collectively referred to as "green colorant”), and more preferably contains a yellow pigment and/or a green pigment.
  • the yellow dye may be any of the above dyes whose hues are classified as yellow
  • the yellow pigment may be any of the above pigments whose hues are classified as yellow.
  • the yellow pigments quinophthalone yellow pigments, metal-containing yellow pigments, and isoindoline yellow pigments are preferred, and at least one selected from the group consisting of C.I. Pigment Yellow 138, 139, 150, 185, 231, and 233 is more preferred, and at least one selected from the group consisting of C.I. Pigment Yellow 138, 139, 150, and 185 is even more preferred.
  • the green dye may be any of the above dyes whose hue is classified as green, and the green pigment may be any of the above pigments whose hue is classified as green.
  • phthalocyanine pigments are preferred, at least one selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferred, at least one selected from the group consisting of C.I. Pigment Green 7, 36, 58, 59, 62, and 63 is even more preferred, and at least one selected from the group consisting of C.I. Pigment Green 58 and 59 is even more preferred.
  • the colorant (A) preferably contains a yellow colorant and/or a green colorant in total in an amount of, for example, 50 mass% or more, preferably 70 mass% or more, more preferably 90 mass% or more, and particularly preferably 95 mass% or more, based on 100 mass% of all colorants.
  • a yellow colorant and a green colorant are contained.
  • the content of the yellow colorant is, for example, 10 mass% or more and 70 mass% or less, preferably 15 mass% or more and 60 mass% or less, and more preferably 20 mass% or more and 55 mass% or less, based on 100 mass% in total of the yellow colorant and the green colorant.
  • the content of the green colorant is, for example, 30% by mass or more and 90% by mass or less, preferably 40% by mass or more and 85% by mass or less, and more preferably 45% by mass or more and 80% by mass or less, based on 100% by mass of the total of the yellow colorant and the green colorant.
  • the green colored curable resin composition may contain a blue colorant, which will be described later, in addition to a green colorant and a yellow colorant.
  • the content of the blue colorant is, for example, 0 mass% or more and 5 mass% or less, preferably 0.1 mass% or more and 4.5 mass% or less, and more preferably 0.2 mass% or more and 4.0 mass% or less, relative to 100 mass% in total of the green colorant, the yellow colorant, and the blue colorant.
  • the colorant (A) preferably contains at least one selected from the group consisting of a yellow colorant, a red dye, and a red pigment (hereinafter, these may be collectively referred to as "red colorant”), and more preferably contains a yellow pigment and/or a red pigment.
  • yellow colorants include those similar to those used to prepare the green colored curable resin composition, and the preferred embodiments are also similar.
  • the red dye may be any of the above dyes whose hue is classified as red
  • the red pigment may be any of the above pigments whose hue is classified as red.
  • the red pigments at least one selected from the group consisting of C.I. Pigment Red 122, 177, 254, 255, 264, 269, 272, and 291 is preferable, and at least one selected from the group consisting of C.I. Pigment Red 177, 254, 269, 272, and 291 is more preferable.
  • the colorant (A) When preparing a red colored curable resin composition, the colorant (A) preferably contains, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and especially 100% by mass of a yellow colorant and/or a red colorant in total, based on 100% by mass of all colorants. It is also preferable that the colorant (A) contains both a yellow colorant and a red colorant.
  • the colorant (A) preferably contains at least one selected from the group consisting of a blue dye and a blue pigment (hereinafter, these may be collectively referred to as "blue colorant”), and more preferably contains a blue pigment.
  • blue dyes include those dyes that have a hue classified as blue among the above dyes
  • blue pigments include those pigments that have a hue classified as blue among the above pigments.
  • a phthalocyanine pigment is preferable, and at least one selected from the group consisting of C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 16 is more preferable.
  • violet colorant When preparing a blue colored curable resin composition, it is preferable to also contain a violet dye and a violet pigment (hereinafter, these may be collectively referred to as "violet colorant”) in addition to the blue colorant.
  • the violet dye may be any of the above dyes whose hues are classified as violet
  • the violet pigment may be any of the above pigments whose hues are classified as violet.
  • a violet pigment is preferable, and among the violet pigments, at least one selected from the group consisting of C.I. Pigment Violet 19, 23, and 29 is more preferable.
  • the colorant (A) preferably contains, for example, 30% by mass or more and 99% by mass or less, preferably 50% by mass or more, and more preferably 60% by mass or more, of the blue colorant in 100% by mass of the total colorants.
  • the content of the blue colorant is, for example, 5% by mass or more and 95% by mass or less, preferably 10% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, in 100% by mass of the total of the blue colorant and the violet colorant.
  • the colorant (A) preferably contains at least one yellow colorant, more preferably contains at least one yellow pigment, and even more preferably contains two or more yellow pigments.
  • the yellow pigment at least one selected from the group consisting of C.I. Pigment Yellow 129, 138, 139, 150, and 185 is preferable, and at least one selected from the group consisting of C.I. Pigment Yellow 138, 139, 150, and 185 is more preferable.
  • the colorant (A) preferably contains a yellow colorant in an amount of, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and especially 100% by mass, based on 100% by mass of all colorants.
  • a colorant-containing liquid containing the colorant (A) and the solvent (E) may be prepared in advance, and then the colorant-containing liquid may be used to prepare the colored curable resin composition.
  • the colorant (A) is not soluble in the solvent (E), for example when the colorant (A) contains a pigment (A2)
  • the colorant-containing liquid can be prepared by dispersing the colorant (A) in the solvent (E) and mixing.
  • the colorant-containing liquid may contain a part or all of the solvent (E) contained in the colored curable resin composition.
  • the solid content in the colorant-containing liquid is less than 100% by mass, preferably 1% by mass to 80% by mass, more preferably 2% by mass to 70% by mass, and even more preferably 5% by mass to 65% by mass, based on the total amount of the colorant-containing liquid.
  • the content of colorant (A) in the colorant-containing liquid is less than 100% by mass, preferably 0.5% by mass to 80% by mass, more preferably 1% by mass to 70% by mass, and even more preferably 2.5% by mass to 65% by mass, based on the total amount of solids in the colorant-containing liquid.
  • the colorant (A) may be subjected to a rosin treatment, a surface treatment using a derivative having an acidic or basic group introduced therein, a grafting treatment to the surface of the colorant (A) using a polymer compound, a micronization treatment using a sulfuric acid micronization method or a salt milling method, a washing treatment using an organic solvent or water to remove impurities, a removal treatment using an ion exchange method for ionic impurities, etc. It is preferable that the particle size of the colorant (A) is approximately uniform.
  • the colorant (A) can be made to be uniformly dispersed in the solution by adding a dispersant and carrying out a dispersion treatment.
  • a dispersant When using a combination of two or more types of colorant (A), each may be dispersed alone, or multiple types may be mixed and dispersed.
  • dispersant examples include surfactants, which may be cationic, anionic, nonionic, or amphoteric. Specific examples include polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more.
  • examples of the dispersant when expressed by trade name, include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWRENE (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and BYK (registered trademark) (manufactured by BYK-Chemie Co.,
  • a resin (B) described later preferably resin [K1], more preferably 3,4-epoxytricyclo[5.2.1.0 2.6 ]decyl acrylate/(meth)acrylic acid copolymer
  • the dispersant preferably contains the above-mentioned acrylic dispersant and resin (B), and preferably does not contain a copper phthalocyanine derivative.
  • the amount of the dispersant (solid content) used is usually 1 part by mass to 10,000 parts by mass, preferably 5 parts by mass to 5,000 parts by mass, more preferably 10 parts by mass to 1,000 parts by mass, and even more preferably 15 parts by mass to 800 parts by mass, per 100 parts by mass of colorant (A) in the colorant-containing liquid.
  • a colorant-containing liquid hereinafter sometimes referred to as a colorant dispersion or pigment dispersion
  • the colorant-containing liquid may already contain a part or all, preferably a part, of the resin (B) contained in the colored curable resin composition.
  • the resin (B) By including the resin (B) in advance, the dispersion stability of the colorant-containing liquid can be further improved.
  • the content of resin (B) is, for example, 10 parts by mass or more and 10,000 parts by mass or less, preferably 20 parts by mass or more and 5,000 parts by mass or less, and more preferably 25 parts by mass or more and 2,500 parts by mass or less, relative to 100 parts by mass of colorant (A) in the colorant-containing liquid.
  • the content of the colorant (A) is preferably 1% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, even more preferably 15% by mass or more and 65% by mass or less, and even more preferably 18% by mass or more and 50% by mass or less, based on the total amount of solids in the colored curable resin composition.
  • the content of the colorant (A) is within the above range, the color density when made into a color filter is sufficient, and the necessary amount of the resin (B) can be contained in the composition, so that a pattern with sufficient mechanical strength can be formed, which is preferable.
  • the content of the colorant (A) is particularly preferably more than 36% by mass and not more than 90% by mass, and most preferably 38% by mass or more and 85% by mass or less, based on the total amount of solids in the colored curable resin composition.
  • the content of the colorant (A) is in the above range, the color of the color filter can be darkened.
  • the "total amount of solids" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition.
  • the total amount of solids and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.
  • Resin (B) is not particularly limited, but is preferably an alkali-soluble resin.
  • resin (B) include the following resins [K1] to [K6], and it is preferably at least one selected from resins [K1] to [K6].
  • Resin [K1] a copolymer having a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as "(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)”) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
  • Resin [K2] a copolymer having a structural unit derived from the (a), a structural unit derived from the (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, may be referred to as "(c)”);
  • Resin [K3] a copolymer having a structural unit derived from the (a) and a structural unit derived from
  • (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and 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 a carboxy group, 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]h
  • (b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond.
  • (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
  • (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.
  • Examples of (b) include 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 sometimes referred to as "(b2)”), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)”), etc.
  • 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 sometimes referred to as "(b2)
  • Examples of (b1) include monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)”) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)”) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.
  • (b1-1) includes glycidyl (meth)acrylate, ⁇ -methyl glycidyl (meth)acrylate, ⁇ -ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, ⁇ -methyl-o-vinylbenzyl glycidyl ether, ⁇ -methyl-m-vinylbenzyl glycidyl ether, ⁇ -methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl Examples include 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene
  • (b1-2) includes vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 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 (I) and compounds represented by formula (II).
  • 1,2-epoxy-4-vinylcyclohexane e.g., Celloxide 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
  • R a and R b 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 hydroxy group.
  • Xa and Xb each represent a single bond, *-R c -, *-R c -O-, *-R c -S- or *-R c -NH-.
  • Rc represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.
  • alkyl group having 1 to 4 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
  • Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group 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, and a 4-hydroxybutyl group.
  • R a and R b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.
  • alkanediyl group examples 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, and a hexane-1,6-diyl group.
  • Xa and Xb are preferably a single bond, a methylene group, an ethylene group, *-CH 2 -O-, and *-CH 2 CH 2 -O-, and more preferably a single bond or *-CH 2 CH 2 -O- (* represents a bond to O).
  • the compound represented by formula (I) includes compounds represented by any of formulas (I-1) to (I-15). Among them, compounds represented by formulas (I-1), (I-3), (I-5), (I-7), (I-9) or (I-11) to (I-15) are preferred, and compounds represented by formulas (I-1), (I-7), (I-9) or (I-15) are more preferred.
  • the compound represented by formula (II) may be any of the compounds represented by formulas (II-1) to (II-15). Among them, compounds represented by formulas (II-1), (II-3), (II-5), (II-7), (II-9) or (II-11) to (II-15) are preferred, and compounds represented by formulas (II-1), (II-7), (II-9) or (II-15) are more preferred.
  • the compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more kinds.
  • the content ratio thereof [compound represented by formula (I): compound represented by formula (II)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.
  • (b2) is a monomer having an oxetanyl group and a (meth)acryloyloxy group.
  • Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, and the like.
  • (b3) a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable.
  • Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.
  • (b1) is preferable since it can improve the reliability of the heat resistance, chemical resistance, etc. of the obtained color filter. Furthermore, (b1-2) is more preferable since the storage stability of the colored curable resin composition is excellent.
  • Examples of (c) include (meth)acrylic acid ester monomers, unsaturated carboxylates such as unsaturated dicarboxylates, and vinyl monomers having an unsaturated aliphatic hydrocarbon ring, an unsaturated heterocycle, or an aromatic ring.
  • Examples of the (meth)acrylic acid ester monomer include (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group, such as 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, and cyclopentyl (meth)acrylate (preferably, C 1-10 alkyl (meth)acrylate); (meth)acrylic acid esters having a linear or branched aliphatic unsaturated hydrocarbon group, such as allyl (meth)acrylate and propargyl (meth)acrylate; (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, such as
  • C 1-10 alkyl (meth)acrylates such as methyl methacrylate and 2-ethylhexyl acrylate;
  • (meth)acrylic acid esters having a cyclic saturated hydrocarbon group such as tricyclo[5.2.1.0 2,6 ]decan-8-yl(meth)acrylate;
  • (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group such as tricyclo[5.2.1.0 2,6 ]decene-8-yl (meth)acrylate;
  • vinyl monomers having an unsaturated aliphatic hydrocarbon ring examples include bicyclo[2.2.1]hept-2-ene (also called 2-norbornene), 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'-hydroxy 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6
  • vinyl monomers having an unsaturated heterocycle include dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide.
  • dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimid
  • vinyl monomers having an aromatic ring examples include styrene-based monomers such as styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.
  • Other vinyl monomers include nitrile group-containing monomers such as acrylonitrile and methacrylonitrile; Halogen atom-containing monomers such as vinyl chloride and vinylidene chloride; Examples of the monomer include acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
  • styrene-based monomers such as styrene and vinyltoluene
  • dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide
  • bicyclo unsaturated compounds such as bicyclo[2.2.1]hept-2-ene (also called 2-norbornene) are preferred.
  • the structural unit obtained by adding (b) to a structural unit derived from (a) refers to a unit formed by bonding (b) by addition to a structural unit derived from (a) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (b).
  • (a) may be any of the above-mentioned examples, and (b) may also be any of the above-mentioned examples.
  • an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable.
  • a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable.
  • the structural unit obtained by adding (a) to a structural unit derived from (b) refers to a unit formed by bonding (a) by addition to a structural unit derived from (b) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (a).
  • (b) may be any of the above-mentioned examples, and (a) may also be any of the above-mentioned examples.
  • a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable.
  • an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable.
  • the structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride refers to a structural unit obtained by half-esterification of a carboxylic anhydride to a hydroxyl group generated by adding (a) to a structural unit derived from (b) constituting the main chain of the copolymer, and has a pendant carboxyl group derived from the carboxylic anhydride and a pendant unsaturated group derived from (a).
  • (b) may be any of the above-mentioned examples, and (a) may also be any of the above-mentioned examples.
  • a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable.
  • an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable.
  • carboxylic acid anhydride examples include saturated aliphatic polycarboxylic acid anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adipic anhydride; unsaturated aliphatic polycarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; aromatic polycarboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride; and alicyclic polycarboxylic acid anhydrides such as 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.
  • saturated aliphatic polycarboxylic acid anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adip
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K1] is as follows: Structural units derived from (a): 2 to 60 mol% Structural units derived from (b): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol % Structural units derived from (b): 50 to 90 mol% It is more preferable that: It is also preferred that the copolymer contains substantially no structural units derived from (c).
  • the total of the structural units derived from (a) and the structural units derived from (b) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K1].
  • the ratio of the structural units of the resin [K1] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and solvent resistance of the obtained color filter.
  • Resin [K1] can be produced, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis” (written by Otsu Takayuki, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the references cited in said literature.
  • Specific examples include a method in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and the atmosphere is deoxygenated, for example by replacing oxygen with nitrogen, and the mixture is heated and kept warm while stirring.
  • the polymerization initiator and solvent used here are not particularly limited, and those commonly used in the relevant field can be used.
  • polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.), and the solvent may be any that dissolves each monomer, such as the solvent (E) described below for the colored curable resin composition of the present invention.
  • the copolymer obtained may be used as it is in the solution after the reaction, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.
  • the solvent contained in the colored curable resin composition of the present invention as the solvent during this polymerization, the solution after the reaction can be used as it is in the preparation of the colored curable resin composition of the present invention, and the manufacturing process of the colored curable resin composition of the present invention can be simplified.
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K2] is as follows: Structural units derived from (a): 2 to 45 mol% Structural units derived from (b): 2 to 95 mol% Structural units derived from (c): 1 to 65 mol% It is preferred that Structural units derived from (a): 5 to 40 mol% Structural units derived from (b): 5 to 80 mol% Structural units derived from (c): 5 to 60 mol% It is more preferable that Structural units derived from (a): 10 to 30 mol % Structural units derived from (b): 10 to 70 mol% Structural units derived from (c): 10 to 40 mol% It is even more preferred that: The total of the structural units derived from (a), the structural units derived from (b), and the structural units derived from (c) is, for example, 90 mol
  • the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and the obtained color filter tends to have excellent solvent resistance, heat resistance, and mechanical strength.
  • (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid.
  • a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferred, and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized is more preferred.
  • (c)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, and dicarbonyl imide derivatives are preferred.
  • Resin [K2] can be produced, for example, in the same manner as described above for producing resin [K1].
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K3] is as follows: Structural units derived from (a): 2 to 60 mol% Structural units derived from (c): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol % Structural units derived from (c): 50 to 90 mol% It is more preferable that Structural units derived from (a): 35 to 45 mol% Structural units derived from (c): 55 to 65 mol% It is even more preferred that: It is also preferred that the copolymer is substantially free of structural units derived from (b).
  • the total of the structural units derived from (a) and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all the structural units constituting the resin [K3].
  • Resin [K3] (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid, and (c) is preferably a (meth)acrylic acid ester having an aromatic ring.
  • Resin [K3] can be produced, for example, in the same manner as described above for producing resin [K1].
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K4] is as follows: Structural units derived from (a) (without (b) added): 1 to 60 mol% Structural units obtained by adding (b) to a structural unit derived from (a): 1 to 50 mol % Structural units derived from (c): 30 to 90 mol% It is preferred that Structural units derived from (a) (without (b) added): 5 to 50 mol % Structural units obtained by adding (b) to a structural unit derived from (a): 5 to 40 mol% Structural units derived from (c): 35 to 80 mol% It is more preferable that Structural units derived from (a) (without (b) added): 10 to 40 mol% Structural units obtained by adding (b) to a structural unit derived from (a): 10 to 25 mol% Structural units derived from (
  • a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.
  • a structural unit in which (b) is added to a structural unit derived from (a) a structural unit in which a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is added to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.
  • one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, bicyclo unsaturated compounds, and styrene-based monomers are preferred, and two or more types are more preferred.
  • (c) has two types of structural units derived from it, it is preferable to select two types from unsaturated carboxylic acid esters such as (meth)acrylic acid esters, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and (meth)acrylic acid esters having an aromatic ring, and to select two or more types from bicyclo unsaturated compounds and vinyl monomers such as styrene-based monomers.
  • unsaturated carboxylic acid esters such as (meth)acrylic acid esters, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and (meth)acrylic acid esters having an aromatic ring
  • bicyclo unsaturated compounds and vinyl monomers such as styrene-based monomers.
  • Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and/or carboxylic acid anhydride contained in (a).
  • a copolymer of (a) and (c) is produced in the same manner as described for the production method of resin [K1].
  • the ratio of the structural units derived from each is preferably the same as that described for resin [K3].
  • a part 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 contained in (b).
  • the atmosphere in the flask is replaced with air instead of nitrogen, and (b) a reaction catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc.
  • the amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By using this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good.
  • 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), and 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 charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.
  • the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K5] is as follows: Structural units derived from (b) ((a) is not added): 0 to 30 mol% Structural units obtained by adding (a) to a structural unit derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b) ((a) is not added): 0 to 10 mol % Structural units obtained by adding (a) to a structural unit derived from (b): 15 to 90 mol% Structural units derived from (c): 10 to 85 mol% It is more preferable that Structural units derived from (b) ((a) is not added): 0 to 5 mol% Structural units obtained by adding (a) to a structural unit derived from (b): 20 to 80 mol% Structural
  • a structural unit derived from (b) (without (a) added) a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred.
  • a structural unit in which (a) is added to a structural unit derived from (b) a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred.
  • one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group are preferred, and two or more types are more preferred.
  • Resin [K5] is produced in the first step by the same method as the above-mentioned method for producing resin [K1] to obtain a copolymer of (b) and (c).
  • the obtained copolymer may be used as a solution after the reaction as it is, a concentrated or diluted solution, or a solid (powder) obtained by a method such as reprecipitation.
  • the ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are, respectively, Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:
  • resin [K5] can be obtained by reacting a cyclic ether derived from (b) contained in a copolymer of (b) and (c) with a carboxylic acid or carboxylic anhydride contained in (a).
  • the amount of (a) to be reacted with the copolymer is preferably 5 to 100 moles per 100 moles of (b). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) for use in resin [K5], and (b1-1) is more preferred.
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K5'] is as follows: Structural units derived from (a) (without (b) added): 0 to 30 mol % Structural units obtained by adding (b) to a structural unit derived from (a): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (a) (without (b) added): 0 to 10 mol % Structural units obtained by adding (b) to a structural unit derived from (a): 15 to 90 mol% Structural units derived from (c): 10 to 85 mol% It is more preferable that Structural units derived from (a) (without (b) added): 0 to 5 mol % Structural units obtained by adding (b) to a structural unit derived from (a): 20 to 80 mol% Struct
  • a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.
  • a structural unit obtained by adding (b) to a structural unit derived from (a) a structural unit obtained by adding a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.
  • Resin [K5'] may be produced by referring to the production method of resin [K4] described above, and the amount of (b) used may be more than 80 mol and 100 mol or less per 100 mol of (a).
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K6] is as follows: Structural units derived from (b) ((a) is not added): 0 to 30 mol% A structural unit obtained by adding (a) to a structural unit derived from (b) (no carboxylic acid anhydride is added); 2 to 80 mol% A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride thereto: 2 to 60 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b) ((a) is not added): 0 to 10 mol% A structural unit obtained by adding (a) to a structural unit derived from (b) (no carboxylic acid anhydride is added); 5 to 70 mol% A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding
  • a structural unit derived from (b) (without (a) added a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred.
  • a structural unit in which (a) is added to a structural unit derived from (b) (without carboxylic anhydride added) a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred.
  • a structural unit in which (a) is added to a structural unit derived from (b) and a carboxylic anhydride is further added a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized and a saturated aliphatic polycarboxylic anhydride such as succinic anhydride is further added.
  • one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group are preferred, and two or more types are more preferred.
  • Resin [K6] is produced in the first step by the same method as that for producing resin [K1] described above, to obtain a copolymer of (b) and (c).
  • the copolymer obtained may be used as it is in the form of a solution after the reaction, or a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.
  • the ratio of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer is, Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:
  • the cyclic ether derived from (b) contained in the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic anhydride contained in (a).
  • the amount of (a) used is preferably 80 to 100 moles per 100 moles of (b).
  • the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic acid anhydride contained in (a) is reacted with the carboxylic acid anhydride.
  • the amount of the carboxylic acid anhydride used is preferably 0.05 to 1 mol, more preferably 0.10 to 0.8 mol, and even more preferably 0.13 to 0.7 mol, relative to 1 mol of the amount of (a) used (in other words, 1 mol of hydroxy groups generated by the use of (a)).
  • the resin (B) include resins [K1] such as 3,4-epoxycyclohexylmethyl(meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate/(meth)acrylic acid copolymer; Glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/tricyclo[5.2.1.0 2,6 ] de
  • the polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.
  • the polydispersity of the resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.1-6, and more preferably 1.2-4.
  • the acid value of resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 25 to 150 mg-KOH/g, and even more preferably 30 to 135 mg-KOH/g, calculated as solid content.
  • the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.
  • the content of resin (B) is preferably 2 to 65 mass% relative to the total amount of solids, more preferably 3 to 60 mass%, even more preferably 5 to 55 mass%, even more preferably 5 to 40 mass%, and particularly preferably 7 to 30 mass%.
  • the content of resin (B) is within the above range, a colored pattern can be formed, and the resolution and remaining film rate of the colored pattern tend to improve.
  • resin (B) a resin having an ethylenic double bond is particularly preferred from the viewpoint of further improving solvent resistance.
  • the double bond equivalent of resin (B) is, for example, 100 to 2000 g/mol, preferably 200 to 1500 g/mol, and more preferably 300 to 1300 g/mol.
  • resin (B) having an ethylenic double bond examples include any of resins [K2] to [K6], which contain at least one monomer selected from (meth)acrylic acid esters having a linear or branched aliphatic unsaturated hydrocarbon group, (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, vinyl monomers having an unsaturated aliphatic hydrocarbon ring, vinyl monomers having an unsaturated heterocycle, and vinyl monomers having an aromatic ring as monomer (c).
  • Resins [K4] to [K6] also have an ethylenic double bond derived from an additional component (preferably the monomer (a) or the monomer (b)).
  • the resin (B) those having a structural unit derived from the monomer (b), such as the resin [K1] and/or the resin [K2], are particularly preferred.
  • the resin (B) is particularly preferably any one of the resins [K2] to [K4], which contains a (meth)acrylic acid ester having an aromatic ring as the monomer (c), and in which the total of the structural units derived from the (meth)acrylic acid ester having an aromatic ring and the structural units derived from the (a) is 60 mol % or more, based on 100 mol % of all structural units.
  • 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 thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylic acid ester compounds.
  • polymerizable compounds having one ethylenically unsaturated bond examples include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-mentioned monomers (a), (b), and (c).
  • polymerizable compounds having two ethylenically unsaturated bonds examples 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.
  • the 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, ethyl Examples of the dipent
  • the weight average molecular weight of the polymerizable compound (C) is preferably 50 or more and 4,000 or less, more preferably 70 or more and 3,500 or less, even more preferably 100 or more and 3,000 or less, even more preferably 150 or more and 2,900 or less, and particularly preferably 250 or more and 1,500 or less.
  • the polymerization initiator (D) may be any compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and includes compounds represented by the following formula (I).
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a hydrocarbon group which may have a substituent.
  • n represents an integer of 0 to 4.
  • the --CH 2 -- contained in the hydrocarbon group may be replaced with --O--, --S--, --CO--, or --OCO--.
  • Examples of the hydrocarbon group represented by R1 , R2 , R3 , R4 , and R5 include saturated hydrocarbon groups having 1 to 20 carbon atoms, unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms.
  • the saturated hydrocarbon group having 1 to 20 carbon atoms includes, for example, linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.
  • the number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 18, more preferably 1 to 15, even more preferably 1 to 10, and even more preferably 1 to 8.
  • the unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms includes alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, hexadecenyl, octadecenyl, and icosenyl; alkynyl groups such as ethynyl, propynyl, hexynyl, decynyl, and icosenyl; cycloalkenyl groups such as cyclopentenyl, cyclohexenyl, and cycloheptenyl; and the like.
  • the number of carbon atoms in the unsaturated aliphatic hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and even more preferably 2 to 10.
  • the aromatic hydrocarbon group having 6 to 20 carbon atoms includes a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di(2,2-dimethylpropyl)phenyl group, a naphthyl group, a benzyl group, a phenylethyl group, a phenylbutyl group, etc.
  • the number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 15, and even more preferably 6 to 12.
  • Examples of the substituent that the hydrocarbon group represented by R 1 , R 2 , R 3 , R 4 , and R 5 may have include a halogen atom, a cyano group, and a nitro group.
  • the halogen atom is preferably a fluorine atom, a bromine atom, a chlorine atom, or an iodine atom.
  • n represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably an integer of 0 or 1, and even more preferably 0.
  • the --CH 2 -- contained in the hydrocarbon group may be replaced by --O--, --S--, --CO--, or --OCO--, provided that adjacent --CH 2 -- are not simultaneously replaced by the same type of group, and that the terminal --CH 2 -- is not replaced.
  • the hydrocarbon groups represented by R 1 , R 2 , R 3 , R 4 , and R 5 are preferably saturated hydrocarbon groups having 1 to 20 carbon atoms or unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, more preferably saturated hydrocarbon groups having 1 to 20 carbon atoms, even more preferably linear or branched saturated hydrocarbon groups having 1 to 10 carbon atoms, and even more preferably linear or branched alkyl groups having 1 to 8 carbon atoms.
  • the hydrocarbon groups represented by R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different, and are preferably different.
  • R 1 is a linear alkyl group having 1 to 8 carbon atoms
  • R 2 is a branched alkyl group having 1 to 8 carbon atoms
  • R 3 and R 4 are linear alkyl groups having 1 to 8 carbon atoms
  • R 5 is a linear or branched alkyl group having 1 to 8 carbon atoms
  • R 1 is a linear alkyl group having 1 to 6 carbon atoms
  • R 2 is a branched alkyl group having 1 to 8 carbon atoms
  • R 3 and R 4 are linear alkyl groups having 1 to 3 carbon atoms
  • R 5 is a linear or branched alkyl group having 1 to 8 carbon atoms.
  • polymerization initiators may be used.
  • examples of other polymerization initiators (D) include O-acyloxime compounds (excluding the compound represented by formula (I) and Irgacure OXE03), alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.
  • the O-acyloxime compound is a compound having a partial structure represented by formula (d-1).
  • * represents a bond.
  • O-acyloxime compounds examples 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-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6- ⁇ 2-methyl-4-(3,3-di N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl
  • IRGACURE OXE01 N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine
  • IRGACURE OXE02 N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine) (both manufactured by BASF)
  • N-1919 manufactured by ADEKA
  • the O-acyloxime compounds include N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine and N-benzoyloxy- At least one selected from the group consisting of 1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred, with N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1
  • the alkylphenone compound is a compound having a partial structure represented by formula (d-2) or a partial structure represented by formula (d-3).
  • the benzene ring may have a substituent.
  • * represents a bond.
  • Examples of compounds having the partial structure represented by formula (d-2) 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.
  • Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) may also be used.
  • Examples of the compound having a partial structure represented by formula (d-3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, ⁇ , ⁇ -diethoxyacetophenone, and benzyl dimethyl ketal.
  • the alkylphenone compound is preferably a compound having a partial structure represented by formula (d-2).
  • triazine compounds examples 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- Examples include [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
  • the acylphosphine oxide compound may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.
  • the biimidazole compound includes, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2- 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-3840
  • polymerization initiator (D) examples 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; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (especially amine), and
  • polymerization initiators that generate acid include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, as well as nitrobenzyl tosylates and benzoin tosylates.
  • onium salts such as 4-hydroxyphenyldimethylsulfonium p-
  • a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound is preferred, a polymerization initiator containing an O-acyloxime compound and/or a biimidazole compound is more preferred, and a polymerization initiator containing an O-acyloxime compound is even more preferred.
  • the content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).
  • the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the optical filter.
  • the contents of the resin (B), the polymerizable compound (C), and the polymerization initiator (D) are preferably 10 mass% or more and less than 46 mass%, more preferably 12 mass% or more and 44 mass% or less, even more preferably 14 mass% or more and 42 mass% or less, and still more preferably 16 mass% or more and 40 mass% or less, in the total amount of the solid contents of the colored curable resin composition.
  • the contents of the resin (B), the polymerizable compound (C), and the polymerization initiator (D) satisfy the above ranges, the remaining film rate of the color filter can be improved even if the amount of the curable component is reduced.
  • the polymerization initiation aid (D1) is a compound used to promote the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D), or a sensitizer. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).
  • Examples of the polymerization initiator aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
  • Amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, with 4,4'-bis(diethylamino)benzophenone being preferred.
  • Commercially available amine compounds such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.
  • 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.
  • Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
  • 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.
  • the 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, relative to 100 parts by mass of the total amount of all the resins (B) and the polymerizable compounds (C) contained in the colored curable resin composition.
  • the solvent (E) is not particularly limited, and any solvent commonly used in the relevant field can be used.
  • the solvent (E) include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. Two or more of these solvents may be used in combination. Two or more of these solvents may be used in combination. Two or more of these solvents may be used in combination.
  • 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 gamma-butyrolactone.
  • 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, phenetole, and methylanisole.
  • 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-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, Examples of such ethers include ethyl
  • 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.
  • Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
  • Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, etc.
  • Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
  • propylene glycol monomethyl ether acetate propylene glycol monomethyl ether, ethyl lactate and cyclohexanone are preferred, and propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are more preferred.
  • the content of the solvent (E) is usually 99.99% by mass or less, preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 97% by mass or less, even more preferably 70% by mass or more and 96% by mass or less, and even more preferably 73% by mass or more and 95% by mass or less, based on the total amount of the colored curable resin composition.
  • the total amount of solids in the colored curable resin composition is usually 0.01% by mass or more, preferably 1% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 50% by mass or less, even more preferably 4% by mass or more and 30% by mass or less, and even more preferably 5% by mass or more and 27% by mass or less.
  • the content of the solvent (E) is within the above range, the flatness during application is good, and the color density is not insufficient when a color filter is formed, so that the display characteristics tend to be good.
  • the colored curable resin composition of the present invention may contain a thiol compound (T).
  • the thiol compound (T) is a compound having a sulfanyl group (-SH) in the molecule.
  • Examples of compounds having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-di
  • Compounds with two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediol bis(3-sulfanylpropionate), butanediol bis(3-sulfanyl acetate), ethylene glycol bis(3-sulfanyl acetate), trimethylolpropane tris(3-sulfanyl acetate), butanediol bis(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanyl acetate), Examples include propane tris(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanyl acetate), pentaerythritol tetrakis(3-sulfanylpropionate), pentaerythritol tetrakis(3
  • the content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the polymerization initiator (D). If the content of the thiol compound (T) is within this range, the sensitivity tends to be high and the developability tends to be good.
  • Leveling Agent (F) examples include silicone surfactants, fluorine-based surfactants, and silicone surfactants having fluorine atoms, which may have a polymerizable group in the side chain.
  • silicone surfactants include surfactants having a siloxane bond in the molecule.
  • Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (product names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and 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).
  • Fluorosurfactants include surfactants having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by AGC Corporation), and E5844 (manufactured by Daikin Fine Chemicals Research Institute Ltd.).
  • Fluorad registered trademark
  • FC430 and FC431 manufactured by Sumitomo 3M Limited
  • Megafac registered trademark
  • F142D F171, F172, F17
  • silicone surfactants containing fluorine atoms include surfactants that have siloxane bonds and fluorocarbon chains in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).
  • the content of the leveling agent (F) 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, based on the total amount of the colored curable resin composition. Note that 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.
  • the colored curable resin composition may contain additives known in the technical field, such as a filler, another polymer compound, an adhesion promoter, a quencher, an antioxidant, a light stabilizer, and a chain transfer agent, as necessary.
  • adhesion promoters examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfur
  • the silane examples include anylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethy
  • the colored curable resin composition can be prepared by mixing the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and optionally the polymerization initiator aid (D1), the solvent (E), the leveling agent (F), and other components.
  • the mixing can be carried out using known or conventional equipment and conditions.
  • the colorant (A) may be used as a colorant-containing liquid obtained by mixing with a part or all of the solvent (E) in advance and dispersing using a bead mill or the like until the average particle size becomes about 0.2 ⁇ m or less, and it is preferable to use it as a colorant-containing liquid.
  • the dispersant and a part or all of the resin (B) may be blended as necessary.
  • the remaining components are mixed into the colorant-containing liquid obtained in this way to a predetermined concentration, whereby the desired colored curable resin composition can be prepared.
  • the dye when a dye is contained as the colorant (A), the dye may be dissolved in advance in a part or all of the solvent (E) to prepare a solution.
  • the solution is preferably filtered through a filter having a pore size of about 0.01 to 1 ⁇ m.
  • a color filter can be formed from the colored curable resin composition of the present invention.
  • methods for producing a colored pattern include a photolithography method, an inkjet method, and a printing method.
  • the photolithography method is preferred.
  • the photolithography method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed.
  • a colored coating film which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and/or not developing.
  • the colored pattern or colored coating film thus formed is the color filter of the present invention.
  • the film thickness of the color filter to be produced is not particularly limited and can be adjusted appropriately depending on the purpose and application, and is, for example, 30 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 6 ⁇ m or less, even more preferably 4.5 ⁇ m or less, and is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, even more preferably 0.3 ⁇ m or more.
  • the substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass with a silica-coated surface; a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate; silicon; or a substrate on which aluminum, silver, or a thin film of a silver/copper/palladium alloy is formed. On these substrates, other color filter layers, resin layers, transistors, circuits, etc. may be formed. A silicon substrate treated with HMDS (hexamethyldisilazane) may also be used.
  • HMDS hexamethyldisilazane
  • each color pixel by photolithography can be carried out using known or conventional devices and conditions.
  • the pixel can be produced as follows. First, the colored curable resin composition is applied onto a substrate, and then dried by heating and drying (pre-baking) and/or drying under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth colored composition layer. Examples of the application method include spin coating, slit coating, and slit and spin coating.
  • the temperature at which the heat drying is performed is preferably 30° C. or higher and 120° C. or lower, and more preferably 50° C. or higher and 110° C. or lower.
  • the heating time is preferably 10 seconds or higher and 60 minutes or lower, and more preferably 30 seconds or higher and 30 minutes or lower.
  • the thickness of the colored composition layer is not particularly limited and may be appropriately selected depending on the thickness of the intended color filter.
  • the colored composition layer is then exposed through a photomask to form the desired colored pattern.
  • a photomask There are no particular limitations on the pattern on the photomask, and a pattern appropriate for the intended application is used.
  • an exposure device such as a mask aligner or stepper, since it is possible to uniformly irradiate the entire exposed surface with parallel light and to accurately align the photomask with the substrate on which the colored composition layer is formed.
  • exposure can be performed without using a photomask.
  • the light source used for exposure is preferably a light source that generates light with a wavelength of 250 nm or more and 450 nm or less.
  • light less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm may 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.
  • the colored composition layer after exposure is brought into contact with a developer and developed to form a colored pattern on the substrate.
  • the unexposed portion of the colored composition layer is dissolved in the developer and removed by development.
  • the developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide.
  • the concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less.
  • the developer may contain a surfactant.
  • the development method may be any of a paddle method, a dipping method, and a spray method.
  • the substrate may be tilted at any angle during development. After development, the substrate is preferably washed with water.
  • the post-baking temperature is preferably from 80° C. to 250° C., and more preferably from 100° C. to 245° C.
  • the post-baking time is preferably from 1 minute to 120 minutes, and more preferably from 2 minutes to 30 minutes.
  • the colored pattern and colored coating film thus obtained are useful as a color filter.
  • the colored coating film is preferably a colored coating film that, after immersion in propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) at a temperature of 23° C. for 5 minutes, has a small color difference ( ⁇ E*ab) before and after immersion.
  • the color difference ( ⁇ E*ab) of the colored coating film to PGME is preferably 5.5 or less, more preferably 5.0 or less, even more preferably 4.5 or less, and even more preferably 4.0 or less.
  • the color filter is useful as a color filter for use in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.), solid-state imaging devices, and the like.
  • Synthesis Example 5 Preparation of Resin (B-1) 276.8 parts of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 120°C.
  • a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate, and 12.3 parts of dicyclopentanyl methacrylate, to which 35.3 parts of t-butylperoxy-2-ethylhexanoate (polymerization initiator) had been added, was dropped into the flask from the dropping funnel over 2 hours. After the dropwise addition was completed, the mixture was stirred for another 30 minutes at 120°C to carry out a copolymerization reaction, and an addition copolymer was produced.
  • Synthesis Example 6 Preparation of Resin (B-2) A flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel was filled with nitrogen at 0.02 L/min to create a nitrogen atmosphere, and 268 parts of ethyl lactate was added and heated to 70° C. with stirring.
  • Synthesis Example 7 Preparation of Dispersion Resin A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring.
  • Resin (B-3) Lipoxy (registered trademark) SPC-2000, manufactured by Resonac Co., Ltd.
  • Synthesis Example 9 Preparation of Resin (B-4) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 241 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 130°C.
  • Synthesis Example 10 Preparation of Resin (B-5) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 258 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 120°C.
  • a monomer mixture consisting of 89.5 parts of 2-ethylhexyl acrylate, 180.0 parts of glycidyl methacrylate, and 11.9 parts of dicyclopentanyl methacrylate, to which 10.9 parts of t-butylperoxy-2-ethylhexanoate had been added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes to carry out a copolymerization reaction.
  • Synthesis Example 11 Preparation of Resin (B-6) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 257 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 120°C.
  • a monomer mixture consisting of 90.5 parts of 2-ethylhexyl acrylate, 181.1 parts of glycidyl methacrylate, and 12.0 parts of dicyclopentanyl methacrylate, to which 6.8 parts of t-butylperoxy-2-ethylhexanoate had been added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes to carry out a copolymerization reaction.
  • Synthesis Example 12 Preparation of Resin (B-7) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 178 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 100°C.
  • a monomer mixture consisting of 115.2 parts of 2-ethylhexyl acrylate, 86.0 parts of glycidyl methacrylate, 72.7 parts of methyl methacrylate, and 13.3 parts of dicyclopentanyl methacrylate, to which 47.1 parts of dimethyl 2,2'-azobis(2-methylpropionate) (polymerization initiator) was added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred at 100°C for an additional 30 minutes to carry out a copolymerization reaction.
  • Synthesis Example 13 Preparation of Resin (B-8) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 349 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 120°C. Next, a monomer mixture consisting of 169.2 parts of benzyl methacrylate, 103.3 parts of methacrylic acid, and 52.9 parts of dicyclopentanyl methacrylate, to which 23.4 parts of t-butylperoxy-2-ethylhexanoate had been added, was dropped into the flask from the dropping funnel over a period of 2 hours.
  • Synthesis Example 14 Preparation of Resin (B-9) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 492.4 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 90°C. Next, a monomer mixture consisting of 208.1 parts of vinyltoluene, 62.1 parts of acrylic acid, and 13.0 parts of norbornene, to which 32.6 parts of dimethyl 2,2'-azobis(2-methylpropionate) and 5.7 parts of thioglycolic acid were added, was dropped into the flask from the dropping funnel over a period of 2 hours.
  • Synthesis Example 15 Preparation of Resin (B-10) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 547 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 120°C. Next, a monomer mixture consisting of 272.0 parts of benzyl methacrylate and 73.8 parts of methacrylic acid, to which 4.2 parts of t-butylperoxy-2-ethylhexanoate had been added, was dropped into the flask from the dropping funnel over a period of 2 hours.
  • Synthesis Example 16 Preparation of Resin (B-11) A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 340 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring.
  • Synthesis Example 17 Preparation of Resin (B-12) An appropriate amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 256 parts of propylene glycol monomethyl ether acetate was added and heated to 80° C. with stirring.
  • copolymer (resin (B-12)) solution having a Brookfield viscosity (23°C) of 51 mPas and a solid content of 36.0%.
  • the weight average molecular weight Mw of the produced copolymer was 11,000 and the dispersity was 1.98.
  • the polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn of the resins obtained in the above Synthesis Examples were measured using a GPC method under the following conditions.
  • Apparatus HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: Tetrahydrofuran Flow rate: 1.0 mL/min Solids concentration of test solution: 0.001 to 0.01% by mass Injection volume: 50 ⁇ L Detector: RI
  • Calibration standard material TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (Manufactured by Tosoh Corporation) The ratio of the weight average molecular weight and the number average molecular weight (Mw/Mn) calculated in terms of polystyrene obtained above was taken as the dispersity.
  • Example 1 and Comparative Example 1 (1) Preparation of Colored Curable Resin Composition
  • the components shown in Table 1 were mixed in the amounts shown in Table 1 to obtain colored curable resin compositions.
  • propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 23.5 mass%.
  • the unit of the amount of each component in Table 1 is "parts by mass", and the amounts of the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), silane coupling agent, and leveling agent (F) are calculated as solid content.
  • the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), silane coupling agent as an adhesion promoter, and leveling agent (F) used are as follows:
  • Polymerizable compound (C): Polymerizable compound (C-1) (manufactured by Shin-Nakamura Chemical Co., Ltd., product name "NK Ester A-TMPT” trimethylolpropane triacrylate)
  • Polymerization initiator (D) is a compound represented by the following formula (manufactured by BASF Ltd., product name "Irgacure OXE03")
  • Polymerization initiator (D) Polymerization initiator (D-2) Compound represented by the following formula
  • Silane coupling agent Compound represented by the following formula, 3-methacryloxypropyltrimethoxysilane (trade name "KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Leveling agent Polyether modified silicone oil (product name "Toray Silicone SH8400” manufactured by Toray Dow Corning Co., Ltd.)
  • each of the colored curable resin compositions shown in Table 1 was applied by spin coating so that the film thickness after post-baking was 1.2 ⁇ m, and then a colored composition layer was obtained.
  • the substrate on which the colored composition layer was formed was irradiated with light at an exposure dose of 200 mJ/cm 2 (based on 365 nm) using an exposure machine (NSR-1755i7A; manufactured by Nikon Corporation).
  • NSR-1755i7A an exposure machine
  • the colored composition layer after light irradiation was immersed and developed in an aqueous developer containing tetramethylammonium hydroxide at 23 ° C.
  • the film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Shinku Gijutsu Co., Ltd.), and it was confirmed to be 1.2 ⁇ m.
  • Example 2 and Comparative Example 2 (1) Preparation of Colored Curable Resin Composition
  • the components shown in Table 2 were mixed in the amounts shown in Table 2 to obtain colored curable resin compositions.
  • propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 14.0%.
  • the unit of the amount of each component in Table 2 is "parts by mass", and the amounts of the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), and leveling agent (F) are calculated as solid content.
  • the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), and leveling agent (F) used are as follows:
  • Polymerizable compound (C) Polymerizable compound (C-2) (manufactured by Toagosei Co., Ltd., product name "Aronix (registered trademark) M-930" glycerin triacrylate)
  • Polymerization initiator (D) is a compound represented by the following formula (manufactured by BASF Ltd., product name "Irgacure OXE03")
  • Polymerization initiator (D) is a compound represented by the following formula
  • Leveling agent Polyether modified silicone oil (product name "Toray Silicone SH8400” manufactured by Toray Dow Corning Co., Ltd.)
  • each colored curable resin composition described in Table 2 was applied by spin coating so that the film thickness after post-baking was 2.0 ⁇ m, and then pre-baked at 70 ° C. for 2 minutes to form a composition layer. After cooling, the substrate on which the composition layer was formed and a quartz glass photomask were spaced apart from each other by 50 ⁇ m, and the substrate was irradiated with light at an exposure dose of 100 mJ / cm 2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation).
  • a photomask on which a 10 ⁇ m line and space pattern was formed was used.
  • the composition layer after light irradiation was developed by immersing it in an aqueous solution containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, washed with water, and then post-baked in an oven at 85 ° C. for 30 minutes to obtain a pattern.
  • the film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Shinku Gijutsu Co., Ltd.) and was confirmed to be 2.0 ⁇ m.
  • Example 3 and Comparative Example 3> Preparation of Colored Curable Resin Compositions Colored curable resin compositions were obtained by mixing the components in the amounts shown in Table 5. In preparing the colored curable resin compositions, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 14.0%. The unit of the amount of each component in Table 5 is "parts by mass", and the amounts of the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), and leveling agent (F) are calculated as solid content.
  • the components (A-3), (B-X), (B-1), (C-1), (D-1), and (D-2) were the same as those described above, and the leveling agent (F) used was a polyether-modified silicone oil (manufactured by Dow Corning Toray Co., Ltd. under the trade name "Toray Silicone SH8400").
  • the amounts of the acrylic pigment dispersant and dispersing resin in Table 5 are shown as amounts derived from the colored dispersion (A-3).
  • each colored curable resin composition described in Table 5 was applied by spin coating so that the film thickness after post-baking was 2.0 ⁇ m, and then pre-baked at 70 ° C. for 2 minutes to form a composition layer.
  • the substrate on which the composition layer was formed and a quartz glass photomask were spaced apart from each other by 50 ⁇ m, and the substrate was irradiated with light at an exposure dose of 100 mJ / cm 2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; Topcon Corporation). Note that a photomask on which a 10 ⁇ m line and space pattern was formed was used.
  • composition layer after light irradiation was developed by immersing it in an aqueous solution containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, washed with water, and then post-baked in an oven at 85 ° C. for 30 minutes to obtain a pattern.
  • the film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Shinku Gijutsu Co., Ltd.) and was confirmed to be 2.0 ⁇ m.
  • the pattern obtained by pattern preparation 3 was immersed in propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) at 23° C. for 5 minutes and rinsed with running water for 10 seconds to carry out a solvent resistance test.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • Spectroscopic measurements were performed using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and evaluation was performed based on color difference and the film thickness retention (film thickness change) before and after the solvent resistance test was measured.
  • the film thickness retention (film thickness change) refers to the ratio of the film thickness after immersion to the film thickness before immersion. The results are shown in Table 6.
  • Colored curable resin compositions were obtained by mixing the components in the amounts shown in Table 7.
  • propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 14.0%.
  • the unit of the amount of each component in Table 7 is "parts by mass", and the amounts of the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), and leveling agent (F) are calculated as solid content.
  • the components (A-4), (B-X), (B-1), (B-3) to (B-12), (C-1), and (D-2) were the same as those described above, and the leveling agent (F) used was a polyether-modified silicone oil (manufactured by Dow Corning Toray Co., Ltd. under the trade name "Toray Silicone SH8400").
  • the amounts of the acrylic pigment dispersant and dispersing resin in Table 7 are shown as amounts derived from the colored dispersion (A-4).
  • each colored curable resin composition described in Table 7 was applied by spin coating so that the film thickness after post-baking was 2.0 ⁇ m, and then pre-baked at 70 ° C. for 2 minutes to form a composition layer. After cooling, the substrate on which the composition layer was formed and a quartz glass photomask were spaced apart from each other by 50 ⁇ m, and the substrate was irradiated with light at an exposure dose of 100 mJ / cm 2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation).
  • a photomask on which a 10 ⁇ m line and space pattern was formed was used.
  • the composition layer after light irradiation was developed by immersing it in an aqueous solution containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, washed with water, and then post-baked in an oven at 85 ° C. for 30 minutes to obtain a pattern.
  • the film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Shinku Gijutsu Co., Ltd.) and was confirmed to be 2.0 ⁇ m.
  • the pattern obtained by pattern preparation 4 was immersed in propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) at 23° C. for 5 minutes and rinsed with running water for 10 seconds to carry out a solvent resistance test.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • Spectroscopic measurements were taken using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and evaluation was performed based on color difference and the film thickness retention (film thickness change) before and after the solvent resistance test was measured.
  • the film thickness retention (film thickness change) refers to the ratio of the film thickness after immersion to the film thickness before immersion. The results are shown in Table 8.

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  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Optical Filters (AREA)

Abstract

The present invention addresses the problem of providing a colored curable resin composition with which it is possible to form a color filter that exhibits superior solvent resistance.　The present invention relates to a colored curable resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator, the polymerization initiator including a compound expressed by formula (I). (In the formula, R1, R2, R3, R4, and R5 each independently represent a hydrocarbon group that optionally has a substituent. n represents an integer of 0 to 4. -CH2- included in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -OCO-.)

Description

着色硬化性樹脂組成物、カラーフィルタ、表示装置、及び固体撮像素子Colored curable resin composition, color filter, display device, and solid-state image pickup device
　本発明は、着色硬化性樹脂組成物、カラーフィルタ、表示装置、及び固体撮像素子に関するものである。 The present invention relates to a colored curable resin composition, a color filter, a display device, and a solid-state imaging device.
　液晶表示装置、エレクトロルミネッセンス表示装置、及びプラズマディスプレイ等の表示装置やＣＣＤやＣＭＯＳセンサ等の固体撮像素子に使用されるカラーフィルタは、着色硬化性樹脂組成物から製造される。この着色硬化性樹脂組成物には、所定の重合開始剤等が使用されることが知られている（特許文献１）。 Color filters used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, as well as solid-state imaging devices such as CCD and CMOS sensors, are manufactured from colored curable resin compositions. It is known that a specific polymerization initiator is used in this colored curable resin composition (Patent Document 1).
国際公開第２０２１／１７５８５５号International Publication No. 2021/175855
　本発明は、耐溶剤性が改善されたカラーフィルタを形成できる着色硬化性樹脂組成物を提供することを課題とする。 The objective of the present invention is to provide a colored curable resin composition that can form a color filter with improved solvent resistance.
　すなわち、本発明の要旨は、以下の通りである。
[１]着色剤、樹脂、重合性化合物、及び重合開始剤を含み、
　前記重合開始剤が、式（Ｉ）で表される化合物を含む着色硬化性樹脂組成物。 That is, the gist of the present invention is as follows.
[1] A composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator;
The colored curable resin composition, wherein the polymerization initiator comprises a compound represented by formula (I).
Figure JPOXMLDOC01-appb-I000002
（式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5は、それぞれ独立して、置換基を有していてもよい炭化水素基を表す。
　ｎは０～４のいずれかの整数を表す。
　前記炭化水素基に含まれる－ＣＨ2－は－Ｏ－、－Ｓ－、－ＣＯ－、又は－ＯＣＯ－に置き換わっていてもよい。）
［２］前記樹脂が、下記樹脂［Ｋ１］から［Ｋ６］から選ばれる少なくとも１つである、［１］に記載の着色硬化性樹脂組成物。
　樹脂［Ｋ１］；不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種の単量体（ａ）に由来する構造単位と、炭素数２～４の環状エーテル構造とエチレン性不飽和結合とを有する単量体（ｂ）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ２］；前記（ａ）に由来する構造単位と前記（ｂ）に由来する構造単位と、前記（ａ）と共重合可能な単量体（ｃ）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ３］；前記（ａ）に由来する構造単位と前記（ｃ）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ４］；前記（ａ）に由来する構造単位に前記（ｂ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ５］；前記（ｂ）に由来する構造単位に前記（ａ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ５’］；前記（ａ）に由来する構造単位に前記（ｂ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ６］；前記（ｂ）に由来する構造単位に前記（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体。［３］前記樹脂が樹脂［Ｋ１］及び／又は樹脂［Ｋ２］である［２］に記載の着色硬化性樹脂組成物。
［４］前記樹脂が樹脂[Ｋ２］～［Ｋ６］のいずれかであって前記単量体（ｃ）として直鎖又は分岐鎖の脂肪族不飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状不飽和脂肪族炭化水素基を有する（メタ）アクリル酸エステル類、不飽和脂肪族炭化水素環を有するビニルモノマー、不飽和複素環を有するビニルモノマー、及び芳香族環を有するビニルモノマーから選ばれる少なくとも１種を含有する樹脂である［２］に記載の着色硬化性樹脂組成物。
［５］前記樹脂が樹脂［Ｋ４］～［Ｋ６］のいずれかである［２］に記載の着色硬化性樹脂組成物。
[６]前記樹脂がエチレン性二重結合を有し、前記樹脂のエチレン性二重結合当量が１００～２０００ｇ／ｍｏｌである[２]に記載の着色硬化性樹脂組成物。
［７］前記樹脂が樹脂［Ｋ２］～［Ｋ４］のいずれかであって、前記単量体（ｃ）として芳香族環を有する（メタ）アクリル酸エステル類を含み、全構造単位１００モル％中、芳香族環を有する（メタ）アクリル酸エステル類由来の構造単位と前記（ａ）に由来する構造単位の合計が６０モル％以上である［２］に記載の着色硬化性樹脂組成物。
［８］着色剤が、緑色顔料及び黄色顔料を含み、
　前記緑色顔料は、Ｃ．Ｉ．ピグメントグリーン７、Ｃ．Ｉ．ピグメントグリーン３６、Ｃ．Ｉ．ピグメントグリーン５８、Ｃ．Ｉ．ピグメントグリーン５９、Ｃ．Ｉ．ピグメントグリーン６２、及びＣ．Ｉ．ピグメントグリーン６３からなる群から選ばれる少なくとも１種を含み、
　前記黄色顔料は、Ｃ．Ｉ．ピグメントイエロー１３８、Ｃ．Ｉ．ピグメントイエロー１３９、Ｃ．Ｉ．ピグメントイエロー１５０、Ｃ．Ｉ．ピグメントイエロー１８５、Ｃ．Ｉ．ピグメントイエロー２３１、及びＣ．Ｉ．ピグメントイエロー２３３からなる群から選ばれる少なくとも１種を含む［２］に記載の着色硬化性樹脂組成物。
［９］着色剤が、赤色顔料及び黄色顔料を含み、
　前記赤色顔料は、Ｃ．Ｉ．ピグメントレッド１２２、Ｃ．Ｉ．ピグメントレッド１７７、Ｃ．Ｉ．ピグメントレッド２５４、Ｃ．Ｉ．ピグメントレッド２５５、Ｃ．Ｉ．ピグメントレッド２６４、Ｃ．Ｉ．ピグメントレッド２６９、Ｃ．Ｉ．ピグメントレッド２７２、及びＣ．Ｉ．ピグメントレッド２９１からなる群から選ばれる少なくとも１種を含み、
　前記黄色顔料は、Ｃ．Ｉ．ピグメントイエロー１３８、Ｃ．Ｉ．ピグメントイエロー１３９、Ｃ．Ｉ．ピグメントイエロー１５０、Ｃ．Ｉ．ピグメントイエロー１８５、Ｃ．Ｉ．ピグメントイエロー２３１、及びＣ．Ｉ．ピグメントイエロー２３３からなる群から選ばれる少なくとも１種を含む［２］に記載の着色硬化性樹脂組成物。
［１０］着色剤が、青色顔料及び紫色顔料を含み、
　前記青色顔料は、Ｃ．Ｉ．ピグメントブルー１５、１５：３、１５：４、１５：６、１６からなる群より選ばれる少なくとも１種を含み、
　前記紫色顔料は、Ｃ．Ｉ．ピグメントバイオレット１９、２３、２９からなる群より選ばれる少なくとも１種を含む[２]に記載の着色硬化性樹脂組成物。
［１１］［１］～［１０］のいずれかに記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［１２］［１１］に記載のカラーフィルタを含む表示装置。
［１３］［１１］に記載のカラーフィルタを含む固体撮像素子。
Figure JPOXMLDOC01-appb-I000002
(In the formula, R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a hydrocarbon group which may have a substituent.
n represents an integer of 0 to 4.
The --CH 2 -- contained in the hydrocarbon group may be replaced with --O--, --S--, --CO--, or --OCO--.
[2] The colored curable resin composition according to [1], wherein the resin is at least one selected from the following resins [K1] to [K6].
Resin [K1]: a copolymer having a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
Resin [K2]: a copolymer having a structural unit derived from the (a), a structural unit derived from the (b), and a structural unit derived from a monomer (c) copolymerizable with the (a);
Resin [K3]: a copolymer having a structural unit derived from the (a) and a structural unit derived from the (c);
Resin [K4]: a copolymer having a structural unit derived from the (a) and a structural unit derived from the (b) by addition, and a structural unit derived from the (c);
Resin [K5]: a copolymer having a structural unit derived from the (b) to which the (a) has been added, and a structural unit derived from the (c);
Resin [K5']: a copolymer having a structural unit derived from the (a) and a structural unit derived from the (b) by addition, and a structural unit derived from the (c);
Resin [K6]: A copolymer having a structural unit obtained by adding the (a) to a structural unit derived from the (b) and further adding a carboxylic acid anhydride, and a structural unit derived from the (c). [3] The colored curable resin composition according to [2], wherein the resin is resin [K1] and/or resin [K2].
[4] The colored curable resin composition according to [2], wherein the resin is any one of resins [K2] to [K6], and the monomer (c) is at least one selected from the group consisting of (meth)acrylic acid esters having a linear or branched aliphatic unsaturated hydrocarbon group, (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, vinyl monomers having an unsaturated aliphatic hydrocarbon ring, vinyl monomers having an unsaturated heterocycle, and vinyl monomers having an aromatic ring.
[5] The colored curable resin composition according to [2], wherein the resin is any one of resins [K4] to [K6].
[6] The colored curable resin composition according to [2], wherein the resin has an ethylenic double bond and the ethylenic double bond equivalent of the resin is 100 to 2000 g/mol.
[7] The colored curable resin composition according to [2], wherein the resin is any one of resins [K2] to [K4], the monomer (c) contains a (meth)acrylic acid ester having an aromatic ring, and the total of the structural units derived from the (meth)acrylic acid ester having an aromatic ring and the structural units derived from the (a) is 60 mol % or more in 100 mol % of all structural units.
[8] The colorant includes a green pigment and a yellow pigment,
The green pigment includes at least one selected from the group consisting of C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62, and C.I. Pigment Green 63;
The yellow pigment includes at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 231, and C.I. Pigment Yellow 233. The colored curable resin composition according to [2].
[9] The colorant includes a red pigment and a yellow pigment,
The red pigment includes at least one selected from the group consisting of C.I. Pigment Red 122, C.I. Pigment Red 177, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Red 269, C.I. Pigment Red 272, and C.I. Pigment Red 291;
The yellow pigment includes at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 231, and C.I. Pigment Yellow 233. The colored curable resin composition according to [2].
[10] The colorant includes a blue pigment and a purple pigment,
The blue pigment includes at least one selected from the group consisting of C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 16;
The colored curable resin composition according to [2], wherein the purple pigment includes at least one selected from the group consisting of C.I. Pigment Violet 19, 23, and 29.
[11] A color filter formed from the colored curable resin composition according to any one of [1] to [10].
[12] A display device comprising the color filter according to [11].
[13] A solid-state imaging device comprising the color filter according to [11].
　本発明によれば、耐溶剤性が改善されたカラーフィルタを形成できる着色硬化性樹脂組成物を提供することが可能となる。 The present invention makes it possible to provide a colored curable resin composition that can form a color filter with improved solvent resistance.
　本発明の着色硬化性樹脂組成物は、着色剤（以下、着色剤（Ａ）という場合がある）、樹脂（以下、樹脂（Ｂ）という場合がある）、重合性化合物（以下、重合性化合物（Ｃ）という場合がある）、及び重合開始剤（以下、重合開始剤（Ｄ）という場合がある）を含む。
　本発明の着色硬化性樹脂組成物は、さらに溶剤（以下、溶剤（Ｅ）という場合がある）を含んでいてもよい。
　本発明の着色硬化性樹脂組成物は、さらに重合開始助剤（以下、重合開始助剤（Ｄ１）という場合がある）を含んでいてもよい。
　本発明の着色硬化性樹脂組成物は、さらにチオール化合物（以下、チオール化合物（Ｔ）という場合がある）を含んでいてもよい。
　本発明の着色硬化性樹脂組成物は、さらにレベリング剤（以下、レベリング剤（Ｆ）という場合がある）を含んでいてもよい。
　なお、本明細書において、各成分として例示する化合物は、特に断りのない限り、単独で又は複数種を組み合わせて使用することができる。 The colored curable resin composition of the present invention contains a colorant (hereinafter, may be referred to as colorant (A)), a resin (hereinafter, may be referred to as resin (B)), a polymerizable compound (hereinafter, may be referred to as polymerizable compound (C)), and a polymerization initiator (hereinafter, may be referred to as polymerization initiator (D)).
The colored curable resin composition of the present invention may further contain a solvent (hereinafter, may be referred to as solvent (E)).
The colored curable resin composition of the present invention may further contain a polymerization initiation aid (hereinafter, may be referred to as polymerization initiation aid (D1)).
The colored curable resin composition of the present invention may further contain a thiol compound (hereinafter, may be referred to as thiol compound (T)).
The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, may be referred to as leveling agent (F)).
In this specification, the compounds exemplified as each component may be used alone or in combination of two or more kinds, unless otherwise specified.
＜着色剤（Ａ）＞
　着色剤（Ａ）としては、染料（Ａ１）及び顔料（Ａ２）が挙げられ、顔料（Ａ２）が好ましい。これらは単独で用いてもよく、又は２種以上を組み合わせて使用してもよい。 <Colorant (A)>
The colorant (A) may be a dye (A1) or a pigment (A2), and the pigment (A2) is preferred. These may be used alone or in combination of two or more.
　染料（Ａ１）は特に限定されず、公知の染料を使用することができ、例えば、溶剤染料、酸性染料、直接染料、媒染染料等が挙げられる。染料としては、例えば、カラーインデックス（Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ出版）で染料に分類されている化合物や、染色ノート（色染社）に記載されている公知の染料が挙げられる。また、化学構造によれば、アゾ染料、シアニン染料、トリフェニルメタン染料、キサンテン染料、アントラキノン染料、ナフトキノン染料、キノンイミン染料、メチン染料、アゾメチン染料、スクアリリウム染料、アクリジン染料、スチリル染料、クマリン染料、キノリン染料、ニトロ染料、フタロシアニン染料、ペリレン染料、キノフタロン染料、イソインドリン染料等が挙げられる。これらのうち、有機溶剤可溶性染料が好ましい。 The dye (A1) is not particularly limited, and known dyes can be used, such as solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in Dyeing Notes (Shikisensha). In addition, examples of dyes that can be used according to their chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, quinophthalone dyes, and isoindoline dyes. Of these, organic solvent-soluble dyes are preferred.
　具体的には、以下のようなカラーインデックス（Ｃ．Ｉ．）番号の染料が挙げられる。
　Ｃ．Ｉ．ソルベントイエロー４、１４、１５、２３、２４、２５、３８、６２、６３、６８、７９、８１、８２、８３、８９、９４、９８、９９、１１７、１６２、１６３、１６７、１８９；
　Ｃ．Ｉ．ソルベントレッド２４、４５、４９、９０，９１、１１１、１１８、１１９、１２２、１２４、１２５、１２７、１３０、１３２、１４３、１４５、１４６、１５０、１５１、１５５、１６０、１６８、１６９、１７２、１７５、１８１、２０７、２１８、２２２、２２７、２３０、２４５、２４７；
　Ｃ．Ｉ．ソルベントオレンジ２、７、１１、１５、２６、４１、５４、５６、７７、８６、９９；
　Ｃ．Ｉ．ソルベントバイオレット１１、１３、１４、２６、３１、３６、３７、３８、４５、４７、４８、５１、５９、６０；
　Ｃ．Ｉ．ソルベントブルー４、５、１４、１８、３５、３６、３７、３８、４４、４５、５８、５９、５９：１、６３、６７、６８、６９、７０、７８、７９、８３、９０、９４、９７、９８、１００、１０１、１０２、１０４、１０５、１１１、１１２、１２２、１２８、１３２、１３６、１３９；
　Ｃ．Ｉ．ソルベントグリーン１、３、４、５、７、２８、２９、３２、３３、３４、３５；等のＣ．Ｉ．ソルベント染料、
　Ｃ．Ｉ．アシッドイエロー１、３、７、９、１１、１７、２３、２５、２９、３４、３６、３８、４０、４２、５４、６５、７２、７３、７６、７９、９８、９９、１１１、１１２、１１３、１１４、１１６、１１９、１２３、１２８、１３４、１３５、１３８、１３９、１４０、１４４、１５０、１５５、１５７、１６０、１６１、１６３、１６８、１６９、１７２、１７７、１７８、１７９、１８４、１９０、１９３、１９６、１９７、１９９、２０２、２０３、２０４、２０５、２０７、２１２、２１４、２２０、２２１、２２８、２３０、２３２、２３５、２３８、２４０、２４２、２４３、２５１；
　Ｃ．Ｉ．アシッドレッド１、４、８、１４、１７、１８、２６、２７、２９、３１、３３、３４、３５、３７、４０、４２、４４、５０、５１、５２、５７、６６、７３、７６、８０、８７、８８、９１、９２、９４、９５、９７、９８、１０３、１０６、１１１、１１４、１２９、１３３、１３４、１３８、１４３、１４５、１５０、１５１、１５５、１５８、１６０、１７２、１７６、１８２、１８３、１９５、１９８、２０６、２１１、２１５、２１６、２１７、２２７、２２８、２４９、２５２、２５７、２５８、２６０、２６１、２６６、２６８、２７０、２７４、２７７、２８０、２８１、２８９、３０８、３１２、３１５、３１６、３３９、３４１、３４５、３４６、３４９、３８２、３８３、３８８、３９４、４０１、４１２、４１７、４１８、４２２、４２６；
　Ｃ．Ｉ．アシッドオレンジ６、７、８、１０、１２、２６、５０、５１、５２、５６、６２、６３、６４、７４、７５、９４、９５、１０７、１０８、１４９、１６２、１６９、１７３；
　Ｃ．Ｉ．アシッドバイオレット６Ｂ、７、９、１５、１６、１７、１９、２１、２３、２４、２５、３０、３４、３８、４９、７２、１０２；
　Ｃ．Ｉ．アシッドブルー１、３、５、７、９、１１、１３、１５、１７、１８、２２、２３、２４、２５、２６、２７、２９、３４、３８、４０、４１、４２、４３、４５、４８、５１、５４、５９、６０、６２、７０、７２、７４、７５、７８、８０、８２、８３、８６、８７、８８、９０、９０：１、９１、９２、９３、９３：１、９６、９９、１００、１０２、１０３、１０４、１０８、１０９、１１０、１１２、１１３、１１７、１１９、１２０、１２３、１２６、１２７、１２９、１３０、１３１、１３８、１４０、１４２、１４３、１４７、１５０、１５１、１５４、１５８、１６１、１６６、１６７、１６８、１７０、１７１、１７５、１８２、１８３、１８４、１８７、１９２、１９９、２０３、２０４、２０５、２１０、２１３、２２９、２３４、２３６、２４２、２４３、２４９、２５６、２５９、２６７、２６９、２７８、２８０、２８５、２９０、２９６、３１５、３２４：１、３３５、３４０；
　Ｃ．Ｉ．アシッドグリーン１、３、５、６、７、８、９、１１、１３、１４、１５、１６、２２、２５、２７、２８、４１、５０、５０：１、５８、６３、６５、８０、１０４、１０５、１０６、１０９；等のＣ．Ｉ．アシッド染料、
　Ｃ．Ｉ．ダイレクトイエロー２、４、２８、３３、３４、３５、３８、３９、４３、４４、４７、５０、５４、５８、６８、６９、７０、７１、８６、９３、９４、９５、９８、１０２、１０８、１０９、１２９、１３２、１３６、１３８、１４１；
　Ｃ．Ｉ．ダイレクトレッド７９、８２、８３、８４、９１、９２、９６、９７、９８、９９、１０５、１０６、１０７、１７２、１７３、１７６、１７７、１７９、１８１、１８２、１８４、２０４、２０７、２１１、２１３、２１８、２２０、２２１、２２２、２３２、２３３、２３４、２４１、２４３、２４６、２５０；
　Ｃ．Ｉ．ダイレクトオレンジ２６、３４、３９、４１、４６、５０、５２、５６、５７、６１、６４、６５、６８、７０、９６、９７、１０６、１０７；
　Ｃ．Ｉ．ダイレクトバイオレット４７、５２、５４、５９、６０、６５、６６、７９、８０、８１、８２、８４、８９、９０、９３、９５、９６、１０３、１０４；
　Ｃ．Ｉ．ダイレクトブルー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、８７、９０、９３、９４、９５、９７、９８、９９、１００、１０１、１０６、１０７、１０８、１０９、１１３、１１４、１１５、１１７、１１９、１２０、１３７、１４９、１５０、１５３、１５５、１５６、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１７０、１７１、１７２、１７３、１８８、１８９、１９０、１９２、１９３、１９４、１９５、１９６、１９８、１９９、２００、２０１、２０２、２０３、２０７、２０９、２１０、２１２、２１３、２１４、２２２、２２５、２２６、２２８、２２９、２３６、２３７、２３８、２４２、２４３、２４４、２４５、２４６、２４７、２４８、２４９、２５０、２５１、２５２、２５６、２５７、２５９、２６０、２６８、２７４、２７５、２９３；
　Ｃ．Ｉ．ダイレクトグリーン２５、２７、３１、３２、３４、３７、６３、６５、６６、６７、６８、６９、７２、７９、８２；等のＣ．Ｉ．ダイレクト染料、
　Ｃ．Ｉ．ディスパースイエロー５１、５４、７６；
　Ｃ．Ｉ．ディスパースバイオレット２６、２７；
　Ｃ．Ｉ．ディスパースブルー１、１４、５６、６；０等のＣ．Ｉ．ディスパース染料、
　Ｃ．Ｉ．ベーシックレッド１、１０；
　Ｃ．Ｉ．ベーシックブルー１、３、５、７、９、１９、２１、２２、２４、２５、２６、２８、２９、４０、４１、４５、４７、５４、５８、５９、６０、６４、６５、６６、６７、６８、８１、８３、８８、８９；
　Ｃ．Ｉ．ベーシックバイオレット２；
　Ｃ．Ｉ．ベーシックレッド９；
　Ｃ．Ｉ．ベーシックグリーン１；等のＣ．Ｉ．ベーシック染料、
　Ｃ．Ｉ．リアクティブイエロー２、７６、１１６；
　Ｃ．Ｉ．リアクティブオレンジ１６；
　Ｃ．Ｉ．リアクティブレッド３６；等のＣ．Ｉ．リアクティブ染料、
　Ｃ．Ｉ．モーダントイエロー５、８、１０、１６、２０、２６、３０、３１、３３、４２、４３、４５、５６、６１、６２、６５；
　Ｃ．Ｉ．モーダントレッド１、２、３、４、９、１１、１２、１４、１７、１８、１９、２２、２３、２４、２５、２６、２７、２９、３０、３２、３３、３６、３７、３８、３９、４１、４２、４３、４５、４６、４８、５２、５３、５６、６２、６３、７１、７４、７６、７８、８５、８６、８８、９０、９４、９５；
　Ｃ．Ｉ．モーダントオレンジ３、４、５、８、１２、１３、１４、２０、２１、２３、２４、２８、２９、３２、３４、３５、３６、３７、４２、４３、４７、４８；
　Ｃ．Ｉ．モーダントバイオレット１、１：１、２、３、４、５、６、７、８、１０、１１、１４、１５、１６、１７、１８、１９、２１、２２、２３、２４、２７、２８、３０、３１、３２、３３、３６、３７、３９、４０、４１、４４、４５、４７、４８、４９、５３、５８；
　Ｃ．Ｉ．モーダントブルー１、２、３、７、８、９、１２、１３、１５、１６、１９、２０、２１、２２、２３、２４、２６、３０、３１、３２、３９、４０、４１、４３、４４、４８、４９、５３、６１、７４、７７、８３、８４；
　Ｃ．Ｉ．モーダントグリーン１、３、４、５、１０、１３、１５、１９、２１、２３、２６、２９、３１、３３、３４、３５、４１、４３、５３；等のＣ．Ｉ．モーダント染料、
　Ｃ．Ｉ．バットグリーン１；等のＣ．Ｉ．バット染料等 Specifically, dyes having the following Color Index (C.I.) numbers are included.
C.I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;
C.I. Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;
C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C.I. Solvent dyes such as C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35;
C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 1 57, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 18 2, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C.I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;
C. I. Acid dyes such as C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109;
C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C.I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166 , 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C.I. Direct dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82;
C.I. Disperse Yellow 51, 54, 76;
C.I. Disperse Violet 26, 27;
C.I. Disperse dyes such as C.I. Disperse Blue 1, 14, 56, 6;0,
C.I. Basic Red 1, 10;
C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C.I. Basic Violet 2;
C.I. Basic Red 9;
C.I. Basic dyes such as C.I. Basic Green 1;
C.I. Reactive Yellow 2, 76, 116;
C.I. Reactive Orange 16;
C.I. Reactive dyes such as C.I. Reactive Red 36;
C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C.I. Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C.I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
C.I. Mordant dyes such as C.I. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53;
C.I. Vat dyes such as C.I. Vat Green 1;
　これらの染料は、所望するカラーフィルタの分光スペクトルに合わせて適宜選択すればよい。 These dyes can be selected appropriately to match the spectral spectrum of the desired color filter.
　顔料（Ａ２）としては、公知の顔料を使用することができ、例えば、カラーインデックス（Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ出版）でピグメントに分類されている顔料が挙げられる。また、化学構造によれば、アゾ系顔料、シアニン系顔料、トリフェニルメタン系顔料、キサンテン系顔料、アントラキノン系顔料、ナフトキノン系顔料、キノンイミン系顔料、メチン系顔料、アゾメチン系顔料、スクアリリウム系顔料、アクリジン系顔料、スチリル系顔料、クマリン系顔料、キノリン系顔料、ニトロ系顔料、フタロシアニン系顔料、ペリレン系顔料、キノフタロン系顔料、イソインドリン系顔料等が挙げられる。これらのうち、フタロシアニン系顔料、キノフタロン系顔料、イソインドリン系顔料等が好ましい。 Pigments (A2) may be any known pigment, including, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). In addition, according to their chemical structure, examples include azo pigments, cyanine pigments, triphenylmethane pigments, xanthene pigments, anthraquinone pigments, naphthoquinone pigments, quinoneimine pigments, methine pigments, azomethine pigments, squarylium pigments, acridine pigments, styryl pigments, coumarin pigments, quinoline pigments, nitro pigments, phthalocyanine pigments, perylene pigments, quinophthalone pigments, and isoindoline pigments. Of these, phthalocyanine pigments, quinophthalone pigments, and isoindoline pigments are preferred.
　ピグメントに分類されている顔料としては、具体的には、Ｃ．Ｉ．ピグメントイエロー１、３、１２、１３、１４、１５、１６、１７、２０、２４、３１、５３、８３、８６、９３、９４、１０９、１１０、１１７、１２５、１２８、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５３、１５４、１６６、１７３、１８５、１９４、２１４、２３１等の黄色顔料；
Ｃ．Ｉ．ピグメントオレンジ１３、３１、３６、３８、４０、４２、４３、５１、５５、５９、６１、６４、６５、７１、７３等のオレンジ色顔料；
Ｃ．Ｉ．ピグメントレッド９、９７、１０５、１２２、１２３、１４４、１４９、１６６、１６８、１７６、１７７、１７８、１７９、１８０、１９０、１９２、２０２、２０９、２１５、２１６、２２４、２４２、２５４、２５５、２６４、２６５、２６６、２６８、２６９、２７２、２７３、２９１等の赤色顔料；
Ｃ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、６０等の青色顔料；
Ｃ．Ｉ．ピグメントバイオレット１、１９、２３、２９、３２、３６、３８等のバイオレット色顔料；
Ｃ．Ｉ．ピグメントグリーン７、３６、５８、５９、６２、６３等の緑色顔料；
Ｃ．Ｉ．ピグメントブラウン２３、２５等のブラウン色顔料；
Ｃ．Ｉ．ピグメントブラック１、７、３１、３２等の黒色顔料；等が挙げられる。 Specific examples of pigments classified as C.I. Pigment include yellow pigments such as 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, 214, and 231;
Orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
red pigments such as C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 272, 273, 291;
blue pigments such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60;
Violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;
green pigments such as C.I. Pigment Green 7, 36, 58, 59, 62, 63;
Brown pigments such as C.I. Pigment Brown 23 and 25;
black pigments such as C.I. Pigment Black 1, 7, 31, and 32;
　これらの顔料は、所望するカラーフィルタの分光スペクトルに合わせて適宜選択すればよい。 These pigments can be selected appropriately to match the spectral spectrum of the desired color filter.
　緑色の着色硬化性樹脂組成物を調製する場合、着色剤（Ａ）としては、黄色染料及び黄色顔料（以下、これらを総称して「黄色着色剤」という場合がある）、緑色染料及び緑色顔料（以下、これらを総称して「緑色着色剤」という場合がある）からなる群から選ばれる少なくとも一種を含むことが好ましく、黄色顔料及び／又は緑色顔料を含むことがより好ましい。 When preparing a green colored curable resin composition, the colorant (A) preferably contains at least one selected from the group consisting of a yellow dye and a yellow pigment (hereinafter, these may be collectively referred to as "yellow colorant"), a green dye and a green pigment (hereinafter, these may be collectively referred to as "green colorant"), and more preferably contains a yellow pigment and/or a green pigment.
　黄色染料としては、上記染料のうち、色相が黄に分類されている染料が挙げられ、黄色顔料としては、上記顔料のうち、色相が黄に分類されている顔料が挙げられる。
　黄色顔料のなかでも、キノフタロン黄色顔料、金属含有黄色顔料、イソインドリン黄色顔料が好ましく、Ｃ．Ｉ．ピグメントイエロー１３８、１３９、１５０、１８５、２３１、２３３からなる群から選ばれる少なくとも１種がより好ましく、Ｃ．Ｉ．ピグメントイエロー１３８、１３９、１５０、１８５からなる群から選ばれる少なくとも１種がさらに好ましい。 The yellow dye may be any of the above dyes whose hues are classified as yellow, and the yellow pigment may be any of the above pigments whose hues are classified as yellow.
Among the yellow pigments, quinophthalone yellow pigments, metal-containing yellow pigments, and isoindoline yellow pigments are preferred, and at least one selected from the group consisting of C.I. Pigment Yellow 138, 139, 150, 185, 231, and 233 is more preferred, and at least one selected from the group consisting of C.I. Pigment Yellow 138, 139, 150, and 185 is even more preferred.
　緑色染料としては、上記染料のうち、色相が緑に分類されている染料が挙げられ、緑色顔料としては、上記顔料のうち、色相が緑に分類されている顔料が挙げられる。
　緑色顔料のなかでも、フタロシアニン顔料が好ましく、ハロゲン化銅フタロシアニン顔料及びハロゲン化亜鉛フタロシアニン顔料からなる群から選ばれる少なくとも一種がより好ましく、Ｃ．Ｉ．ピグメントグリーン７、３６、５８、５９、６２、６３からなる群から選ばれる少なくとも１種がさらに好ましく、Ｃ．Ｉ．ピグメントグリーン５８、５９からなる群から選ばれる少なくとも１種がさらにより好ましい。 The green dye may be any of the above dyes whose hue is classified as green, and the green pigment may be any of the above pigments whose hue is classified as green.
Among the green pigments, phthalocyanine pigments are preferred, at least one selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferred, at least one selected from the group consisting of C.I. Pigment Green 7, 36, 58, 59, 62, and 63 is even more preferred, and at least one selected from the group consisting of C.I. Pigment Green 58 and 59 is even more preferred.
　緑色の着色硬化性樹脂組成物を調製する場合、着色剤（Ａ）は、全着色剤１００質量％中、黄色着色剤及び／又は緑色着色剤を合計で、例えば、５０質量％以上、好ましくは７０質量％以上、より好ましくは９０質量％以上、特に９５質量以上％含むことが好ましい。
　また、黄色着色剤及び緑色着色剤の両方を含むことが好ましく、黄色着色剤及び緑色着色剤の両方を含む場合、黄色着色剤の含有率は、黄色着色剤及び緑色着色剤の合計１００質量％中、例えば、１０質量％以上７０質量％以下であり、１５質量％以上６０質量％以下が好ましく、２０質量％以上５５質量％以下がより好ましい。
　黄色着色剤及び緑色着色剤の両方を含む場合、緑色着色剤の含有率は、黄色着色剤及び緑色着色剤の合計１００質量％中、例えば、３０質量％以上９０質量％以下であり、４０質量％以上８５質量％以下が好ましく、４５質量％以上８０質量％以下がより好ましい。 In the case of preparing a green colored curable resin composition, the colorant (A) preferably contains a yellow colorant and/or a green colorant in total in an amount of, for example, 50 mass% or more, preferably 70 mass% or more, more preferably 90 mass% or more, and particularly preferably 95 mass% or more, based on 100 mass% of all colorants.
In addition, it is preferable that both a yellow colorant and a green colorant are contained. In the case where both a yellow colorant and a green colorant are contained, the content of the yellow colorant is, for example, 10 mass% or more and 70 mass% or less, preferably 15 mass% or more and 60 mass% or less, and more preferably 20 mass% or more and 55 mass% or less, based on 100 mass% in total of the yellow colorant and the green colorant.
In the case where both a yellow colorant and a green colorant are contained, the content of the green colorant is, for example, 30% by mass or more and 90% by mass or less, preferably 40% by mass or more and 85% by mass or less, and more preferably 45% by mass or more and 80% by mass or less, based on 100% by mass of the total of the yellow colorant and the green colorant.
　緑色の着色硬化性樹脂組成物は、緑色着色剤、黄色着色剤に加えて、後述する青色着色剤を含んでいてもよい。
　青色着色剤の含有率は、緑色着色剤、黄色着色剤、及び青色着色剤の合計１００質量％中、例えば０質量％以上、５質量％以下、好ましくは０．１質量％以上、４．５質量％以下、より好ましくは０．２質量％以上、４．０質量％以下である。 The green colored curable resin composition may contain a blue colorant, which will be described later, in addition to a green colorant and a yellow colorant.
The content of the blue colorant is, for example, 0 mass% or more and 5 mass% or less, preferably 0.1 mass% or more and 4.5 mass% or less, and more preferably 0.2 mass% or more and 4.0 mass% or less, relative to 100 mass% in total of the green colorant, the yellow colorant, and the blue colorant.
　赤色の着色硬化性樹脂組成物を調製する場合、着色剤（Ａ）としては、黄色着色剤、赤色染料及び赤色顔料（以下、これらを総称して「赤色着色剤」という場合がある）からなる群から選ばれる少なくとも一種を含むことが好ましく、黄色顔料及び／又は赤色顔料を含むことがより好ましい。 When preparing a red colored curable resin composition, the colorant (A) preferably contains at least one selected from the group consisting of a yellow colorant, a red dye, and a red pigment (hereinafter, these may be collectively referred to as "red colorant"), and more preferably contains a yellow pigment and/or a red pigment.
　黄色着色剤としては、緑色の着色硬化性樹脂組成物を調製する場合と同様の例が挙げられ、好ましい態様も同様である。 Examples of yellow colorants include those similar to those used to prepare the green colored curable resin composition, and the preferred embodiments are also similar.
　赤色染料としては、上記染料のうち、色相が赤に分類されている染料が挙げられ、赤色顔料としては、上記顔料のうち、色相が赤に分類されている顔料が挙げられる。
　赤色顔料のなかでも、Ｃ．Ｉ．ピグメントレッド１２２、１７７、２５４、２５５、２６４、２６９、２７２、２９１からなる群から選ばれる少なくとも１種が好ましく、Ｃ．Ｉ．ピグメントレッド１７７、２５４、２６９、２７２、２９１からなる群から選ばれる少なくとも１種がより好ましい。 The red dye may be any of the above dyes whose hue is classified as red, and the red pigment may be any of the above pigments whose hue is classified as red.
Among the red pigments, at least one selected from the group consisting of C.I. Pigment Red 122, 177, 254, 255, 264, 269, 272, and 291 is preferable, and at least one selected from the group consisting of C.I. Pigment Red 177, 254, 269, 272, and 291 is more preferable.
　赤色の着色硬化性樹脂組成物を調製する場合、着色剤（Ａ）は、全着色剤１００質量％中、黄色着色剤及び／又は赤色着色剤を合計で、例えば、５０質量％以上、好ましくは７０質量％以上、より好ましくは９０質量％以上、特に１００質量％含むことが好ましい。また、黄色着色剤及び赤色着色剤の両方を含むことが好ましい。 When preparing a red colored curable resin composition, the colorant (A) preferably contains, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and especially 100% by mass of a yellow colorant and/or a red colorant in total, based on 100% by mass of all colorants. It is also preferable that the colorant (A) contains both a yellow colorant and a red colorant.
　青色の着色硬化性樹脂組成物を調製する場合、着色剤（Ａ）としては、青色染料及び青色顔料（以下、これらを総称して「青色着色剤」という場合がある）からなる群から選ばれる少なくとも一種を含むことが好ましく、青色顔料を含むことがより好ましい。 When preparing a blue colored curable resin composition, the colorant (A) preferably contains at least one selected from the group consisting of a blue dye and a blue pigment (hereinafter, these may be collectively referred to as "blue colorant"), and more preferably contains a blue pigment.
　青色染料としては、上記染料のうち、色相が青に分類されている染料が挙げられ、青色顔料としては、上記顔料のうち、色相が青に分類されている顔料が挙げられる。
　青色顔料としては、フタロシアニン顔料が好ましく、Ｃ．Ｉ．ピグメントブルー１５、１５：３、１５：４、１５：６、１６からなる群から選ばれる少なくとも１種がより好ましい。 Examples of blue dyes include those dyes that have a hue classified as blue among the above dyes, and examples of blue pigments include those pigments that have a hue classified as blue among the above pigments.
As the blue pigment, a phthalocyanine pigment is preferable, and at least one selected from the group consisting of C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 16 is more preferable.
　青色の着色硬化性樹脂組成物を調製する場合、青色着色剤以外に、バイオレット色染料及びバイオレット色顔料（以下、これらを総称して「バイオレット色着色剤」という場合がある）も含有することが好ましい。 When preparing a blue colored curable resin composition, it is preferable to also contain a violet dye and a violet pigment (hereinafter, these may be collectively referred to as "violet colorant") in addition to the blue colorant.
　バイオレット色染料としては、上記染料のうち、色相がバイオレットに分類されている染料が挙げられ、バイオレット色顔料としては、上記顔料のうち、色相がバイオレットに分類されている顔料が挙げられる。
　バイオレット色着色剤としては、バイオレット色顔料が好ましく、バイオレット色顔料のなかでも、Ｃ．Ｉ．ピグメントバイオレット１９、２３、２９からなる群から選ばれる少なくとも１種がより好ましい。 The violet dye may be any of the above dyes whose hues are classified as violet, and the violet pigment may be any of the above pigments whose hues are classified as violet.
As the violet colorant, a violet pigment is preferable, and among the violet pigments, at least one selected from the group consisting of C.I. Pigment Violet 19, 23, and 29 is more preferable.
　青色の着色硬化性樹脂組成物を調製する場合、着色剤（Ａ）は、全着色剤１００質量％中、青色着色剤を、例えば、３０質量％以上９９質量％以下、好ましくは５０質量％以上、より好ましくは６０質量％以上含むことが好ましい。また、バイオレット色着色剤を含む場合、青色着色剤の含有率は、青色着色剤及びバイオレット色着色剤の合計１００質量％中、例えば、５質量％以上９５質量％以下であり、１０質量％以上８０質量％以下が好ましく、２０質量％以上６０質量％以下がより好ましい。 When preparing a blue colored curable resin composition, the colorant (A) preferably contains, for example, 30% by mass or more and 99% by mass or less, preferably 50% by mass or more, and more preferably 60% by mass or more, of the blue colorant in 100% by mass of the total colorants. Also, when a violet colorant is contained, the content of the blue colorant is, for example, 5% by mass or more and 95% by mass or less, preferably 10% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, in 100% by mass of the total of the blue colorant and the violet colorant.
　黄色の着色硬化性樹脂組成物を調製する場合、着色剤（Ａ）としては、黄色着色剤を少なくとも一種を含むことが好ましく、黄色顔料を少なくとも一種を含むことがより好ましく、黄色顔料を二種以上含むことがさらに好ましい。 When preparing a yellow colored curable resin composition, the colorant (A) preferably contains at least one yellow colorant, more preferably contains at least one yellow pigment, and even more preferably contains two or more yellow pigments.
　黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１２９、１３８、１３９、１５０、１８５からなる群から選ばれる少なくとも１種が好ましく、Ｃ．Ｉ．ピグメントイエロー１３８、１３９、１５０、１８５からなる群から選ばれる少なくとも１種がより好ましい。 As the yellow pigment, at least one selected from the group consisting of C.I. Pigment Yellow 129, 138, 139, 150, and 185 is preferable, and at least one selected from the group consisting of C.I. Pigment Yellow 138, 139, 150, and 185 is more preferable.
　黄色の着色硬化性樹脂組成物を調製する場合、着色剤（Ａ）は、全着色剤１００質量％中、黄色着色剤を、例えば、５０質量％以上、好ましくは７０質量％以上、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上、特に１００質量％含むことが好ましい。 When preparing a yellow colored curable resin composition, the colorant (A) preferably contains a yellow colorant in an amount of, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and especially 100% by mass, based on 100% by mass of all colorants.
　着色硬化性樹脂組成物が溶剤（Ｅ）を含む場合、予め着色剤（Ａ）と溶剤（Ｅ）とを含む着色剤含有液を調製した後、該着色剤含有液を使用して着色硬化性樹脂組成物を調製してもよい。着色剤（Ａ）が溶剤（Ｅ）に溶解しない場合、例えば着色剤（Ａ）が顔料（Ａ２）を含む場合等には、着色剤含有液は、着色剤（Ａ）を溶剤（Ｅ）に分散させて混合することにより調製できる。着色剤含有液は、着色硬化性樹脂組成物に含有される溶剤（Ｅ）の一部又は全部を含んでいてもよい。 When the colored curable resin composition contains a solvent (E), a colorant-containing liquid containing the colorant (A) and the solvent (E) may be prepared in advance, and then the colorant-containing liquid may be used to prepare the colored curable resin composition. When the colorant (A) is not soluble in the solvent (E), for example when the colorant (A) contains a pigment (A2), the colorant-containing liquid can be prepared by dispersing the colorant (A) in the solvent (E) and mixing. The colorant-containing liquid may contain a part or all of the solvent (E) contained in the colored curable resin composition.
　着色剤含有液中の固形分の含有率は、着色剤含有液の総量に対して、１００質量％未満であり、好ましくは１質量％以上８０質量％以下、より好ましくは２質量％以上７０質量％以下、さらに好ましくは５質量％以上６５質量％以下である。 The solid content in the colorant-containing liquid is less than 100% by mass, preferably 1% by mass to 80% by mass, more preferably 2% by mass to 70% by mass, and even more preferably 5% by mass to 65% by mass, based on the total amount of the colorant-containing liquid.
　着色剤含有液中の着色剤（Ａ）の含有率は、着色剤含有液中の固形分の総量に対して、１００質量％未満であり、好ましくは０．５質量％以上８０質量％以下であり、より好ましくは１質量％以上７０質量％以下であり、さらに好ましくは２．５質量％以上６５質量％以下である。 The content of colorant (A) in the colorant-containing liquid is less than 100% by mass, preferably 0.5% by mass to 80% by mass, more preferably 1% by mass to 70% by mass, and even more preferably 2.5% by mass to 65% by mass, based on the total amount of solids in the colorant-containing liquid.
　着色剤（Ａ）は、必要に応じて、ロジン処理、酸性基又は塩基性基が導入された誘導体等を用いた表面処理、高分子化合物等による着色剤（Ａ）表面へのグラフト処理、硫酸微粒化法、ソルトミリング法等による微粒化処理、不純物を除去するための有機溶剤や水等による洗浄処理、イオン性不純物のイオン交換法等による除去処理等が施されていてもよい。着色剤（Ａ）の粒径は、略均一であることが好ましい。 If necessary, the colorant (A) may be subjected to a rosin treatment, a surface treatment using a derivative having an acidic or basic group introduced therein, a grafting treatment to the surface of the colorant (A) using a polymer compound, a micronization treatment using a sulfuric acid micronization method or a salt milling method, a washing treatment using an organic solvent or water to remove impurities, a removal treatment using an ion exchange method for ionic impurities, etc. It is preferable that the particle size of the colorant (A) is approximately uniform.
　着色剤（Ａ）は、分散剤を含有させて分散処理を行うことで、着色剤（Ａ）が溶液中で均一に分散した状態にすることができる。着色剤（Ａ）として２種以上を組み合わせて使用する場合は、それぞれを単独で分散処理してもよく、複数種を混合して分散処理してもよい。 The colorant (A) can be made to be uniformly dispersed in the solution by adding a dispersant and carrying out a dispersion treatment. When using a combination of two or more types of colorant (A), each may be dispersed alone, or multiple types may be mixed and dispersed.
　分散剤としては、例えば、界面活性剤等が挙げられ、カチオン系、アニオン系、ノニオン系及び両性のいずれの界面活性剤であってもよい。具体的にはポリエステル系、ポリアミン系及びアクリル系等の界面活性剤等が挙げられる。これらの分散剤は、単独で又は２種以上を組み合わせて用いてもよい。分散剤としては、商品名で表すと、ＫＰ（信越化学工業（株）製）、フローレン（共栄社化学（株）製）、ソルスパース（登録商標）（ゼネカ（株）製）、ＥＦＫＡ（登録商標）（ＢＡＳＦ社製）、アジスパー（登録商標）（味の素ファインテクノ（株）製）及びＤｉｓｐｅｒｂｙｋ（登録商標）（ビックケミー（株）製）、ＢＹＫ（登録商標）（ビックケミー（株）製）等が挙げられる。また、分散剤として、後述する樹脂（Ｂ）（好ましくは樹脂［Ｋ１］、より好ましくは３，４－エポキシトリシクロ［５．２．１．０2.6］デシルアクリレート／（メタ）アクリル酸共重合体）を用いてもよい。分散剤は、上記のアクリル系分散剤及び樹脂（Ｂ）を含むことが好ましく、銅フタロシアニン誘導体を含まないことが好ましい。 Examples of the dispersant include surfactants, which may be cationic, anionic, nonionic, or amphoteric. Specific examples include polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. Examples of the dispersant, when expressed by trade name, include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWRENE (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.). In addition, as the dispersant, a resin (B) described later (preferably resin [K1], more preferably 3,4-epoxytricyclo[5.2.1.0 2.6 ]decyl acrylate/(meth)acrylic acid copolymer) may be used. The dispersant preferably contains the above-mentioned acrylic dispersant and resin (B), and preferably does not contain a copper phthalocyanine derivative.
　分散剤を用いる場合、該分散剤（固形分）の使用量は、着色剤含有液中の着色剤（Ａ）１００質量部に対して、通常１質量部以上１００００質量部以下であり、好ましくは５質量部以上５０００質量部以下であり、より好ましくは１０質量部以上１０００質量部以下であり、さらに好ましくは１５質量部以上８００質量部以下である。該分散剤の使用量が前記の範囲にあると、より均一な分散状態の着色剤含有液（以下、着色剤分散液又は顔料分散液という場合がある）が得られる傾向がある。 When a dispersant is used, the amount of the dispersant (solid content) used is usually 1 part by mass to 10,000 parts by mass, preferably 5 parts by mass to 5,000 parts by mass, more preferably 10 parts by mass to 1,000 parts by mass, and even more preferably 15 parts by mass to 800 parts by mass, per 100 parts by mass of colorant (A) in the colorant-containing liquid. When the amount of the dispersant used is within the above range, a colorant-containing liquid (hereinafter sometimes referred to as a colorant dispersion or pigment dispersion) in a more uniformly dispersed state tends to be obtained.
　着色剤（Ａ）と溶剤（Ｅ）とを含む着色剤含有液を予め調製した後、該着色剤含有液を使用して着色硬化性樹脂組成物を調製する場合、着色剤含有液は、着色硬化性樹脂組成物に含有される樹脂（Ｂ）の一部又は全部、好ましくは一部を予め含んでいてもよい。樹脂（Ｂ）を予め含ませておくことで、着色剤含有液の分散安定性をさらに改善できる。 When a colorant-containing liquid containing a colorant (A) and a solvent (E) is prepared in advance and then the colorant-containing liquid is used to prepare a colored curable resin composition, the colorant-containing liquid may already contain a part or all, preferably a part, of the resin (B) contained in the colored curable resin composition. By including the resin (B) in advance, the dispersion stability of the colorant-containing liquid can be further improved.
　着色剤含有液が樹脂（Ｂ）を含有する場合、樹脂（Ｂ）の含有量は、着色剤含有液中の着色剤（Ａ）１００質量部に対して、例えば、１０質量部以上１００００質量部以下であり、２０質量部以上５０００質量部以下が好ましく、２５質量部以上２５００質量部以下がより好ましい。 When the colorant-containing liquid contains resin (B), the content of resin (B) is, for example, 10 parts by mass or more and 10,000 parts by mass or less, preferably 20 parts by mass or more and 5,000 parts by mass or less, and more preferably 25 parts by mass or more and 2,500 parts by mass or less, relative to 100 parts by mass of colorant (A) in the colorant-containing liquid.
　着色剤（Ａ）の含有率は、着色硬化性樹脂組成物の固形分の総量中、好ましくは１質量％以上８０質量％以下であり、より好ましくは１０質量％以上７０質量％以下であり、さらに好ましくは１５質量％以上６５質量％以下であり、よりさらに好ましくは１８質量％以上５０質量％以下である。着色剤（Ａ）の含有率が前記の範囲にあると、カラーフィルタとしたときの色濃度が十分であり、かつ組成物中に樹脂（Ｂ）を必要量含有させることができるので、機械的強度が十分なパターンを形成することができることから好ましい。
　着色剤（Ａ）の含有率は、着色硬化性樹脂組成物の固形分の総量中、３６質量％超、９０質量％以下であることが特に好ましく、３８質量％以上、８５質量％以下であることが最も好ましい。着色剤（Ａ）の含有率が上記の範囲にあると、カラーフィルタの濃色化が可能となる。
　ここで、本明細書における「固形分の総量」とは、着色硬化性樹脂組成物の総量から溶剤の含有量を除いた量のことをいう。固形分の総量及びこれに対する各成分の含有量は、例えば、液体クロマトグラフィー又はガスクロマトグラフィーなどの公知の分析手段で測定することができる。 The content of the colorant (A) is preferably 1% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, even more preferably 15% by mass or more and 65% by mass or less, and even more preferably 18% by mass or more and 50% by mass or less, based on the total amount of solids in the colored curable resin composition. When the content of the colorant (A) is within the above range, the color density when made into a color filter is sufficient, and the necessary amount of the resin (B) can be contained in the composition, so that a pattern with sufficient mechanical strength can be formed, which is preferable.
The content of the colorant (A) is particularly preferably more than 36% by mass and not more than 90% by mass, and most preferably 38% by mass or more and 85% by mass or less, based on the total amount of solids in the colored curable resin composition. When the content of the colorant (A) is in the above range, the color of the color filter can be darkened.
Here, the "total amount of solids" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.
＜樹脂（Ｂ）＞
　樹脂（Ｂ）は、特に限定されないが、アルカリ可溶性樹脂であることが好ましい。樹脂（Ｂ）としては、以下の樹脂［Ｋ１］～［Ｋ６］等が挙げられ、樹脂［Ｋ１］から［Ｋ６］から選ばれる少なくとも１つであることが好ましい。
　樹脂［Ｋ１］；不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種の単量体（ａ）（以下「（ａ）」という場合がある）に由来する構造単位と、炭素数２～４の環状エーテル構造とエチレン性不飽和結合とを有する単量体（ｂ）（以下「（ｂ）」という場合がある）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ２］；前記（ａ）に由来する構造単位と前記（ｂ）に由来する構造単位と、（ａ）と共重合可能な単量体（ｃ）（ただし、（ａ）及び（ｂ）とは異なる。）（以下「（ｃ）」という場合がある）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ３］；前記（ａ）に由来する構造単位と前記（ｃ）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ４］；前記（ａ）に由来する構造単位に前記（ｂ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体（好ましくは（ｂ）が付加しない（ａ）に由来する構造単位を含む）；
　樹脂［Ｋ５］；前記（ｂ）に由来する構造単位に前記（ａ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体（（ａ）が付加しない（ｂ）に由来する構造単位を含んでもよいが、含まないことが好ましい）；
　樹脂［Ｋ５’］；前記（ａ）に由来する構造単位に前記（ｂ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体（（ｂ）が付加しない（ａ）に由来する構造単位を含んでもよいが、含まないことが好ましい）；
　樹脂［Ｋ６］；前記（ｂ）に由来する構造単位に前記（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体。 <Resin (B)>
Resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of resin (B) include the following resins [K1] to [K6], and it is preferably at least one selected from resins [K1] to [K6].
Resin [K1]: a copolymer having a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
Resin [K2]: a copolymer having a structural unit derived from the (a), a structural unit derived from the (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, may be referred to as "(c)");
Resin [K3]: a copolymer having a structural unit derived from the (a) and a structural unit derived from the (c);
Resin [K4]: a copolymer having a structural unit derived from the (a) and a structural unit derived from the (c) (preferably containing a structural unit derived from the (a) to which the (b) is not added);
Resin [K5]: a copolymer having a structural unit in which the (a) is added to a structural unit derived from the (b) and a structural unit derived from the (c) (which may contain a structural unit derived from the (b) to which the (a) is not added, but preferably does not contain such a structural unit);
Resin [K5']: a copolymer having a structural unit derived from the (a) to which the (b) has been added and a structural unit derived from the (c) (which may contain, but preferably does not contain, a structural unit derived from the (a) to which the (b) has not been added);
Resin [K6]: A copolymer having a structural unit obtained by adding the (a) to a structural unit derived from the (b) and further adding a carboxylic acid anhydride, and a structural unit derived from the (c).
　（ａ）としては、具体的には、例えば、アクリル酸、メタクリル酸、クロトン酸、ｏ－、ｍ－、ｐ－ビニル安息香酸等の不飽和モノカルボン酸類；
　マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、３－ビニルフタル酸、４－ビニルフタル酸、３，４，５，６－テトラヒドロフタル酸、１，２，３，６－テトラヒドロフタル酸、ジメチルテトラヒドロフタル酸、１、４－シクロヘキセンジカルボン酸等の不飽和ジカルボン酸類；
　メチル－５－ノルボルネン－２，３－ジカルボン酸、５－カルボキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－６－メチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－６－エチルビシクロ［２．２．１］ヘプト－２－エン等のカルボキシ基を含有するビシクロ不飽和化合物類；
　無水マレイン酸、シトラコン酸無水物、イタコン酸無水物、３－ビニルフタル酸無水物、４－ビニルフタル酸無水物、３，４，５，６－テトラヒドロフタル酸無水物、１，２，３，６－テトラヒドロフタル酸無水物、ジメチルテトラヒドロフタル酸無水物、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン無水物等の不飽和ジカルボン酸類無水物；
　こはく酸モノ〔２－（メタ）アクリロイルオキシエチル〕、フタル酸モノ〔２－（メタ）アクリロイルオキシエチル〕等の２価以上の多価カルボン酸の不飽和モノ〔（メタ）アクリロイルオキシアルキル〕エステル類；
　α－（ヒドロキシメチル）アクリル酸のような、同一分子中にヒドロキシ基及びカルボキシ基を含有する不飽和アクリレート類等が挙げられる。
　これらのうち、共重合反応性の点や得られる樹脂のアルカリ水溶液への溶解性の点から、アクリル酸、メタクリル酸、無水マレイン酸等が好ましい。 Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and 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 a carboxy group, 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-5-ethylbicyclo[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;
Unsaturated dicarboxylic acid anhydrides such as 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]hept-2-ene anhydride;
Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the standpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkaline solution.
　（ｂ）は、例えば、炭素数２～４の環状エーテル構造（例えば、オキシラン環、オキセタン環及びテトラヒドロフラン環からなる群から選ばれる少なくとも１種）とエチレン性不飽和結合とを有する重合性化合物をいう。（ｂ）は、炭素数２～４の環状エーテルと（メタ）アクリロイルオキシ基とを有する単量体が好ましい。
　尚、本明細書において、「（メタ）アクリル酸」とは、アクリル酸及びメタクリル酸よりなる群から選ばれる少なくとも１種を表す。「（メタ）アクリロイル」及び「（メタ）アクリレート」等の表記も、同様の意味を有する。 (b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
In this specification, the term "(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.
　（ｂ）としては、例えば、オキシラニル基とエチレン性不飽和結合とを有する単量体（ｂ１）（以下「（ｂ１）」という場合がある）、オキセタニル基とエチレン性不飽和結合とを有する単量体（ｂ２）（以下「（ｂ２）」という場合がある）、テトラヒドロフリル基とエチレン性不飽和結合とを有する単量体（ｂ３）（以下「（ｂ３）」という場合がある）等が挙げられる。 Examples of (b) include 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 sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.
　（ｂ１）としては、例えば、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）（以下「（ｂ１－１）」という場合がある）、脂環式不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－２）（以下「（ｂ１－２）」という場合がある）が挙げられる。 Examples of (b1) include monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.
　（ｂ１－１）としては、グリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート、β－エチルグリシジル（メタ）アクリレート、グリシジルビニルエーテル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、α－メチル－ｏ－ビニルベンジルグリシジルエーテル、α－メチル－ｍ－ビニルベンジルグリシジルエーテル、α－メチル－ｐ－ビニルベンジルグリシジルエーテル、２，３－ビス（グリシジルオキシメチル）スチレン、２，４－ビス（グリシジルオキシメチル）スチレン、２，５－ビス（グリシジルオキシメチル）スチレン、２，６－ビス（グリシジルオキシメチル）スチレン、２，３，４－トリス（グリシジルオキシメチル）スチレン、２，３，５－トリス（グリシジルオキシメチル）スチレン、２，３，６－トリス（グリシジルオキシメチル）スチレン、３，４，５－トリス（グリシジルオキシメチル）スチレン、２，４，６－トリス（グリシジルオキシメチル）スチレン等が挙げられる。 (b1-1) includes glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl Examples include 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.
　（ｂ１－２）としては、ビニルシクロヘキセンモノオキサイド、１，２－エポキシ－４－ビニルシクロヘキサン（例えば、セロキサイド２０００；（株）ダイセル製）、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート（例えば、サイクロマーＡ４００；（株）ダイセル製）、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート（例えば、サイクロマーＭ１００；（株）ダイセル製）、式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物等が挙げられる。 (b1-2) includes vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 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 (I) and compounds represented by formula (II).
Figure JPOXMLDOC01-appb-I000003
Figure JPOXMLDOC01-appb-I000003
［式（Ｉ）及び式（ＩＩ）中、Ｒａ及びＲｂは、水素原子、又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
　Ｘａ及びＸｂは、単結合、＊－Ｒｃ－、＊－Ｒｃ－Ｏ－、＊－Ｒｃ－Ｓ－又は＊－Ｒｃ－ＮＨ－を表す。
　Ｒｃは、炭素数１～６のアルカンジイル基を表す。
　＊は、Ｏとの結合手を表す。］ In formula (I) and formula (II), R a and R b 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 hydroxy group.
Xa and Xb each represent a single bond, *-R c -, *-R c -O-, *-R c -S- or *-R c -NH-.
Rc represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond to O.
　炭素数１～４のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等が挙げられる。
　水素原子がヒドロキシで置換されたアルキル基としては、ヒドロキシメチル基、１－ヒドロキシエチル基、２－ヒドロキシエチル基、１－ヒドロキシプロピル基、２－ヒドロキシプロピル基、３－ヒドロキシプロピル基、１－ヒドロキシ－１－メチルエチル基、２－ヒドロキシ－１－メチルエチル基、１－ヒドロキシブチル基、２－ヒドロキシブチル基、３－ヒドロキシブチル基、４－ヒドロキシブチル基等が挙げられる。
　Ｒａ及びＲｂとしては、好ましくは水素原子、メチル基、ヒドロキシメチル基、１－ヒドロキシエチル基、２－ヒドロキシエチル基が挙げられ、より好ましくは水素原子、メチル基が挙げられる。 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, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group 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, and a 4-hydroxybutyl group.
R a and R b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.
　アルカンジイル基としては、メチレン基、エチレン基、プロパン－１，２－ジイル基、プロパン－１，３－ジイル基、ブタン－１，４－ジイル基、ペンタン－１，５－ジイル基、ヘキサン－１，６－ジイル基等が挙げられる。
　Ｘａ及びＸｂとしては、好ましくは単結合、メチレン基、エチレン基、＊－ＣＨ２－Ｏ－及び＊－ＣＨ２ＣＨ２－Ｏ－が挙げられ、より好ましくは単結合、＊－ＣＨ２ＣＨ２－Ｏ－が挙げられる（＊はＯとの結合手を表す）。 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, and a hexane-1,6-diyl group.
Xa and Xb are preferably a single bond, a methylene group, an ethylene group, *-CH 2 -O-, and *-CH 2 CH 2 -O-, and more preferably a single bond or *-CH 2 CH 2 -O- (* represents a bond to O).
　式（Ｉ）で表される化合物としては、式（Ｉ－１）～式（Ｉ－１５）のいずれかで表される化合物等が挙げられる。中でも、式（Ｉ－１）、式（Ｉ－３）、式（Ｉ－５）、式（Ｉ－７）、式（Ｉ－９）又は式（Ｉ－１１）～式（Ｉ－１５）で表される化合物が好ましく、式（Ｉ－１）、式（Ｉ－７）、式（Ｉ－９）又は式（Ｉ－１５）で表される化合物がより好ましい。 The compound represented by formula (I) includes compounds represented by any of formulas (I-1) to (I-15). Among them, compounds represented by formulas (I-1), (I-3), (I-5), (I-7), (I-9) or (I-11) to (I-15) are preferred, and compounds represented by formulas (I-1), (I-7), (I-9) or (I-15) are more preferred.
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000005
　式（ＩＩ）で表される化合物としては、式（ＩＩ－１）～式（ＩＩ－１５）のいずれかで表される化合物等が挙げられる。中でも、式（ＩＩ－１）、式（ＩＩ－３）、式（ＩＩ－５）、式（ＩＩ－７）、式（ＩＩ－９）又は式（ＩＩ－１１）～式（ＩＩ－１５）で表される化合物が好ましく、式（ＩＩ－１）、式（ＩＩ－７）、式（ＩＩ－９）又は式（ＩＩ－１５）で表される化合物がより好ましい。 The compound represented by formula (II) may be any of the compounds represented by formulas (II-1) to (II-15). Among them, compounds represented by formulas (II-1), (II-3), (II-5), (II-7), (II-9) or (II-11) to (II-15) are preferred, and compounds represented by formulas (II-1), (II-7), (II-9) or (II-15) are more preferred.
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000007
　式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物は、それぞれ単独で用いても、２種以上を併用してもよい。式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物を併用する場合、これらの含有比率〔式（Ｉ）で表される化合物：式（ＩＩ）で表される化合物〕はモル基準で、好ましくは５：９５～９５：５、より好ましくは２０：８０～８０：２０である。 The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more kinds. When the compound represented by formula (I) and the compound represented by formula (II) are used in combination, the content ratio thereof [compound represented by formula (I): compound represented by formula (II)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.
　（ｂ２）としては、オキセタニル基と（メタ）アクリロイルオキシ基とを有する単量体がより好ましい。（ｂ２）としては、３－メチル－３－メタクリルロイルオキシメチルオキセタン、３－メチル－３－アクリロイルオキシメチルオキセタン、３－エチル－３－メタクリロイルオキシメチルオキセタン、３－エチル－３－アクリロイルオキシメチルオキセタン、３－メチル－３－メタクリロイルオキシエチルオキセタン、３－メチル－３－アクリロイルオキシエチルオキセタン、３－エチル－３－メタクリロイルオキシエチルオキセタン、３－エチル－３－アクリロイルオキシエチルオキセタン等が挙げられる。 More preferably, (b2) is a monomer having an oxetanyl group and a (meth)acryloyloxy group. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, and the like.
　（ｂ３）としては、テトラヒドロフリル基と（メタ）アクリロイルオキシ基とを有する単量体がより好ましい。（ｂ３）としては、具体的には、テトラヒドロフルフリルアクリレート（例えば、ビスコートＶ＃１５０、大阪有機化学工業（株）製）、テトラヒドロフルフリルメタクリレート等が挙げられる。 As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.
　（ｂ）としては、得られるカラーフィルタの耐熱性、耐薬品性等の信頼性をより高くすることができる点で、（ｂ１）であることが好ましい。さらに、着色硬化性樹脂組成物の保存安定性が優れるという点で、（ｂ１－２）がより好ましい。 As (b), (b1) is preferable since it can improve the reliability of the heat resistance, chemical resistance, etc. of the obtained color filter. Furthermore, (b1-2) is more preferable since the storage stability of the colored curable resin composition is excellent.
　（ｃ）としては、（メタ）アクリル酸エステル系モノマー、不飽和ジカルボン酸エステルなどの不飽和カルボン酸エステル類；不飽和脂肪族炭化水素環、不飽和複素環、または芳香族環を有するビニルモノマーなどが挙げられる。
　（メタ）アクリル酸エステル系モノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロペンチル（メタ）アクリレートなどの直鎖又は分岐鎖の脂肪族飽和炭化水素基を有する（メタ）アクリル酸エステル類（好ましくは、Ｃ１－１０アルキル（メタ）アクリレート）；
　アリル（メタ）アクリレート、プロパルギル（メタ）アクリレートなどの直鎖又は分岐鎖の脂肪族不飽和炭化水素基を有する（メタ）アクリル酸エステル類；
　シクロヘキシル（メタ）アクリレート、２－メチルシクロヘキシル（メタ）アクリレート、トリシクロ［５．２．１．０2,6］デカン－８－イル（メタ）アクリレート（当該技術分野では、慣用名として「ジシクロペンタニル（メタ）アクリレート」といわれている。また、「トリシクロデシル（メタ）アクリレート」という場合がある。）、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレートなどの環状飽和炭化水素基を有する（メタ）アクリル酸エステル類；
　トリシクロ［５．２．１．０2,6］デセン－８－イル（メタ）アクリレート（当該技術分野では、慣用名として「ジシクロペンテニル（メタ）アクリレート」といわれている。）、ジシクロペンタニルオキシエチル（メタ）アクリレートなどの環状不飽和脂肪族炭化水素基を有する（メタ）アクリル酸エステル類；
　フェニル（メタ）アクリレート、ナフチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシベンジル（メタ）アクリレート等の芳香族環を有する（メタ）アクリル酸エステル類；
　２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシ基含有（メタ）アクリル酸エステル類が挙げられる。
　不飽和ジカルボン酸エステルとしては、マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル等のジカルボン酸ジエステルが挙げられる。 Examples of (c) include (meth)acrylic acid ester monomers, unsaturated carboxylates such as unsaturated dicarboxylates, and vinyl monomers having an unsaturated aliphatic hydrocarbon ring, an unsaturated heterocycle, or an aromatic ring.
Examples of the (meth)acrylic acid ester monomer include (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group, such as 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, and cyclopentyl (meth)acrylate (preferably, C 1-10 alkyl (meth)acrylate);
(meth)acrylic acid esters having a linear or branched aliphatic unsaturated hydrocarbon group, such as allyl (meth)acrylate and propargyl (meth)acrylate;
(meth)acrylic acid esters having a cyclic saturated hydrocarbon group, such as cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]decan-8-yl (meth)acrylate (commonly known in the technical field as "dicyclopentanyl (meth)acrylate" and sometimes called "tricyclodecyl (meth)acrylate"), isobornyl (meth)acrylate, and adamantyl (meth)acrylate;
(meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, such as tricyclo[5.2.1.0 2,6 ]decen-8-yl(meth)acrylate (commonly known as "dicyclopentenyl(meth)acrylate" in the technical field), and dicyclopentanyloxyethyl(meth)acrylate;
(meth)acrylic acid esters having an aromatic ring, such as phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, and phenoxybenzyl (meth)acrylate;
Examples of the hydroxyl group-containing (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.
Examples of the unsaturated dicarboxylic acid ester include dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate.
　これらの不飽和カルボン酸エステル類のうち、メチルメタクリレート、２－エチルヘキシルアクリレートなどのＣ１－１０アルキル（メタ）アクリレート；
トリシクロ［５．２．１．０2,6］デカン－８－イル（メタ）アクリレートなどの環状飽和炭化水素基を有する（メタ）アクリル酸エステル類；
トリシクロ［５．２．１．０2,6］デセン－８－イル（メタ）アクリレートなどの環状不飽和脂肪族炭化水素基を有する（メタ）アクリル酸エステル類；
　ベンジル（メタ）アクリレート、フェノキシベンジル（メタ）アクリレート等の芳香族環を有する（メタ）アクリル酸エステル類などが好ましい。 Among these unsaturated carboxylic acid esters, C 1-10 alkyl (meth)acrylates such as methyl methacrylate and 2-ethylhexyl acrylate;
(meth)acrylic acid esters having a cyclic saturated hydrocarbon group, such as tricyclo[5.2.1.0 2,6 ]decan-8-yl(meth)acrylate;
(meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, such as tricyclo[5.2.1.0 2,6 ]decene-8-yl (meth)acrylate;
Preferred are (meth)acrylic acid esters having an aromatic ring, such as benzyl (meth)acrylate and phenoxybenzyl (meth)acrylate.
　不飽和脂肪族炭化水素環を有するビニルモノマーとしては、ビシクロ［２．２．１］ヘプト－２－エン（または２－ノルボルネンともいう）、５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシメチルビシクロ［２．２．１］ヘプト－２－エン、５－（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５－メトキシビシクロ［２．２．１］ヘプト－２－エン、５－エトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジヒドロキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジ（ヒドロキシメチル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ジ（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ジメトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジエトキシビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシ－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシ－５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシメチル－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－ｔｅｒｔ－ブトキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－シクロヘキシルオキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－フェノキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５，６－ビス（ｔｅｒｔ－ブトキシカルボニル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ビス（シクロヘキシルオキシカルボニル）ビシクロ［２．２．１］ヘプト－２－エン等のビシクロ不飽和化合物類が挙げられる。
　不飽和複素環を有するビニルモノマーとしては、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド、Ｎ－スクシンイミジル－３－マレイミドベンゾエート、Ｎ－スクシンイミジル－４－マレイミドブチレート、Ｎ－スクシンイミジル－６－マレイミドカプロエート、Ｎ－スクシンイミジル－３－マレイミドプロピオネート、Ｎ－（９－アクリジニル）マレイミド等のジカルボニルイミド誘導体類が挙げられる。
　芳香族環を有するビニルモノマーとしては、スチレン、α－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ビニルトルエン、ｐ－メトキシスチレンなどのスチレン系モノマーが挙げられる。
　その他のビニルモノマーとして、アクリロニトリル、メタクリロニトリルなどのニトリル基含有モノマー；
　塩化ビニル、塩化ビニリデンなどのハロゲン原子含有モノマー；
　アクリルアミド、メタクリルアミド、酢酸ビニル、１，３－ブタジエン、イソプレン、２，３－ジメチル－１，３－ブタジエン等が挙げられる。
　これらのビニルモノマーのうち、共重合反応性及び耐熱性の点から、スチレン、ビニルトルエンなどのスチレン系モノマー、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミドなどのジカルボニルイミド誘導体、ビシクロ［２．２．１］ヘプト－２－エン（または２－ノルボルネンともいう）等のビシクロ不飽和化合物が好ましい。 Examples of vinyl monomers having an unsaturated aliphatic hydrocarbon ring include bicyclo[2.2.1]hept-2-ene (also called 2-norbornene), 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'-hydroxy 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6- Dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1 ]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene are examples of bicyclo unsaturated compounds.
Examples of vinyl monomers having an unsaturated heterocycle include dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide.
Examples of vinyl monomers having an aromatic ring include styrene-based monomers such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.
Other vinyl monomers include nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Halogen atom-containing monomers such as vinyl chloride and vinylidene chloride;
Examples of the monomer include acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
Among these vinyl monomers, from the viewpoints of copolymerization reactivity and heat resistance, styrene-based monomers such as styrene and vinyltoluene, dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide, and bicyclo unsaturated compounds such as bicyclo[2.2.1]hept-2-ene (also called 2-norbornene) are preferred.
　（ａ）に由来する構造単位に（ｂ）を付加させた構造単位とは、共重合体の主鎖を構成する（ａ）由来の構造単位に付加によって（ｂ）が結合して構成される単位のことをいい、（ｂ）に由来するペンダント不飽和基を有する。この構造単位において、（ａ）は前記例示のいずれでもよく、（ｂ）も前記例示のいずれでもよい。（ａ）としては、（メタ）アクリル酸などの不飽和モノカルボン酸が好ましい。（ｂ）としては、オキシラニル基とエチレン性不飽和結合とを有する単量体（ｂ１）が好ましく、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）がより好ましい。 The structural unit obtained by adding (b) to a structural unit derived from (a) refers to a unit formed by bonding (b) by addition to a structural unit derived from (a) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (b). In this structural unit, (a) may be any of the above-mentioned examples, and (b) may also be any of the above-mentioned examples. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable. As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable.
　（ｂ）に由来する構造単位に（ａ）を付加させた構造単位とは、共重合体の主鎖を構成する（ｂ）由来の構造単位に付加によって（ａ）が結合して構成される単位のことをいい、（ａ）に由来するペンダント不飽和基を有する。この構造単位において、（ｂ）は前記例示のいずれでもよく、（ａ）も前記例示のいずれでもよい。（ｂ）としては、オキシラニル基とエチレン性不飽和結合とを有する単量体（ｂ１）が好ましく、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）がより好ましい。（ａ）としては、（メタ）アクリル酸などの不飽和モノカルボン酸が好ましい。 The structural unit obtained by adding (a) to a structural unit derived from (b) refers to a unit formed by bonding (a) by addition to a structural unit derived from (b) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (a). In this structural unit, (b) may be any of the above-mentioned examples, and (a) may also be any of the above-mentioned examples. As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable.
　（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位とは、共重合体の主鎖を構成する（ｂ）由来の構造単位に付加によって（ａ）が結合して生じる水酸基に、カルボン酸無水物がハーフエステル化することによって結合した構造単位のことをいい、カルボン酸無水物に由来するペンダントカルボキシ基と、（ａ）に由来するペンダント不飽和基を有する。この構造単位において、（ｂ）は前記例示のいずれでもよく、（ａ）も前記例示のいずれでもよい。（ｂ）としては、オキシラニル基とエチレン性不飽和結合とを有する単量体（ｂ１）が好ましく、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）がより好ましい。（ａ）としては、（メタ）アクリル酸などの不飽和モノカルボン酸が好ましい。
　カルボン酸無水物としては、マロン酸無水物、コハク酸無水物、グルタル酸無水物、アジピン酸無水物などの飽和脂肪族多価カルボン酸無水物；無水マレイン酸、シトラコン酸無水物、イタコン酸無水物などの不飽和脂肪族多価カルボン酸無水物；３－ビニルフタル酸無水物、４－ビニルフタル酸無水物などの芳香族多価カルボン酸無水物；３，４，５，６－テトラヒドロフタル酸無水物、１，２，３，６－テトラヒドロフタル酸無水物、ジメチルテトラヒドロフタル酸無水物、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン無水物などの脂環式多価カルボン酸無水物等の多価カルボン酸無水物が挙げられる。 The structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride refers to a structural unit obtained by half-esterification of a carboxylic anhydride to a hydroxyl group generated by adding (a) to a structural unit derived from (b) constituting the main chain of the copolymer, and has a pendant carboxyl group derived from the carboxylic anhydride and a pendant unsaturated group derived from (a). In this structural unit, (b) may be any of the above-mentioned examples, and (a) may also be any of the above-mentioned examples. As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable.
Examples of the carboxylic acid anhydride include saturated aliphatic polycarboxylic acid anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adipic anhydride; unsaturated aliphatic polycarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; aromatic polycarboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride; and alicyclic polycarboxylic acid anhydrides such as 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.
　樹脂［Ｋ１］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ１］を構成する全構造単位中、
（ａ）に由来する構造単位；２～６０モル％
（ｂ）に由来する構造単位；４０～９８モル％
であることが好ましく、
（ａ）に由来する構造単位；１０～５０モル％
（ｂ）に由来する構造単位；５０～９０モル％
であることがより好ましい。
　また（ｃ）に由来する構造単位は実質的に含まないことが好ましい。
　（ａ）に由来する構造単位と（ｂ）に由来する構造単位の合計は、樹脂［Ｋ１］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。
　樹脂［Ｋ１］の構造単位の比率が、上記の範囲にあると、着色硬化性樹脂組成物の保存安定性、着色パターンを形成する際の現像性、及び得られるカラーフィルタの耐溶剤性に優れる傾向がある。 In the resin [K1], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K1] is as follows:
Structural units derived from (a): 2 to 60 mol%
Structural units derived from (b): 40 to 98 mol%
It is preferred that
Structural units derived from (a): 10 to 50 mol %
Structural units derived from (b): 50 to 90 mol%
It is more preferable that:
It is also preferred that the copolymer contains substantially no structural units derived from (c).
The total of the structural units derived from (a) and the structural units derived from (b) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K1].
When the ratio of the structural units of the resin [K1] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and solvent resistance of the obtained color filter.
　樹脂［Ｋ１］は、例えば、文献「高分子合成の実験法」（大津隆行著　発行所（株）化学同人　第１版第１刷　１９７２年３月１日発行）に記載された方法及び当該文献に記載された引用文献を参考にして製造することができる。 Resin [K1] can be produced, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (written by Otsu Takayuki, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the references cited in said literature.
　具体的には、（ａ）及び（ｂ）の所定量、重合開始剤及び溶剤等を反応容器中に入れて、例えば、窒素により酸素を置換することにより、脱酸素雰囲気にし、攪拌しながら、加熱及び保温する方法が挙げられる。なお、ここで用いられる重合開始剤及び溶剤等は、特に限定されず、当該分野で通常使用されているものを使用することができる。例えば、重合開始剤としては、アゾ化合物（２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）等）や有機過酸化物（ベンゾイルペルオキシド等）が挙げられ、溶剤としては、各モノマーを溶解するものであればよく、本発明の着色硬化性樹脂組成物の溶剤（Ｅ）として後述する溶剤等が挙げられる。 Specific examples include a method in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and the atmosphere is deoxygenated, for example by replacing oxygen with nitrogen, and the mixture is heated and kept warm while stirring. The polymerization initiator and solvent used here are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.), and the solvent may be any that dissolves each monomer, such as the solvent (E) described below for the colored curable resin composition of the present invention.
　なお、得られた共重合体は、反応後の溶液をそのまま使用してもよいし、濃縮あるいは希釈した溶液を使用してもよいし、再沈殿等の方法で固体（粉体）として取り出したものを使用してもよい。特に、この重合の際に溶剤として、本発明の着色硬化性樹脂組成物に含まれる溶剤を使用することにより、反応後の溶液をそのまま本発明の着色硬化性樹脂組成物の調製に使用することができるため、本発明の着色硬化性樹脂組成物の製造工程を簡略化することができる。 The copolymer obtained may be used as it is in the solution after the reaction, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as the solvent during this polymerization, the solution after the reaction can be used as it is in the preparation of the colored curable resin composition of the present invention, and the manufacturing process of the colored curable resin composition of the present invention can be simplified.
　樹脂［Ｋ２］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ２］を構成する全構造単位中、
（ａ）に由来する構造単位；２～４５モル％
（ｂ）に由来する構造単位；２～９５モル％
（ｃ）に由来する構造単位；１～６５モル％
であることが好ましく、
（ａ）に由来する構造単位；５～４０モル％
（ｂ）に由来する構造単位；５～８０モル％
（ｃ）に由来する構造単位；５～６０モル％
であることがより好ましく、
（ａ）に由来する構造単位；１０～３０モル％
（ｂ）に由来する構造単位；１０～７０モル％
（ｃ）に由来する構造単位；１０～４０モル％
であることがよりさらに好ましい。
　（ａ）に由来する構造単位、（ｂ）に由来する構造単位、及び（ｃ）に由来する構造単位の合計は、樹脂［Ｋ２］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。
　樹脂［Ｋ２］の構造単位の比率が、上記の範囲にあると、着色硬化性樹脂組成物の保存安定性、着色パターンを形成する際の現像性、並びに、得られるカラーフィルタの耐溶剤性、耐熱性及び機械強度に優れる傾向がある。 In the resin [K2], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K2] is as follows:
Structural units derived from (a): 2 to 45 mol%
Structural units derived from (b): 2 to 95 mol%
Structural units derived from (c): 1 to 65 mol%
It is preferred that
Structural units derived from (a): 5 to 40 mol%
Structural units derived from (b): 5 to 80 mol%
Structural units derived from (c): 5 to 60 mol%
It is more preferable that
Structural units derived from (a): 10 to 30 mol %
Structural units derived from (b): 10 to 70 mol%
Structural units derived from (c): 10 to 40 mol%
It is even more preferred that:
The total of the structural units derived from (a), the structural units derived from (b), and the structural units derived from (c) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K2].
When the ratio of the structural units of the resin [K2] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and the obtained color filter tends to have excellent solvent resistance, heat resistance, and mechanical strength.
　樹脂［Ｋ２］において（ａ）は（メタ）アクリル酸などの不飽和モノカルボン酸が好ましい。（ｂ）としてはオキシラニル基とエチレン性不飽和結合とを有する単量体（ｂ１）が好ましく、脂環式不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－２）がより好ましい。（ｃ）としては、環状不飽和脂肪族炭化水素基を有する（メタ）アクリル酸エステル類、芳香族環を有する（メタ）アクリル酸エステル類、ジカルボニルイミド誘導体が好ましい。 In the resin [K2], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferred, and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized is more preferred. As (c), (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, and dicarbonyl imide derivatives are preferred.
　樹脂［Ｋ２］は、例えば、樹脂［Ｋ１］の製造方法として記載した方法と同様に製造することができる。 Resin [K2] can be produced, for example, in the same manner as described above for producing resin [K1].
　樹脂［Ｋ３］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ３］を構成する全構造単位中、
（ａ）に由来する構造単位；２～６０モル％
（ｃ）に由来する構造単位；４０～９８モル％
であることが好ましく、
（ａ）に由来する構造単位；１０～５０モル％
（ｃ）に由来する構造単位；５０～９０モル％
であることがより好ましく、
（ａ）に由来する構造単位；３５～４５モル％
（ｃ）に由来する構造単位；５５～６５モル％
であることがよりさらに好ましい。
　また（ｂ）に由来する構造単位は実質的に含まないことが好ましい。
　（ａ）に由来する構造単位と（ｃ）に由来する構造単位の合計は、樹脂［Ｋ３］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。 In the resin [K3], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K3] is as follows:
Structural units derived from (a): 2 to 60 mol%
Structural units derived from (c): 40 to 98 mol%
It is preferred that
Structural units derived from (a): 10 to 50 mol %
Structural units derived from (c): 50 to 90 mol%
It is more preferable that
Structural units derived from (a): 35 to 45 mol%
Structural units derived from (c): 55 to 65 mol%
It is even more preferred that:
It is also preferred that the copolymer is substantially free of structural units derived from (b).
The total of the structural units derived from (a) and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all the structural units constituting the resin [K3].
　樹脂［Ｋ３］において（ａ）は（メタ）アクリル酸などの不飽和モノカルボン酸が好ましい。（ｃ）は芳香族環を有する（メタ）アクリル酸エステル類が好ましい。
　樹脂［Ｋ３］は、例えば、樹脂［Ｋ１］の製造方法として記載した方法と同様に製造することができる。 In the resin [K3], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid, and (c) is preferably a (meth)acrylic acid ester having an aromatic ring.
Resin [K3] can be produced, for example, in the same manner as described above for producing resin [K1].
　樹脂［Ｋ４］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ４］を構成する全構造単位中、
（ａ）に由来する構造単位（（ｂ）は付加していない）；１～６０モル％
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；１～５０モル％
（ｃ）に由来する構造単位；３０～９０モル％
であることが好ましく、
（ａ）に由来する構造単位（（ｂ）は付加していない）；５～５０モル％
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；５～４０モル％
（ｃ）に由来する構造単位；３５～８０モル％
であることがより好ましく、
（ａ）に由来する構造単位（（ｂ）は付加していない）；１０～４０モル％
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；１０～２５モル％
（ｃ）に由来する構造単位；４０～７５モル％
であることがよりさらに好ましい。
　（ａ）に由来する構造単位（（ｂ）は付加していない）と、（ａ）に由来する構造単位に（ｂ）を付加させた構造単位と、（ｃ）に由来する構造単位の合計は、樹脂［Ｋ４］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。 In the resin [K4], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K4] is as follows:
Structural units derived from (a) (without (b) added): 1 to 60 mol%
Structural units obtained by adding (b) to a structural unit derived from (a): 1 to 50 mol %
Structural units derived from (c): 30 to 90 mol%
It is preferred that
Structural units derived from (a) (without (b) added): 5 to 50 mol %
Structural units obtained by adding (b) to a structural unit derived from (a): 5 to 40 mol%
Structural units derived from (c): 35 to 80 mol%
It is more preferable that
Structural units derived from (a) (without (b) added): 10 to 40 mol%
Structural units obtained by adding (b) to a structural unit derived from (a): 10 to 25 mol%
Structural units derived from (c): 40 to 75 mol%
It is even more preferred that:
The total of the structural units derived from (a) (to which (b) is not added), the structural units obtained by adding (b) to the structural units derived from (a), and the structural units derived from (c) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K4].
　（ａ）に由来する構造単位（（ｂ）は付加していない）としては、（メタ）アクリル酸などの不飽和モノカルボン酸に由来する構造単位が好ましい。（ａ）に由来する構造単位に（ｂ）を付加させた構造単位としては、（メタ）アクリル酸などの不飽和モノカルボン酸に由来する構造単位に、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）を付加させた構造単位が好ましい。（ｃ）に由来する構造単位としては、直鎖又は分岐鎖の脂肪族飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状飽和炭化水素基を有する（メタ）アクリル酸エステル類、芳香族環を有する（メタ）アクリル酸エステル類、ビシクロ不飽和化合物、及びスチレン系モノマーから選ばれる１種以上が好ましく、２種以上がより好ましい。（ｃ）に由来する構成単位を２種有する場合の（ｃ）は、（メタ）アクリル酸エステル類、環状飽和炭化水素基を有する（メタ）アクリル酸エステル類、芳香族環を有する（メタ）アクリル酸エステル類などの不飽和カルボン酸エステル類から２種を選択し、ビシクロ不飽和化合物、及びスチレン系モノマーなどのビニルモノマーから選ばれる２種以上を選択することが好ましい。 As the structural unit derived from (a) (without the addition of (b)), a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit in which (b) is added to a structural unit derived from (a), a structural unit in which a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is added to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit derived from (c), one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, bicyclo unsaturated compounds, and styrene-based monomers are preferred, and two or more types are more preferred. When (c) has two types of structural units derived from it, it is preferable to select two types from unsaturated carboxylic acid esters such as (meth)acrylic acid esters, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and (meth)acrylic acid esters having an aromatic ring, and to select two or more types from bicyclo unsaturated compounds and vinyl monomers such as styrene-based monomers.
　樹脂［Ｋ４］は、（ａ）と（ｃ）との共重合体を得て、（ｂ）が有する炭素数２～４の環状エーテルを（ａ）が有するカルボン酸及び／又はカルボン酸無水物に付加させることにより製造することができる。
　まず（ａ）と（ｃ）との共重合体を、樹脂［Ｋ１］の製造方法として記載した方法と同様に製造する。この場合、それぞれに由来する構造単位の比率は、樹脂［Ｋ３］で挙げたもの同じ比率であることが好ましい。 Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and/or carboxylic acid anhydride contained in (a).
First, a copolymer of (a) and (c) is produced in the same manner as described for the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that described for resin [K3].
　次に、前記共重合体中の（ａ）に由来するカルボン酸及び／又はカルボン酸無水物の一部に、（ｂ）が有する炭素数２～４の環状エーテルを反応させる。
　（ａ）と（ｃ）との共重合体の製造に引き続き、フラスコ内雰囲気を窒素から空気に置換し、（ｂ）、カルボン酸又はカルボン酸無水物と環状エーテルとの反応触媒（例えばトリス（ジメチルアミノメチル）フェノール等）及び重合禁止剤（例えばハイドロキノン等）等をフラスコ内に入れて、例えば、６０～１３０℃で、１～１０時間反応することにより、樹脂［Ｋ４］を製造することができる。
　（ｂ）の使用量は、（ａ）１００モルに対して、５～８０モルが好ましく、より好ましくは１０～７５モルである。この範囲にすることにより、着色硬化性樹脂組成物の保存安定性、パターンを形成する際の現像性、並びに、得られるパターンの耐溶剤性、耐熱性、機械強度及び感度のバランスが良好になる傾向がある。
　前記反応触媒の使用量は、（ａ）、（ｂ）及び（ｃ）の合計量１００質量部に対して０．００１～５質量部が好ましい。前記重合禁止剤の使用量は、（ａ）、（ｂ）及び（ｃ）の合計量１００質量部に対して０．００１～５質量部が好ましい。
　仕込方法、反応温度及び時間等の反応条件は、製造設備や重合による発熱量等を考慮して適宜調整することができる。なお、重合条件と同様に、製造設備や重合による発熱量等を考慮し、仕込方法や反応温度を適宜調整することができる。 Next, a part 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 contained in (b).
Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air instead of nitrogen, and (b) a reaction catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the mixture is reacted, for example, at 60 to 130° C. for 1 to 10 hours, thereby producing the resin [K4].
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By using this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good.
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), and 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 charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc. As with the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.
　樹脂［Ｋ５］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ５］を構成する全構造単位中、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～３０モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位；５～９５モル％
（ｃ）に由来する構造単位；５～９５モル％
であることが好ましく、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～１０モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位；１５～９０モル％
（ｃ）に由来する構造単位；１０～８５モル％
であることがより好ましく、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～５モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位；２０～８０モル％
（ｃ）に由来する構造単位；２０～８０モル％
であることがよりさらに好ましい。
　（ｂ）に由来する構造単位（（ａ）は付加していない）と、（ｂ）に由来する構造単位に（ａ）を付加させた構造単位と、（ｃ）に由来する構造単位の合計は、樹脂［Ｋ５］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。
　（ｂ）に由来する構造単位（（ａ）は付加していない）としては、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）に由来する構造単位が好ましい。（ｂ）に由来する構造単位に（ａ）を付加させた構造単位としては、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）に由来する構造単位に（メタ）アクリル酸などの不飽和モノカルボン酸を付加させた構造単位が好ましい。（ｃ）に由来する構造単位としては、直鎖又は分岐鎖の脂肪族飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状飽和炭化水素基を有する（メタ）アクリル酸エステル類から選ばれる１種以上が好ましく、２種以上がより好ましい。 In the resin [K5], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K5] is as follows:
Structural units derived from (b) ((a) is not added): 0 to 30 mol%
Structural units obtained by adding (a) to a structural unit derived from (b): 5 to 95 mol%
Structural units derived from (c): 5 to 95 mol%
It is preferred that
Structural units derived from (b) ((a) is not added): 0 to 10 mol %
Structural units obtained by adding (a) to a structural unit derived from (b): 15 to 90 mol%
Structural units derived from (c): 10 to 85 mol%
It is more preferable that
Structural units derived from (b) ((a) is not added): 0 to 5 mol%
Structural units obtained by adding (a) to a structural unit derived from (b): 20 to 80 mol%
Structural units derived from (c): 20 to 80 mol%
It is even more preferred that:
The total of the structural units derived from (b) (to which (a) is not added), the structural units obtained by adding (a) to the structural units derived from (b), and the structural units derived from (c) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K5].
As the structural unit derived from (b) (without (a) added), a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit in which (a) is added to a structural unit derived from (b), a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit derived from (c), one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group are preferred, and two or more types are more preferred.
　樹脂［Ｋ５］は、第一段階として、上述した樹脂［Ｋ１］の製造方法と同様にして、（ｂ）と（ｃ）との共重合体を得る。上記と同様に、得られた共重合体は、反応後の溶液をそのまま使用してもよいし、濃縮あるいは希釈した溶液を使用してもよいし、再沈殿等の方法で固体（粉体）として取り出したものを使用してもよい。
　（ｂ）及び（ｃ）に由来する構造単位の比率は、前記の共重合体を構成する全構造単位の合計モル数に対して、それぞれ、
（ｂ）に由来する構造単位；５～９５モル％
（ｃ）に由来する構造単位；５～９５モル％
であることが好ましく、
（ｂ）に由来する構造単位；１０～９０モル％
（ｃ）に由来する構造単位；１０～９０モル％
であることがより好ましい。 Resin [K5] is produced in the first step by the same method as the above-mentioned method for producing resin [K1] to obtain a copolymer of (b) and (c). As in the above, the obtained copolymer may be used as a solution after the reaction as it is, a concentrated or diluted solution, or a solid (powder) obtained by a method such as reprecipitation.
The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are, respectively,
Structural units derived from (b): 5 to 95 mol%
Structural units derived from (c): 5 to 95 mol%
It is preferred that
Structural units derived from (b): 10 to 90 mol%
Structural units derived from (c): 10 to 90 mol%
It is more preferable that:
　さらに、樹脂［Ｋ４］の製造方法と同様の条件で、（ｂ）と（ｃ）との共重合体が有する（ｂ）に由来する環状エーテルに、（ａ）が有するカルボン酸又はカルボン酸無水物を反応させることにより、樹脂［Ｋ５］を得ることができる。
　前記の共重合体に反応させる（ａ）の使用量は、（ｂ）１００モルに対して、５～１００モルが好ましい。環状エーテルの反応性が高く、未反応の（ｂ）が残存しにくいことから、樹脂［Ｋ５］に用いる（ｂ）としては（ｂ１）が好ましく、さらに（ｂ１－１）が好ましい。 Furthermore, under the same conditions as in the production method of resin [K4], resin [K5] can be obtained by reacting a cyclic ether derived from (b) contained in a copolymer of (b) and (c) with a carboxylic acid or carboxylic anhydride contained in (a).
The amount of (a) to be reacted with the copolymer is preferably 5 to 100 moles per 100 moles of (b). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) for use in resin [K5], and (b1-1) is more preferred.
　樹脂［Ｋ５’］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ５’］を構成する全構造単位中、
（ａ）に由来する構造単位（（ｂ）は付加していない）；０～３０モル％
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；５～９５モル％
（ｃ）に由来する構造単位；５～９５モル％
であることが好ましく、
（ａ）に由来する構造単位（（ｂ）は付加していない）；０～１０モル％
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；１５～９０モル％
（ｃ）に由来する構造単位；１０～８５モル％
であることがより好ましく、
（ａ）に由来する構造単位（（ｂ）は付加していない）；０～５モル％
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；２０～８０モル％
（ｃ）に由来する構造単位；２０～８０モル％
であることがよりさらに好ましい。
　（ａ）に由来する構造単位（（ｂ）は付加していない）と、（ａ）に由来する構造単位に（ｂ）を付加させた構造単位と、（ｃ）に由来する構造単位の合計は、樹脂［Ｋ５’］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。
　（ａ）に由来する構造単位（（ｂ）は付加していない）としては、（メタ）アクリル酸などの不飽和モノカルボン酸に由来する構造単位が好ましい。（ａ）に由来する構造単位に（ｂ）を付加させた構造単位としては、（メタ）アクリル酸などの不飽和モノカルボン酸に由来する構造単位に、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）を付加させた構造単位が好ましい。（ｃ）に由来する構造単位としては、直鎖又は分岐鎖の脂肪族飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状飽和炭化水素基を有する（メタ）アクリル酸エステル類から選ばれる１種以上が好ましく、２種以上がより好ましい。
　樹脂［Ｋ５’］は、上記の樹脂［Ｋ４］の製造方法を参照して行ってもよく、（ｂ）の使用量は、（ａ）１００モルに対して、８０モル超１００モル以下であればよい。 In the resin [K5'], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K5'] is as follows:
Structural units derived from (a) (without (b) added): 0 to 30 mol %
Structural units obtained by adding (b) to a structural unit derived from (a): 5 to 95 mol%
Structural units derived from (c): 5 to 95 mol%
It is preferred that
Structural units derived from (a) (without (b) added): 0 to 10 mol %
Structural units obtained by adding (b) to a structural unit derived from (a): 15 to 90 mol%
Structural units derived from (c): 10 to 85 mol%
It is more preferable that
Structural units derived from (a) (without (b) added): 0 to 5 mol %
Structural units obtained by adding (b) to a structural unit derived from (a): 20 to 80 mol%
Structural units derived from (c): 20 to 80 mol%
It is even more preferred that:
The total of the structural units derived from (a) (without (b) added), the structural units derived from (a) with (b) added, and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all structural units constituting the resin [K5'].
As the structural unit derived from (a) (without the addition of (b)), a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit obtained by adding (b) to a structural unit derived from (a), a structural unit obtained by adding a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit derived from (c), one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group are preferred, and two or more types are more preferred.
Resin [K5'] may be produced by referring to the production method of resin [K4] described above, and the amount of (b) used may be more than 80 mol and 100 mol or less per 100 mol of (a).
　樹脂［Ｋ６］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ６］を構成する全構造単位中、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～３０モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位（カルボン酸無水物は付加していない）；２～８０モル％
（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位；２～６０モル％
（ｃ）に由来する構造単位；５～９５モル％
であることが好ましく、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～１０モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位（カルボン酸無水物は付加していない）；５～７０モル％
（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位；５～５０モル％
（ｃ）に由来する構造単位；１０～８５モル％
であることがより好ましく、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～５モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位（カルボン酸無水物は付加していない）；１０～６５モル％
（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位；２０～８０モル％
（ｃ）に由来する構造単位；２０～８０モル％
であることがよりさらに好ましい。
　（ｂ）に由来する構造単位（（ａ）は付加していない）と、（ｂ）に由来する構造単位に（ａ）を付加させた構造単位（カルボン酸無水物は付加していない）と、（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位と、（ｃ）に由来する構造単位の合計は、樹脂［Ｋ６］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。 In the resin [K6], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K6] is as follows:
Structural units derived from (b) ((a) is not added): 0 to 30 mol%
A structural unit obtained by adding (a) to a structural unit derived from (b) (no carboxylic acid anhydride is added); 2 to 80 mol%
A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride thereto: 2 to 60 mol%
Structural units derived from (c): 5 to 95 mol%
It is preferred that
Structural units derived from (b) ((a) is not added): 0 to 10 mol%
A structural unit obtained by adding (a) to a structural unit derived from (b) (no carboxylic acid anhydride is added); 5 to 70 mol%
A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride thereto: 5 to 50 mol %
Structural units derived from (c): 10 to 85 mol%
It is more preferable that
Structural units derived from (b) ((a) is not added): 0 to 5 mol%
Structural units in which (a) is added to a structural unit derived from (b) (no carboxylic acid anhydride is added): 10 to 65 mol%
A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride thereto: 20 to 80 mol%
Structural units derived from (c): 20 to 80 mol%
It is even more preferred that:
The total of the structural unit derived from (b) (to which (a) is not added), the structural unit obtained by adding (a) to the structural unit derived from (b) (to which carboxylic acid anhydride is not added), the structural unit obtained by adding (a) to the structural unit derived from (b) and further adding a carboxylic acid anhydride, and the structural unit derived from (c) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K6].
　（ｂ）に由来する構造単位（（ａ）は付加していない）としては、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）に由来する構造単位が好ましい。（ｂ）に由来する構造単位に（ａ）を付加させた構造単位（カルボン酸無水物は付加していない）としては、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）に由来する構造単位に（メタ）アクリル酸などの不飽和モノカルボン酸を付加させた構造単位が好ましい。（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位としては、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）に由来する構造単位に（メタ）アクリル酸などの不飽和モノカルボン酸を付加させ、無水コハク酸などの飽和脂肪族多価カルボン酸無水物をさらに付加させた構造単位が好ましい。（ｃ）に由来する構造単位としては、直鎖又は分岐鎖の脂肪族飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状飽和炭化水素基を有する（メタ）アクリル酸エステル類から選ばれる１種以上が好ましく、２種以上がより好ましい。 As the structural unit derived from (b) (without (a) added), a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit in which (a) is added to a structural unit derived from (b) (without carboxylic anhydride added), a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit in which (a) is added to a structural unit derived from (b) and a carboxylic anhydride is further added, a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized and a saturated aliphatic polycarboxylic anhydride such as succinic anhydride is further added. As the structural unit derived from (c), one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group are preferred, and two or more types are more preferred.
　樹脂［Ｋ６］は、第一段階として、上述した樹脂［Ｋ１］の製造方法と同様にして、（ｂ）と（ｃ）との共重合体を得る。上記と同様に、得られた共重合体は、反応後の溶液をそのまま使用してもよいし、濃縮あるいは希釈した溶液を使用してもよいし、再沈殿等の方法で固体（粉体）として取り出したものを使用してもよい。
　（ｂ）及び（ｃ）に由来する構造単位の比率は、前記の共重合体を構成する全構造単位の合計モル数に対して、それぞれ、
（ｂ）に由来する構造単位；５～９５モル％
（ｃ）に由来する構造単位；５～９５モル％
であることが好ましく、
（ｂ）に由来する構造単位；１０～９０モル％
（ｃ）に由来する構造単位；１０～９０モル％
であることがより好ましい。 Resin [K6] is produced in the first step by the same method as that for producing resin [K1] described above, to obtain a copolymer of (b) and (c). As in the above, the copolymer obtained may be used as it is in the form of a solution after the reaction, or a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.
The ratio of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer is,
Structural units derived from (b): 5 to 95 mol%
Structural units derived from (c): 5 to 95 mol%
It is preferred that
Structural units derived from (b): 10 to 90 mol%
Structural units derived from (c): 10 to 90 mol%
It is more preferable that:
　さらに、樹脂［Ｋ４］の製造方法と同様の条件で、（ｂ）と（ｃ）との共重合体が有する（ｂ）に由来する環状エーテルに、（ａ）が有するカルボン酸又はカルボン酸無水物を反応させる。（ａ）の使用量は、（ｂ）１００モルに対して、８０～１００モルが好ましい。 Furthermore, under the same conditions as in the manufacturing method of resin [K4], the cyclic ether derived from (b) contained in the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic anhydride contained in (a). The amount of (a) used is preferably 80 to 100 moles per 100 moles of (b).
　前記環状エーテルと（ａ）が有するカルボン酸又はカルボン酸無水物との反応により発生するヒドロキシ基に、カルボン酸無水物を反応させる。
カルボン酸無水物の使用量は、（ａ）の使用量１モル（言い換えれば（ａ）の使用によって生じたヒドロキシ基１モル）に対して、０．０５～１モルが好ましく、０．１０～０．８モルがより好ましく、０．１３～０．７モルがよりさらに好ましい。 The hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic acid anhydride contained in (a) is reacted with the carboxylic acid anhydride.
The amount of the carboxylic acid anhydride used is preferably 0.05 to 1 mol, more preferably 0.10 to 0.8 mol, and even more preferably 0.13 to 0.7 mol, relative to 1 mol of the amount of (a) used (in other words, 1 mol of hydroxy groups generated by the use of (a)).
　樹脂（Ｂ）としては、具体的に、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート／（メタ）アクリル酸共重合体、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸共重合体等の樹脂［Ｋ１］；
　グリシジル（メタ）アクリレート／ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、グリシジル（メタ）アクリレート／スチレン／（メタ）アクリル酸共重合体、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド共重合体、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド／トリシクロ［５．２．１．０2,6］デセン－８－イル（メタ）アクリレート共重合体、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸／ベンジル（メタ）アクリレート共重合体、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸／フェノキシベンジル（メタ）アクリレート共重合体、３－メチル－３－（メタ）アクリルロイルオキシメチルオキセタン／（メタ）アクリル酸／スチレン共重合体等の樹脂［Ｋ２］；
　ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、スチレン／（メタ）アクリル酸共重合体等の樹脂［Ｋ３］；
　ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体のカルボン酸基の一部にグリシジル（メタ）アクリレートを付加させた樹脂、トリシクロデシル（メタ）アクリレート／スチレン／（メタ）アクリル酸共重合体のカルボン酸基の一部にグリシジル（メタ）アクリレートを付加させた樹脂、トリシクロデシル（メタ）アクリレート／ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体のカルボン酸基の一部にグリシジル（メタ）アクリレートを付加させた樹脂、ノルボルネン／ビニルトルエン／（メタ）アクリル酸共重合体のカルボン酸基の一部にグリシジル（メタ）アクリレートを付加させた樹脂、ノルボルネン／スチレン／（メタ）アクリル酸共重合体のカルボン酸基の一部にグリシジル（メタ）アクリレートを付加させた樹脂等の樹脂［Ｋ４］；
　トリシクロデシル（メタ）アクリレート／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂、トリシクロデシル（メタ）アクリレート／スチレン／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂等の樹脂［Ｋ５］；
　トリシクロデシル（メタ）アクリレート／（メタ）アクリル酸の共重合体にグリシジル（メタ）アクリレートを反応させた樹脂、トリシクロデシル（メタ）アクリレート／スチレン／（メタ）アクリル酸の共重合体にグリシジル（メタ）アクリレートを反応させた樹脂等の樹脂［Ｋ５’］；
　トリシクロデシル（メタ）アクリレート／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂にさらにテトラヒドロフタル酸無水物を反応させた樹脂、２－エチルヘキシル（メタ）アクリレート／トリシクロデシル（メタ）アクリレート／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂にさらに無水コハク酸を反応させた樹脂、メチル（メタ）アクリレート／２－エチルヘキシル（メタ）アクリレート／トリシクロデシル（メタ）アクリレート／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂にさらに無水コハク酸を反応させた樹脂等の樹脂［Ｋ６］等が挙げられる。 Specific examples of the resin (B) include resins [K1] such as 3,4-epoxycyclohexylmethyl(meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate/(meth)acrylic acid copolymer;
Glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/tricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/tricyclo[5.2.1.0 2,6 ] decene-8-yl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/benzyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate/(meth)acrylic acid/phenoxybenzyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, and other resins [K2];
Resins such as benzyl (meth)acrylate/(meth)acrylic acid copolymers and styrene/(meth)acrylic acid copolymers [K3];
Resins [K4] such as a resin in which glycidyl (meth)acrylate is added to a portion of the carboxylic acid groups of a benzyl (meth)acrylate/(meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to a portion of the carboxylic acid groups of a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to a portion of the carboxylic acid groups of a tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to a portion of the carboxylic acid groups of a norbornene/vinyl toluene/(meth)acrylic acid copolymer, and a resin in which glycidyl (meth)acrylate is added to a portion of the carboxylic acid groups of a norbornene/styrene/(meth)acrylic acid copolymer;
Resins [K5] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid, and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate with (meth)acrylic acid;
Resins [K5'] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/(meth)acrylic acid with glycidyl (meth)acrylate, and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid with glycidyl (meth)acrylate;
Examples of the resin [K6] include a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting the resulting resin with tetrahydrophthalic anhydride, a resin obtained by reacting a copolymer of 2-ethylhexyl (meth)acrylate/tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting the resulting resin with succinic anhydride, and a resin obtained by reacting a copolymer of methyl (meth)acrylate/2-ethylhexyl (meth)acrylate/tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting the resulting resin with succinic anhydride.
　樹脂（Ｂ）のポリスチレン換算の重量平均分子量は、好ましくは３，０００～１００，０００であり、より好ましくは５，０００～５０，０００であり、さらに好ましくは５，０００～３０，０００である。分子量が前記の範囲内にあると、カラーフィルタの硬度が向上し、残膜率が高く、未露光部の現像液に対する溶解性が良好で、着色パターンの解像度が向上する傾向がある。
　樹脂（Ｂ）の分散度［重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）］は、好ましくは１．１～６であり、より好ましくは１．２～４である。 The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.
The polydispersity of the resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.1-6, and more preferably 1.2-4.
　樹脂（Ｂ）の酸価は、固形分換算で、好ましくは２０～１７０ｍｇ－ＫＯＨ／ｇであり、より好ましくは２５～１５０ｍｇ－ＫＯＨ／ｇ、さらに好ましくは３０～１３５ｍｇ－ＫＯＨ／ｇである。ここで酸価は樹脂（Ｂ）１ｇを中和するために必要な水酸化カリウムの量（ｍｇ）として測定される値であり、例えば水酸化カリウム水溶液を用いて滴定することにより求めることができる。 The acid value of resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 25 to 150 mg-KOH/g, and even more preferably 30 to 135 mg-KOH/g, calculated as solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.
　樹脂（Ｂ）の含有率は、固形分の総量に対して、好ましくは２～６５質量％であり、より好ましくは３～６０質量％であり、さらに好ましくは５～５５質量％、さらにより好ましくは５～４０質量％、特に好ましくは７～３０質量％である。樹脂（Ｂ）の含有率が、前記の範囲内にあると、着色パターンが形成でき、また着色パターンの解像度及び残膜率が向上する傾向がある。 The content of resin (B) is preferably 2 to 65 mass% relative to the total amount of solids, more preferably 3 to 60 mass%, even more preferably 5 to 55 mass%, even more preferably 5 to 40 mass%, and particularly preferably 7 to 30 mass%. When the content of resin (B) is within the above range, a colored pattern can be formed, and the resolution and remaining film rate of the colored pattern tend to improve.
　樹脂（Ｂ）としては、エチレン性二重結合を有する樹脂が耐溶剤性をさらに改善する観点から特に好ましい。エチレン性二重結合を有する場合、樹脂（Ｂ）の二重結合当量は、例えば、１００～２０００ｇ／ｍｏｌ、好ましくは２００～１５００ｇ／ｍｏｌ、より好ましくは３００～１３００ｇ／ｍｏｌである。エチレン性二重結合を有する樹脂（Ｂ）としては、例えば、樹脂[Ｋ２］～［Ｋ６］のいずれかであって、単量体（ｃ）として直鎖又は分岐鎖の脂肪族不飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状不飽和脂肪族炭化水素基を有する（メタ）アクリル酸エステル類、不飽和脂肪族炭化水素環を有するビニルモノマー、不飽和複素環を有するビニルモノマー、及び芳香族環を有するビニルモノマーから選ばれる少なくとも１種を含有する樹脂が挙げられる。また樹脂［Ｋ４］～［Ｋ６］も付加成分（好ましくは前記単量体（ａ）又は前記単量体（ｂ））に由来するエチレン性二重結合を有する。 As resin (B), a resin having an ethylenic double bond is particularly preferred from the viewpoint of further improving solvent resistance. When it has an ethylenic double bond, the double bond equivalent of resin (B) is, for example, 100 to 2000 g/mol, preferably 200 to 1500 g/mol, and more preferably 300 to 1300 g/mol. Examples of resin (B) having an ethylenic double bond include any of resins [K2] to [K6], which contain at least one monomer selected from (meth)acrylic acid esters having a linear or branched aliphatic unsaturated hydrocarbon group, (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, vinyl monomers having an unsaturated aliphatic hydrocarbon ring, vinyl monomers having an unsaturated heterocycle, and vinyl monomers having an aromatic ring as monomer (c). Resins [K4] to [K6] also have an ethylenic double bond derived from an additional component (preferably the monomer (a) or the monomer (b)).
　また樹脂（Ｂ）としては、樹脂［Ｋ１］及び／又は樹脂［Ｋ２］などの単量体（ｂ）に由来する構造単位を有するものも特に好ましい。
　さらに樹脂（Ｂ）としては、樹脂［Ｋ２］～［Ｋ４］のいずれかであって、前記単量体（ｃ）として芳香族環を有する（メタ）アクリル酸エステル類を含み、全構造単位１００モル%中、芳香族環を有する（メタ）アクリル酸エステル類由来の構造単位と前記（ａ）に由来する構造単位の合計が６０モル％以上であるものも特に好ましい。 Furthermore, as the resin (B), those having a structural unit derived from the monomer (b), such as the resin [K1] and/or the resin [K2], are particularly preferred.
Furthermore, the resin (B) is particularly preferably any one of the resins [K2] to [K4], which contains a (meth)acrylic acid ester having an aromatic ring as the monomer (c), and in which the total of the structural units derived from the (meth)acrylic acid ester having an aromatic ring and the structural units derived from the (a) is 60 mol % or more, based on 100 mol % of all structural units.
＜重合性化合物（Ｃ）＞
　重合性化合物（Ｃ）は、重合開始剤（Ｄ）から発生した活性ラジカル及び／又は酸によって重合しうる化合物であり、例えば、重合性のエチレン性不飽和結合を有する化合物等が挙げられ、好ましくは（メタ）アクリル酸エステル化合物である。 <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 thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylic acid ester compounds.
　エチレン性不飽和結合を１つ有する重合性化合物としては、例えば、ノニルフェニルカルビトールアクリレート、２－ヒドロキシ－３－フェノキシプロピルアクリレート、２－エチルヘキシルカルビトールアクリレート、２－ヒドロキシエチルアクリレート、Ｎ－ビニルピロリドン等、並びに、上述の単量体（ａ）、単量体（ｂ）及び単量体（ｃ）等が挙げられる。 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 the above-mentioned monomers (a), (b), and (c).
　エチレン性不飽和結合を２つ有する重合性化合物としては、例えば、１，６－ヘキサンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ビスフェノールＡのビス（アクリロイロキシエチル）エーテル及び３－メチルペンタンジオールジ（メタ）アクリレート等が挙げられる。 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.
　重合性化合物（Ｃ）は、エチレン性不飽和結合を３つ以上有する重合性化合物であることが好ましい。このような重合性化合物としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールオクタ（メタ）アクリレート、トリペンタエリスリトールヘプタ（メタ）アクリレート、テトラペンタエリスリトールデカ（メタ）アクリレート、テトラペンタエリスリトールノナ（メタ）アクリレート、トリス（２－（メタ）アクリロイルオキシエチル）イソシアヌレート、エチレングリコール変性ペンタエリスリトールテトラ（メタ）アクリレート、エチレングリコール変性ジペンタエリスリトールヘキサ（メタ）アクリレート、プロピレングリコール変性ペンタエリスリトールテトラ（メタ）アクリレート、プロピレングリコール変性ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールテトラ（メタ）アクリレート及びカプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられ、好ましくはジペンタエリスリトールペンタ（メタ）アクリレート及びジペンタエリスリトールヘキサ（メタ）アクリレートが挙げられる。 The 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, ethyl Examples of the dipentaerythritol hexa(meth)acrylate include ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, and caprolactone modified dipentaerythritol hexa(meth)acrylate, and preferably dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.
　重合性化合物（Ｃ）の重量平均分子量は、好ましくは５０以上４，０００以下であり、より好ましくは７０以上３，５００以下であり、さらに好ましくは１００以上３，０００以下であり、よりさらに好ましくは１５０以上２，９００以下であり、特に好ましくは２５０以上１，５００以下である。 The weight average molecular weight of the polymerizable compound (C) is preferably 50 or more and 4,000 or less, more preferably 70 or more and 3,500 or less, even more preferably 100 or more and 3,000 or less, even more preferably 150 or more and 2,900 or less, and particularly preferably 250 or more and 1,500 or less.
　重合性化合物（Ｃ）の含有率は、着色硬化性樹脂組成物の固形分の総量に対して、例えば１質量％以上９９質量％以下であってよく、好ましくは３質量％以上９０質量％以下であり、より好ましくは５質量％以上８０質量％以下であり、さらに好ましくは７質量％以上７０質量％以下である。 The content of the polymerizable compound (C) may be, for example, 1% by mass or more and 99% by mass or less, preferably 3% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 80% by mass or less, and even more preferably 7% by mass or more and 70% by mass or less, based on the total amount of solids in the colored curable resin composition.
＜重合開始剤（Ｄ）＞
　重合開始剤（Ｄ）は、光や熱の作用により活性ラジカル、酸等を発生し、重合を開始しうる化合物であればよく、以下の式（Ｉ）で表される化合物を含む。 <Polymerization initiator (D)>
The polymerization initiator (D) may be any compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and includes compounds represented by the following formula (I).
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000008
（式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5は、それぞれ独立して、置換基を有していてもよい炭化水素基を表す。
　ｎは０～４のいずれかの整数を表す。
　前記炭化水素基に含まれる－ＣＨ2－は－Ｏ－、－Ｓ－、－ＣＯ－、又は－ＯＣＯ－に置き換わっていてもよい。） (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a hydrocarbon group which may have a substituent.
n represents an integer of 0 to 4.
The --CH 2 -- contained in the hydrocarbon group may be replaced with --O--, --S--, --CO--, or --OCO--.
　Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で表される炭化水素基としては、炭素数１～２０の飽和炭化水素基、炭素数１～２０の不飽和脂肪族炭化水素基、炭素数６～２０の芳香族炭化水素基等が挙げられる。 Examples of the hydrocarbon group represented by R1 , R2 , R3 , R4 , and R5 include saturated hydrocarbon groups having 1 to 20 carbon atoms, unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms.
　前記炭素数１～２０の飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、ヘキサデシル基、イコシル基等の直鎖状アルキル基；イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基、２－エチルヘキシル基等の分岐鎖状アルキル基；シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、トリシクロデシル基等の炭素数３～２０の脂環式飽和炭化水素基が挙げられる。飽和炭化水素基の炭素数は、好ましくは１～１８、より好ましくは１～１５、さらに好ましくは１～１０、さらにより好ましくは１～８である。 The saturated hydrocarbon group having 1 to 20 carbon atoms includes, for example, linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 18, more preferably 1 to 15, even more preferably 1 to 10, and even more preferably 1 to 8.
　前記炭素数１～２０の不飽和脂肪族炭化水素基としては、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、ヘキサデセニル基、オクタデセニル基、イコセニル基等のアルケニル基；エチニル基、プロピニル基、ヘキシニル基、デシニル基、イコシニル基等のアルキニル基；シクロペンテニル基、シクロヘキセニル基、シクロヘプテニル基等のシクロアルケニル基；等が挙げられる。不飽和脂肪族炭化水素基の炭素数は、好ましくは２～１８、より好ましくは２～１５、さらに好ましくは２～１０である。 The unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms includes alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, hexadecenyl, octadecenyl, and icosenyl; alkynyl groups such as ethynyl, propynyl, hexynyl, decynyl, and icosenyl; cycloalkenyl groups such as cyclopentenyl, cyclohexenyl, and cycloheptenyl; and the like. The number of carbon atoms in the unsaturated aliphatic hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and even more preferably 2 to 10.
　前記炭素数６～２０の芳香族炭化水素基としては、フェニル基、キシリル基、トリメチルフェニル基、ジプロピルフェニル基、ジ（２，２－ジメチルプロピル）フェニル基、ナフチル基、ベンジル基、フェニルエチル基、フェニルブチル基等が挙げられる。芳香族炭化水素基の炭素数は、好ましくは６～１８、より好ましくは６～１５、さらに好ましくは６～１２である。 The aromatic hydrocarbon group having 6 to 20 carbon atoms includes a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di(2,2-dimethylpropyl)phenyl group, a naphthyl group, a benzyl group, a phenylethyl group, a phenylbutyl group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 15, and even more preferably 6 to 12.
　Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で表される炭化水素基が有していてもよい置換基としては、ハロゲン原子、シアノ基、ニトロ基が挙げられる。ハロゲン原子は、フッ素原子、臭素原子、塩素原子、ヨウ素原子であることが好ましい。 Examples of the substituent that the hydrocarbon group represented by R 1 , R 2 , R 3 , R 4 , and R 5 may have include a halogen atom, a cyano group, and a nitro group. The halogen atom is preferably a fluorine atom, a bromine atom, a chlorine atom, or an iodine atom.
　ｎは０～４のいずれかの整数を表し、好ましくは０～３の整数、より好ましくは０～２の整数、さらに好ましくは０又は１の整数、さらにより好ましくは０である。
　該炭化水素基に含まれる－ＣＨ2－は－Ｏ－、－Ｓ－、－ＣＯ－、又は－ＯＣＯ－に置き換わっていてもよく、隣接する－ＣＨ2－が同時に同種の基に置換されることはなく、末端の－ＣＨ2－が置換されることはない。 n represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably an integer of 0 or 1, and even more preferably 0.
The --CH 2 -- contained in the hydrocarbon group may be replaced by --O--, --S--, --CO--, or --OCO--, provided that adjacent --CH 2 -- are not simultaneously replaced by the same type of group, and that the terminal --CH 2 -- is not replaced.
　Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で表される炭化水素基は、炭素数１～２０の飽和炭化水素基、炭素数１～２０の不飽和脂肪族炭化水素基であることが好ましく、炭素数１～２０の飽和炭化水素基であることがより好ましく、炭素数１～１０の鎖状又は分岐状の飽和炭化水素基であることがさらに好ましく、炭素数１～８の鎖状又は分岐状のアルキル基であることがさらにより好ましい。
　Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で表される炭化水素基は、それぞれ、同一であっても異なってもよく、異なっていることが好ましい。 The hydrocarbon groups represented by R 1 , R 2 , R 3 , R 4 , and R 5 are preferably saturated hydrocarbon groups having 1 to 20 carbon atoms or unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, more preferably saturated hydrocarbon groups having 1 to 20 carbon atoms, even more preferably linear or branched saturated hydrocarbon groups having 1 to 10 carbon atoms, and even more preferably linear or branched alkyl groups having 1 to 8 carbon atoms.
The hydrocarbon groups represented by R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different, and are preferably different.
　なかでも、Ｒ1は、炭素数１～８の鎖状アルキル基、Ｒ2は、炭素数１～８の分岐状アルキル基、Ｒ3及びＲ4は、炭素数１～８の鎖状アルキル基、Ｒ5は、炭素数１～８の鎖状又は分岐状のアルキル基であることが好ましく、Ｒ1は、炭素数１～６の鎖状アルキル基、Ｒ2は、炭素数１～８の分岐状アルキル基、Ｒ3及びＲ4は、炭素数１～３の鎖状アルキル基、Ｒ5は、炭素数１～８の鎖状又は分岐状のアルキル基であることがより好ましい。 Among these, it is preferable that R 1 is a linear alkyl group having 1 to 8 carbon atoms, R 2 is a branched alkyl group having 1 to 8 carbon atoms, R 3 and R 4 are linear alkyl groups having 1 to 8 carbon atoms, and R 5 is a linear or branched alkyl group having 1 to 8 carbon atoms, and it is more preferable that R 1 is a linear alkyl group having 1 to 6 carbon atoms, R 2 is a branched alkyl group having 1 to 8 carbon atoms, R 3 and R 4 are linear alkyl groups having 1 to 3 carbon atoms, and R 5 is a linear or branched alkyl group having 1 to 8 carbon atoms.
　重合開始剤は、式（Ｉ）で表される化合物の他に、他の重合開始剤を使用してもよい。他の重合開始剤（Ｄ）としては、Ｏ－アシルオキシム化合物（式（Ｉ）で表される化合物、イルガキュアＯＸＥ０３を除く）、アルキルフェノン化合物、ビイミダゾール化合物、トリアジン化合物及びアシルホスフィンオキサイド化合物等が挙げられる。 In addition to the compound represented by formula (I), other polymerization initiators may be used. Examples of other polymerization initiators (D) include O-acyloxime compounds (excluding the compound represented by formula (I) and Irgacure OXE03), alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.
　前記Ｏ－アシルオキシム化合物は、式（ｄ－１）で表される部分構造を有する化合物である。式中、＊は結合手を表す。 The O-acyloxime compound is a compound having a partial structure represented by formula (d-1). In the formula, * represents a bond.
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000009
　前記Ｏ－アシルオキシム化合物としては、例えば、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）ブタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロペンチルプロパン－１－オン－２－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－｛２－メチル－４－（３，３－ジメチル－２，４－ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－イミン、Ｎ－ベンゾイルオキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－オン－２－イミン、Ｎ－アセチルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－１－オン－２－イミン等が挙げられる。イルガキュアＯＸＥ０１（Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン）、イルガキュアＯＸＥ０２（Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタン－１－イミン）（以上、ＢＡＳＦ製）、Ｎ－１９１９（ＡＤＥＫＡ製）等の市販品を用いてもよい。中でも、Ｏ－アシルオキシム化合物は、Ｎ－アセチルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）ブタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタン－１－イミン及びＮ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロペンチルプロパン－１－オン－２－イミンからなる群から選ばれる少なくとも１種が好ましく、Ｎ－アセチルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタン－１－イミンがより好ましい。これらのＯ－アシルオキシム化合物であると、高明度な光学フィルタが得られる傾向にある。 Examples of the 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-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-di N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, and the like. Commercially available products such as IRGACURE OXE01 (N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine), IRGACURE OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine) (both manufactured by BASF), and N-1919 (manufactured by ADEKA) may also be used. Among them, the O-acyloxime compounds include N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine and N-benzoyloxy- At least one selected from the group consisting of 1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred, with N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine being more preferred. These O-acyloxime compounds tend to produce optical filters with high brightness.
　前記アルキルフェノン化合物は、式（ｄ－２）で表される部分構造又は式（ｄ－３）で表される部分構造を有する化合物である。これらの部分構造中、ベンゼン環は置換基を有していてもよい。式中、＊は結合手を表す。 The alkylphenone compound is a compound having a partial structure represented by formula (d-2) or a partial structure represented by formula (d-3). In these partial structures, the benzene ring may have a substituent. In the formula, * represents a bond.
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000010
　式（ｄ－２）で表される部分構造を有する化合物としては、例えば、２－メチル－２－モルホリノ－１－（４－メチルスルファニルフェニル）プロパン－１－オン、２－ジメチルアミノ－１－（４－モルホリノフェニル）－２－ベンジルブタン－１－オン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］ブタン－１－オン等が挙げられる。イルガキュア３６９、９０７、３７９（以上、ＢＡＳＦ製）等の市販品を用いてもよい。 Examples of compounds having the partial structure represented by formula (d-2) 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. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) may also be used.
　式（ｄ－３）で表される部分構造を有する化合物としては、例えば、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－〔４－（２－ヒドロキシエトキシ）フェニル〕プロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－（４－イソプロペニルフェニル）プロパン－１－オンのオリゴマー、α，α－ジエトキシアセトフェノン、ベンジルジメチルケタール等が挙げられる。
　感度の点で、アルキルフェノン化合物としては、式（ｄ－２）で表される部分構造を有する化合物が好ましい。 Examples of the compound having a partial structure represented by formula (d-3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d-2).
　前記トリアジン化合物としては、例えば、２，４－ビス（トリクロロメチル）－６－（４－メトキシフェニル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－（４－メトキシナフチル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－ピペロニル－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－(４－メトキシスチリル)－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（５－メチルフラン－２－イル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（フラン－２－イル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（４－ジエチルアミノ－２－メチルフェニル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（３，４－ジメトキシフェニル）エテニル〕－１，３，５－トリアジン等が挙げられる。 Examples of the 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- Examples include [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, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.
　前記アシルホスフィンオキサイド化合物としては、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド等が挙げられる。イルガキュア（登録商標）８１９（ＢＡＳＦ製）等の市販品を用いてもよい。 The acylphosphine oxide compound may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.
　前記ビイミダゾール化合物としては、例えば、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（２，３－ジクロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール（例えば、特開平６－７５３７２号公報、特開平６－７５３７３号公報等参照）、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（アルコキシフェニル）ビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（ジアルコキシフェニル）ビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（トリアルコキシフェニル）ビイミダゾール（例えば、特公昭４８－３８４０３号公報、特開昭６２－１７４２０４号公報等参照）、４，４’，５，５’－位のフェニル基がカルボアルコキシ基により置換されているビイミダゾール化合物（例えば、特開平７－１０９１３号公報等参照）等が挙げられる。中でも、下記式で表される化合物及びこれらの混合物が好ましい。 The biimidazole compound includes, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2- 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913). Among these, the compounds represented by the following formula and mixtures thereof are preferred.
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-I000011
　さらに重合開始剤（Ｄ）としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン化合物；ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、３，３’，４，４’－テトラ（ｔｅｒｔ－ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６－トリメチルベンゾフェノン等のベンゾフェノン化合物；９，１０－フェナンスレンキノン、２－エチルアントラキノン、カンファーキノン等のキノン化合物；１０－ブチル－２－クロロアクリドン、ベンジル、フェニルグリオキシル酸メチル、チタノセン化合物等が挙げられる。これらは、後述の重合開始助剤（Ｄ１）（特にアミン類）と組み合わせて用いることが好ましい。 Further examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone 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; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (especially amines) described below.
　酸を発生する重合開始剤としては、例えば、４－ヒドロキシフェニルジメチルスルホニウムｐ－トルエンスルホナート、４－ヒドロキシフェニルジメチルスルホニウムヘキサフルオロアンチモネート、４－アセトキシフェニルジメチルスルホニウムｐ－トルエンスルホナート、４－アセトキシフェニルメチルベンジルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムｐ－トルエンスルホナート、トリフェニルスルホニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムｐ－トルエンスルホナート、ジフェニルヨードニウムヘキサフルオロアンチモネート等のオニウム塩類や、ニトロベンジルトシレート類、ベンゾイントシレート類等が挙げられる。 Examples of polymerization initiators that generate acid include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, as well as nitrobenzyl tosylates and benzoin tosylates.
　重合開始剤（Ｄ）としては、アルキルフェノン化合物、トリアジン化合物、アシルホスフィンオキサイド化合物、Ｏ－アシルオキシム化合物及びビイミダゾール化合物からなる群から選ばれる少なくとも１種を含む重合開始剤が好ましく、Ｏ－アシルオキシム化合物及び又はビイミダゾール化合物を含む重合開始剤がより好ましく、Ｏ－アシルオキシム化合物を含む重合開始剤がさらに好ましい。 As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound is preferred, a polymerization initiator containing an O-acyloxime compound and/or a biimidazole compound is more preferred, and a polymerization initiator containing an O-acyloxime compound is even more preferred.
　重合開始剤（Ｄ）の含有量は、樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、好ましくは０．１質量部以上３０質量部以下であり、より好ましくは１質量部以上２０質量部以下である。重合開始剤（Ｄ）の含有量が、前記の範囲内にあると、高感度化して露光時間が短縮される傾向があるため光学フィルタの生産性が向上する。 The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the optical filter.
　樹脂（Ｂ）、重合性化合物（Ｃ）、及び重合開始剤（Ｄ）の含有率は、着色硬化性樹脂組成物の固形分の総量中、好ましくは１０質量％以上、４６質量％未満、より好ましくは１２質量％以上、４４質量％以下、さらに好ましくは１４質量％以上、４２質量％以下、さらにより好ましくは１６質量％以上、４０質量％以下である。
　樹脂（Ｂ）、重合性化合物（Ｃ）、及び重合開始剤（Ｄ）の含有率が、上記の範囲を満たすと、硬化成分を少なくしてもカラーフィルタの残膜率を改善することができる。 The contents of the resin (B), the polymerizable compound (C), and the polymerization initiator (D) are preferably 10 mass% or more and less than 46 mass%, more preferably 12 mass% or more and 44 mass% or less, even more preferably 14 mass% or more and 42 mass% or less, and still more preferably 16 mass% or more and 40 mass% or less, in the total amount of the solid contents of the colored curable resin composition.
When the contents of the resin (B), the polymerizable compound (C), and the polymerization initiator (D) satisfy the above ranges, the remaining film rate of the color filter can be improved even if the amount of the curable component is reduced.
＜重合開始助剤（Ｄ１）＞
　重合開始助剤（Ｄ１）は、重合開始剤（Ｄ）によって重合が開始された重合性化合物（Ｃ）の重合を促進するために用いられる化合物、もしくは増感剤である。重合開始助剤（Ｄ１）を含む場合、通常、重合開始剤（Ｄ）と組み合わせて用いられる。 <Polymerization Initiator Auxiliary Agent (D1)>
The polymerization initiation aid (D1) is a compound used to promote the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D), or a sensitizer. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).
　重合開始助剤（Ｄ１）としては、アミン化合物、アルコキシアントラセン化合物、チオキサントン化合物及びカルボン酸化合物等が挙げられる。 Examples of the polymerization initiator aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
　アミン化合物としては、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、４－ジメチルアミノ安息香酸メチル、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸イソアミル、安息香酸２－ジメチルアミノエチル、４－ジメチルアミノ安息香酸２－エチルヘキシル、Ｎ，Ｎ－ジメチルパラトルイジン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン（通称ミヒラーズケトン）、４，４’－ビス（ジエチルアミノ）ベンゾフェノン及び４，４’－ビス（エチルメチルアミノ）ベンゾフェノン等が挙げられ、好ましくは４，４’－ビス（ジエチルアミノ）ベンゾフェノンが挙げられる。また、アミン化合物として、ＥＡＢ－Ｆ（保土谷化学工業（株）製）等の市販品を用いてもよい。 Amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, with 4,4'-bis(diethylamino)benzophenone being preferred. Commercially available amine compounds such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.
　アルコキシアントラセン化合物としては、９，１０－ジメトキシアントラセン、２－エチル－９，１０－ジメトキシアントラセン、９，１０－ジエトキシアントラセン、２－エチル－９，１０－ジエトキシアントラセン、９，１０－ジブトキシアントラセン及び２－エチル－９，１０－ジブトキシアントラセン等が挙げられる。 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.
　チオキサントン化合物としては、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン及び１－クロロ－４－プロポキシチオキサントン等が挙げられる。 Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
　カルボン酸化合物としては、フェニルスルファニル酢酸、メチルフェニルスルファニル酢酸、エチルフェニルスルファニル酢酸、メチルエチルフェニルスルファニル酢酸、ジメチルフェニルスルファニル酢酸、メトキシフェニルスルファニル酢酸、ジメトキシフェニルスルファニル酢酸、クロロフェニルスルファニル酢酸、ジクロロフェニルスルファニル酢酸、Ｎ－フェニルグリシン、フェノキシ酢酸、ナフチルチオ酢酸、Ｎ－ナフチルグリシン及びナフトキシ酢酸等が挙げられる。 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.
　これらの重合開始助剤（Ｄ１）を用いる場合、その含有量は、着色硬化性樹脂組成物に含まれる全樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、好ましくは０．１質量部以上３０質量部以下、より好ましくは１質量部以上２０質量部以下である。 When these polymerization initiator aids (D1) are used, the 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, relative to 100 parts by mass of the total amount of all the resins (B) and the polymerizable compounds (C) contained in the colored curable resin composition.
＜溶剤（Ｅ）＞
　溶剤（Ｅ）は、特に限定されず、当該分野で通常使用される溶剤を用いることができる。
　溶剤（Ｅ）は、例えば、エステル溶剤（分子内に－ＣＯＯ－を含み、－Ｏ－を含まない溶剤）、エーテル溶剤（分子内に－Ｏ－を含み、－ＣＯＯ－を含まない溶剤）、エーテルエステル溶剤（分子内に－ＣＯＯ－と－Ｏ－とを含む溶剤）、ケトン溶剤（分子内に－ＣＯ－を含み、－ＣＯＯ－を含まない溶剤）、アルコール溶剤（分子内にＯＨを含み、－Ｏ－、－ＣＯ－及び－ＣＯＯ－を含まない溶剤）、芳香族炭化水素溶剤、アミド溶剤、ジメチルスルホキシド等が挙げられる。これらの溶剤は、２種以上を併用してもよい。 <Solvent (E)>
The solvent (E) is not particularly limited, and any solvent commonly used in the relevant field can be used.
Examples of the solvent (E) include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. Two or more of these solvents may be used in combination.
　エステル溶剤としては、乳酸メチル、乳酸エチル、乳酸ブチル、２－ヒドロキシイソブタン酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル、ギ酸ペンチル、酢酸イソペンチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、シクロヘキサノールアセテート及びγ－ブチロラクトン等が挙げられる。 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 gamma-butyrolactone.
　エーテル溶剤としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、３－メトキシ－１－ブタノール、３－メトキシ－３－メチルブタノール、テトラヒドロフラン、テトラヒドロピラン、１，４－ジオキサン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、アニソール、フェネトール及びメチルアニソール等が挙げられる。 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, phenetole, and methylanisole.
　エーテルエステル溶剤としては、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート及びジプロピレングリコールメチルエーテルアセテート等が挙げられる。 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-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, Examples of such ethers 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.
　ケトン溶剤としては、４－ヒドロキシ－４－メチル－２－ペンタノン、アセトン、２－ブタノン、２－ヘプタノン、３－ヘプタノン、４－ヘプタノン、４－メチル－２－ペンタノン、シクロペンタノン、シクロヘキサノン及びイソホロン等が挙げられる。 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.
　アルコール溶剤としては、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール及びグリセリン等が挙げられる。 Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
　芳香族炭化水素溶剤としては、ベンゼン、トルエン、キシレン、メシチレン等が挙げられる。 Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, etc.
　アミド溶剤としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド及びＮ－メチルピロリドン等が挙げられる。 Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
　溶剤（Ｅ）としては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、乳酸エチル及びシクロヘキサノンが好ましく、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルがより好ましい。 As the solvent (E), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and cyclohexanone are preferred, and propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are more preferred.
　溶剤（Ｅ）を含む場合、溶剤（Ｅ）の含有率は、着色硬化性樹脂組成物の総量に対して、通常９９．９９質量％以下であり、好ましくは４０質量％以上９９質量％以下であり、より好ましくは５０質量％以上９７質量％以下であり、さらに好ましくは７０質量％以上９６質量％以下であり、よりさらに好ましくは７３質量％以上９５質量％以下である。言い換えると、着色硬化性樹脂組成物の固形分の総量は、通常０．０１質量％以上であり、好ましくは１質量％以上６０質量％以下であり、より好ましくは３質量％以上５０質量％以下であり、さらに好ましくは４質量％以上３０質量％以下であり、よりさらに好ましくは５質量％以上２７質量％以下である。溶剤（Ｅ）の含有率が前記の範囲内にあると、塗布時の平坦性が良好になり、またカラーフィルタを形成した際に色濃度が不足しないために表示特性が良好となる傾向がある。 When the solvent (E) is included, the content of the solvent (E) is usually 99.99% by mass or less, preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 97% by mass or less, even more preferably 70% by mass or more and 96% by mass or less, and even more preferably 73% by mass or more and 95% by mass or less, based on the total amount of the colored curable resin composition. In other words, the total amount of solids in the colored curable resin composition is usually 0.01% by mass or more, preferably 1% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 50% by mass or less, even more preferably 4% by mass or more and 30% by mass or less, and even more preferably 5% by mass or more and 27% by mass or less. When the content of the solvent (E) is within the above range, the flatness during application is good, and the color density is not insufficient when a color filter is formed, so that the display characteristics tend to be good.
＜チオール化合物（Ｔ）＞
　本発明の着色硬化性樹脂組成物は、チオール化合物（Ｔ）を含んでいてもよい。
チオール化合物（Ｔ）は、分子内にスルファニル基（－ＳＨ）を有する化合物である。 <Thiol Compound (T)>
The colored curable resin composition of the present invention may contain a thiol compound (T).
The thiol compound (T) is a compound having a sulfanyl group (-SH) in the molecule.
　分子内にスルファニル基を１つ有する化合物としては、例えば、２－スルファニルオキサゾール、２－スルファニルチアゾール、２－スルファニルベンズイミダゾール、２－スルファニルベンゾチアゾール、２－スルファニルベンゾオキサゾール、２－スルファニルニコチン酸、２－スルファニルピリジン、２－スルファニルピリジン－３－オール、２－スルファニルピリジン－Ｎ－オキサイド、４－アミノ－６－ヒドロキシ－２－スルファニルピリミジン、４－アミノ－６－ヒドロキシ－２－スルファニルピリミジン、４－アミノ－２－スルファニルピリミジン、６－アミノ－５－ニトロソ－２－チオウラシル、４，５－ジアミノ－６－ヒドロキシ－２－スルファニルピリミジン、４，６－ジアミノ－２－スルファニルピリミジン、２，４－ジアミノ－６－スルファニルピリミジン、４，６－ジヒドロキシ－２－スルファニルピリミジン、４，６－ジメチル－２－スルファニルピリミジン、４－ヒドロキシ－２－スルファニル－６－メチルピリミジン、４－ヒドロキシ－２－スルファニル－６－プロピルピリミジン、２－スルファニル－４－メチルピリミジン、２－スルファニルピリミジン、２－チオウラシル、３，４，５，６－テトラヒドロピリミジン－２－チオール、４，５－ジフェニルイミダゾール－２－チオール、２－スルファニルイミダゾール、２－スルファニル－１－メチルイミダゾール、４－アミノ－３－ヒドラジノ－５－スルファニル－１，２，４－トリアゾール、３－アミノ－５－スルファニル－１，２，４－トリアゾール、２－メチル－４Ｈ－１，２，４－トリアゾール－３－チオール、４－メチル－４Ｈ－１，２，４－トリアゾール－３－チオール、３－スルファニル－１Ｈ－１，２，４－トリアゾール－３－チオール、２－アミノ－５－スルファニル－１，３，４－チアジアゾール、５－アミノ－１，３，４－チアジアゾール－２－チオール、２，５－ジスルファニル－１，３，４－チアジアゾール、(フラン－２－イル)メタンチオール、２－スルファニル－５－チアゾリドン、２－スルファニルチアゾリン、２－スルファニル－４（３Ｈ）－キナゾリノン、１－フェニル－１Ｈ－テトラゾール－５－チオール、２－キノリンチオール、２－スルファニル－５－メチルベンズイミダゾール、２－スルファニル－５－ニトロベンズイミダゾール、６－アミノ－２－スルファニルベンゾチアゾール、５－クロロ－２－スルファニルベンゾチアゾール、６－エトキシ－２－スルファニルベンゾチアゾール、６－ニトロ－２－スルファニルベンゾチアゾール、２－スルファニルナフトイミダゾール、２－スルファニルナフトオキサゾール、３－スルファニル－１，２，４－トリアゾール、４－アミノ－６－スルファニルピラゾロ［２，４－ｄ］ピリジン、２－アミノ－６－プリンチオール、６－スルファニルプリン、４－スルファニル－１Ｈ－ピラゾロ［２，４－ｄ］ピリミジン等が挙げられる。 Examples of compounds having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1 , 2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl-1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol , 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo[2,4-d]pyrimidine, etc.
　分子内にスルファニル基を２つ以上有する化合物としては、ヘキサンジチオール、デカンジチオール、１，４－ビス（メチルスルファニル）ベンゼン、ブタンジオールビス（３－スルファニルプロピオネート）、ブタンジオールビス（３－スルファニルアセテート）、エチレングリコールビス（３－スルファニルアセテート）、トリメチロールプロパントリス（３－スルファニルアセテート）、ブタンジオールビス（３－スルファニルプロピオネート）、トリメチロールプロパントリス（３－スルファニルプロピオネート）、トリメチロールプロパントリス（３－スルファニルアセテート）、ペンタエリスリトールテトラキス（３－スルファニルプロピオネート）、ペンタエリスリトールテトラキス（３－スルファニルアセテート）、トリスヒドロキシエチルトリス（３－スルファニルプロピオネート）、ペンタエリスリトールテトラキス（３－スルファニルブチレート）、１，４－ビス（３－スルファニルブチルオキシ）ブタン等が挙げられる。 Compounds with two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediol bis(3-sulfanylpropionate), butanediol bis(3-sulfanyl acetate), ethylene glycol bis(3-sulfanyl acetate), trimethylolpropane tris(3-sulfanyl acetate), butanediol bis(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanyl acetate), Examples include propane tris(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanyl acetate), pentaerythritol tetrakis(3-sulfanylpropionate), pentaerythritol tetrakis(3-sulfanyl acetate), trishydroxyethyl tris(3-sulfanylpropionate), pentaerythritol tetrakis(3-sulfanyl butyrate), and 1,4-bis(3-sulfanylbutyloxy)butane.
　チオール化合物（Ｔ）の含有量は、重合開始剤（Ｄ）１００質量部に対して、好ましくは０．５～５０質量部、より好ましくは５～４５質量部であり、更に好ましくは１０～４０質量部である。チオール化合物（Ｔ）の含有量がこの範囲内にあると、感度が高くなり、また現像性が良好になる傾向がある。 The content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the polymerization initiator (D). If the content of the thiol compound (T) is within this range, the sensitivity tends to be high and the developability tends to be good.
＜レベリング剤（Ｆ）＞
　レベリング剤（Ｆ）としては、シリコーン系界面活性剤、フッ素系界面活性剤及びフッ素原子を有するシリコーン系界面活性剤等が挙げられる。これらは、側鎖に重合性基を有していてもよい。 <Leveling Agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine-based surfactants, and silicone surfactants having fluorine atoms, which may have a polymerizable group in the side chain.
　シリコーン系界面活性剤としては、分子内にシロキサン結合を有する界面活性剤等が挙げられる。具体的には、トーレシリコーンＤＣ３ＰＡ、同ＳＨ７ＰＡ、同ＤＣ１１ＰＡ、同ＳＨ２１ＰＡ、同ＳＨ２８ＰＡ、同ＳＨ２９ＰＡ、同ＳＨ３０ＰＡ、同ＳＨ８４００（商品名：東レ・ダウコーニング（株）製）、ＫＰ３２１、ＫＰ３２２、ＫＰ３２３、ＫＰ３２４、ＫＰ３２６、ＫＰ３４０、ＫＰ３４１（信越化学工業（株）製）、ＴＳＦ４００、ＴＳＦ４０１、ＴＳＦ４１０、ＴＳＦ４３００、ＴＳＦ４４４０、ＴＳＦ４４４５、ＴＳＦ４４４６、ＴＳＦ４４５２及びＴＳＦ４４６０（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）等が挙げられる。 Examples of silicone surfactants include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (product names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and 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).
　フッ素系界面活性剤としては、分子内にフルオロカーボン鎖を有する界面活性剤等が挙げられる。具体的には、フロラード（登録商標）ＦＣ４３０、同ＦＣ４３１（住友スリーエム（株）製）、メガファック（登録商標）Ｆ１４２Ｄ、同Ｆ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７７、同Ｆ１８３、同Ｆ５５４、同Ｒ３０、同ＲＳ－７１８－Ｋ（ＤＩＣ（株）製）、エフトップ（登録商標）ＥＦ３０１、同ＥＦ３０３、同ＥＦ３５１、同ＥＦ３５２（三菱マテリアル電子化成（株）製）、サーフロン（登録商標）Ｓ３８１、同Ｓ３８２、同ＳＣ１０１、同ＳＣ１０５（ＡＧＣ（株）製）及びＥ５８４４（（株）ダイキンファインケミカル研究所製）等が挙げられる。 Fluorosurfactants include surfactants having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by AGC Corporation), and E5844 (manufactured by Daikin Fine Chemicals Research Institute Ltd.).
　フッ素原子を有するシリコーン系界面活性剤としては、分子内にシロキサン結合及びフルオロカーボン鎖を有する界面活性剤等が挙げられる。具体的には、メガファック（登録商標）Ｒ０８、同ＢＬ２０、同Ｆ４７５、同Ｆ４７７及び同Ｆ４４３（ＤＩＣ（株）製）等が挙げられる。 Examples of silicone surfactants containing fluorine atoms include surfactants that have siloxane bonds and fluorocarbon chains in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).
　レベリング剤（Ｆ）を含有する場合、レベリング剤（Ｆ）の含有率は、着色硬化性樹脂組成物の総量に対して、好ましくは０．０００５質量％以上１質量％以下であり、より好ましくは０．００１質量％以上０．５質量％以下であり、さらに好ましくは０．００５質量％以上０．１質量％以下である。なおこの含有量に、顔料分散剤の含有量は含まれない。レベリング剤（Ｆ）の含有率が前記の範囲内にあると、カラーフィルタの平坦性を良好にすることができる。 When the leveling agent (F) is contained, 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, based on the total amount of the colored curable resin composition. Note that 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.
＜その他の成分＞
　着色硬化性樹脂組成物は、必要に応じて、充填剤、他の高分子化合物、密着促進剤、クエンチャー、酸化防止剤、光安定剤、連鎖移動剤等、当該技術分野で公知の添加剤を含んでもよい。
　密着促進剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、３－グリシジルオキシプロピルトリメトキシシラン、３－グリシジルオキシプロピルメチルジメトキシシラン、３－グリシジルオキシプロピルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－クロロプロピルメチルジメトキシシラン、３－クロロプロピルトリメトキシシラン、３－メタクリロイルオキシプロピルトリメトキシシラン、３－スルファニルプロピルトリメトキシシラン、３－イソシアナトプロピルトリエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン及びＮ－フェニル－３－アミノプロピルトリエトキシシラン等が挙げられる。 <Other ingredients>
The colored curable resin composition may contain additives known in the technical field, such as a filler, another polymer compound, an adhesion promoter, a quencher, an antioxidant, a light stabilizer, and a chain transfer agent, as necessary.
Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfur Examples of the silane include anylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.
＜着色硬化性樹脂組成物の製造方法＞
　着色硬化性樹脂組成物は、着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）、重合開始剤（Ｄ）、並びに必要に応じて用いられる重合開始助剤（Ｄ１）、溶剤（Ｅ）、レベリング剤（Ｆ）及びその他の成分を混合することにより調製できる。混合は公知又は慣用の装置や条件により行うことができる。
　着色剤（Ａ）は、予め溶剤（Ｅ）の一部又は全部と混合し、平均粒子径が０．２μｍ以下程度となるまで、ビーズミル等を用いて分散させて得られた着色剤含有液として用いてもよく、着色剤含有液として用いることが好ましい。この際、必要に応じて前記分散剤、樹脂（Ｂ）の一部又は全部を配合してもよい。このようにして得られた着色剤含有液に、残りの成分を、所定の濃度となるように混合することにより、目的の着色硬化性樹脂組成物を調製できる。
　また着色剤（Ａ）として染料を含む場合の該染料は、予め溶剤（Ｅ）の一部又は全部に溶解させて溶液を調製してもよい。該溶液を、孔径０．０１～１μｍ程度のフィルタでろ過することが好ましい。 <Method for producing colored curable resin composition>
The colored curable resin composition can be prepared by mixing the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and optionally the polymerization initiator aid (D1), the solvent (E), the leveling agent (F), and other components. The mixing can be carried out using known or conventional equipment and conditions.
The colorant (A) may be used as a colorant-containing liquid obtained by mixing with a part or all of the solvent (E) in advance and dispersing using a bead mill or the like until the average particle size becomes about 0.2 μm or less, and it is preferable to use it as a colorant-containing liquid. In this case, the dispersant and a part or all of the resin (B) may be blended as necessary. The remaining components are mixed into the colorant-containing liquid obtained in this way to a predetermined concentration, whereby the desired colored curable resin composition can be prepared.
In addition, when a dye is contained as the colorant (A), the dye may be dissolved in advance in a part or all of the solvent (E) to prepare a solution. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
＜カラーフィルタの製造方法＞
　本発明の着色硬化性樹脂組成物からカラーフィルタを形成することができる。着色パターンを製造する方法としては、フォトリソグラフ法、インクジェット法、印刷法等が挙げられる。中でも、フォトリソグラフ法が好ましい。フォトリソグラフ法は、前記着色硬化性樹脂組成物を基板に塗布し、乾燥させて着色組成物層を形成し、フォトマスクを介して該着色組成物層を露光して、現像する方法である。フォトリソグラフ法において、露光の際にフォトマスクを用いないこと、及び／又は現像しないことにより、前記着色組成物層の硬化物である着色塗膜を形成することができる。このように形成した着色パターンや着色塗膜が本発明のカラーフィルタである。 <Manufacturing method of color filter>
A color filter can be formed from the colored curable resin composition of the present invention. Examples of methods for producing a colored pattern include a photolithography method, an inkjet method, and a printing method. Among these, the photolithography method is preferred. The photolithography method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film, which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and/or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.
　作製するカラーフィルタの膜厚は、特に限定されず、目的や用途等に応じて適宜調整することができ、例えば、３０μｍ以下、好ましくは２０μｍ以下、より好ましくは６μｍ以下、さらに好ましくは４．５μｍ以下であり、好ましくは０．１μｍ以上、より好ましくは０．２μｍ以上、さらに好ましくは０．３μｍ以上である。 The film thickness of the color filter to be produced is not particularly limited and can be adjusted appropriately depending on the purpose and application, and is, for example, 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, even more preferably 4.5 μm or less, and is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more.
　基板としては、石英ガラス、ホウケイ酸ガラス、アルミナケイ酸塩ガラス、表面をシリカコートしたソーダライムガラスなどのガラス板や、ポリカーボネート、ポリメタクリル酸メチル、ポリエチレンテレフタレートなどの樹脂板、シリコン、前記基板上にアルミニウム、銀、銀／銅／パラジウム合金薄膜などを形成したものが用いられる。これらの基板上には、別のカラーフィルタ層、樹脂層、トランジスタ、回路等が形成されていてもよい。またシリコン基板上にＨＭＤＳ（ヘキサメチルジシラザン）処理を施した基板を使用してもよい。 The substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass with a silica-coated surface; a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate; silicon; or a substrate on which aluminum, silver, or a thin film of a silver/copper/palladium alloy is formed. On these substrates, other color filter layers, resin layers, transistors, circuits, etc. may be formed. A silicon substrate treated with HMDS (hexamethyldisilazane) may also be used.
　フォトリソグラフ法による各色画素の形成は、公知又は慣用の装置や条件で行うことができる。例えば、下記のようにして作製することができる。
　まず、着色硬化性樹脂組成物を基板上に塗布し、加熱乾燥（プリベーク）及び／又は減圧乾燥することにより溶剤等の揮発成分を除去して乾燥させ、平滑な着色組成物層を得る。塗布方法としては、スピンコート法、スリットコート法、スリット　アンド　スピンコート法等が挙げられる。加熱乾燥を行う場合の温度は、３０℃以上１２０℃以下が好ましく、５０℃以上１１０℃以下がより好ましい。また加熱時間としては、１０秒間以上６０分間以下であることが好ましく、３０秒間以上３０分間以下であることがより好ましい。
　減圧乾燥を行う場合は、５０Ｐａ以上１５０Ｐａ以下の圧力下、２０℃以上２５℃以下の温度範囲で行うことが好ましい。着色組成物層の膜厚は、特に限定されず、目的とするカラーフィルタの膜厚に応じて適宜選択すればよい。 The formation of each color pixel by photolithography can be carried out using known or conventional devices and conditions. For example, the pixel can be produced as follows.
First, the colored curable resin composition is applied onto a substrate, and then dried by heating and drying (pre-baking) and/or drying under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth colored composition layer. Examples of the application method include spin coating, slit coating, and slit and spin coating. The temperature at which the heat drying is performed is preferably 30° C. or higher and 120° C. or lower, and more preferably 50° C. or higher and 110° C. or lower. The heating time is preferably 10 seconds or higher and 60 minutes or lower, and more preferably 30 seconds or higher and 30 minutes or lower.
When drying under reduced pressure is performed, it is preferable to perform the drying under a pressure of 50 Pa or more and 150 Pa or less at a temperature range of 20° C. or more and 25° C. or less. The thickness of the colored composition layer is not particularly limited and may be appropriately selected depending on the thickness of the intended color filter.
　次に、着色組成物層は、目的の着色パターンを形成するためのフォトマスクを介して露光される。該フォトマスク上のパターンは特に限定されず、目的とする用途に応じたパターンが用いられる。また、露光面全体に均一に平行光線を照射することや、フォトマスクと着色組成物層が形成された基板との正確な位置合わせを行うことができるため、マスクアライナ及びステッパ等の露光装置を使用することが好ましい。着色塗膜を形成する場合には、フォトマスクを用いずに露光すればよい。 The colored composition layer is then exposed through a photomask to form the desired colored pattern. There are no particular limitations on the pattern on the photomask, and a pattern appropriate for the intended application is used. In addition, it is preferable to use an exposure device such as a mask aligner or stepper, since it is possible to uniformly irradiate the entire exposed surface with parallel light and to accurately align the photomask with the substrate on which the colored composition layer is formed. When a colored coating film is formed, exposure can be performed without using a photomask.
　露光に用いられる光源としては、２５０ｎｍ以上４５０ｎｍ以下の波長の光を発生する光源が好ましい。例えば、３５０ｎｍ未満の光を、この波長域をカットするフィルタを用いてカットしたり、４３６ｎｍ付近、４０８ｎｍ付近、３６５ｎｍ付近の光を、これらの波長域を取り出すバンドパスフィルタを用いて選択的に取り出したりしてもよい。具体的には、水銀灯、発光ダイオード、メタルハライドランプ、ハロゲンランプ等が挙げられる。 The light source used for exposure is preferably a light source that generates light with a wavelength of 250 nm or more and 450 nm or less. For example, light less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm may 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.
　露光後の着色組成物層を現像液に接触させて現像することにより、基板上に着色パターンが形成される。現像により、着色組成物層の未露光部が現像液に溶解して除去される。現像液としては、例えば、水酸化カリウム、炭酸水素ナトリウム、炭酸ナトリウム、水酸化テトラメチルアンモニウム等のアルカリ性化合物の水溶液が好ましい。これらのアルカリ性化合物の水溶液中の濃度は、好ましくは０．０１質量％以上１０質量％以下であり、より好ましくは０．０３質量％以上５質量％以下である。さらに、現像液は、界面活性剤を含んでいてもよい。現像方法は、パドル法、ディッピング法及びスプレー法等のいずれでもよい。さらに現像時に基板を任意の角度に傾けてもよい。
　現像後の基板は、水洗されることが好ましい。 The colored composition layer after exposure is brought into contact with a developer and developed to form a colored pattern on the substrate. The unexposed portion of the colored composition layer is dissolved in the developer and removed by development. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less. Furthermore, the developer may contain a surfactant. The development method may be any of a paddle method, a dipping method, and a spray method. Furthermore, the substrate may be tilted at any angle during development.
After development, the substrate is preferably washed with water.
　さらに、得られた着色パターン又は着色塗膜に、ポストベークを行うことが好ましい。ポストベーク温度は、８０℃以上２５０℃以下が好ましく、１００℃以上２４５℃以下がより好ましい。ポストベーク時間は、１分間以上１２０分間以下が好ましく、２分間以上３０分間以下がより好ましい。
　このようにして得られた着色パターン及び着色塗膜は、カラーフィルタとして有用である。 Furthermore, it is preferable to perform post-baking on the obtained colored pattern or colored coating film. The post-baking temperature is preferably from 80° C. to 250° C., and more preferably from 100° C. to 245° C. The post-baking time is preferably from 1 minute to 120 minutes, and more preferably from 2 minutes to 30 minutes.
The colored pattern and colored coating film thus obtained are useful as a color filter.
　着色塗膜は、耐溶剤性の観点から、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）あるいはプロピレングリコールモノメチルエーテル（ＰＧＭＥ）に温度２３℃で５分間浸漬した後、浸漬前後での色差（ΔＥ*ａｂ）が小さい着色塗膜であることが好ましい。
　ＰＧＭＥに対する着色塗膜の色差（ΔＥ*ａｂ）は、好ましくは５．５以下、より好ましくは５．０以下、さらに好ましくは４．５以下、さらにより好ましくは４．０以下である。 From the viewpoint of solvent resistance, the colored coating film is preferably a colored coating film that, after immersion in propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) at a temperature of 23° C. for 5 minutes, has a small color difference (ΔE*ab) before and after immersion.
The color difference (ΔE*ab) of the colored coating film to PGME is preferably 5.5 or less, more preferably 5.0 or less, even more preferably 4.5 or less, and even more preferably 4.0 or less.
＜表示装置、固体撮像素子＞
　前記カラーフィルタは、表示装置（例えば、液晶表示装置、有機ＥＬ装置、電子ペーパー等）、及び固体撮像素子等に用いられるカラーフィルタとして有用である。 <Display device, solid-state image sensor>
The color filter is useful as a color filter for use in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.), solid-state imaging devices, and the like.
　以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。なお、以下においては、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味する。 The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples, and it is of course possible to carry out the invention with appropriate modifications within the scope of the intent described above and below, all of which are included in the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."
＜合成例１：顔料分散液の調製(Ａ－１)＞
　Ｃ．Ｉ．ピグメントグリーン５９　　　　　　　　　　　　６．５部
　Ｃ．Ｉ．ピグメントイエロー１３９　　　　　　　　　　　１．０部
　Ｃ．Ｉ．ピグメントイエロー１８５　　　　　　　　　　　３．４部
　Ｃ．Ｉ．ピグメントブルー１５：４　　　　　　　　　　　０．４部
　アクリル系顔料分散剤　　　　　　　　　　　　　　　　　３．２部
　分散樹脂（樹脂（Ｂ－Ｘ））　　　　　　　　　　　　　　３．２部
　エチレングリコールモノブチルエーテル　　　　　　　　　０．８部
　ジアセトンアルコール　　　　　　　　　　　　　　　　　０．３部
　プロピレングリコールモノメチルエーテル　　　　　　　　２．５部
　プロピレングリコールモノメチルエーテルアセテート　　７８．７部
を混合し、ビーズミルを用いて顔料を十分に分散させることにより、顔料分散液（Ａ－１）を得た。 Synthesis Example 1: Preparation of Pigment Dispersion (A-1)
C.I. Pigment Green 59 6.5 parts C.I. Pigment Yellow 139 1.0 parts C.I. Pigment Yellow 185 3.4 parts C.I. Pigment Blue 15:4 0.4 parts Acrylic pigment dispersant 3.2 parts Dispersion resin (resin (B-X)) 3.2 parts Ethylene glycol monobutyl ether 0.8 parts Diacetone alcohol 0.3 parts Propylene glycol monomethyl ether 2.5 parts Propylene glycol monomethyl ether acetate 78.7 parts were mixed and the pigment was thoroughly dispersed using a bead mill to obtain a pigment dispersion (A-1).
＜合成例２：顔料分散液の調製(Ａ－２)＞
　Ｃ．Ｉ．ピグメントブルー１５：６　　　　　　　　　　　４．８部
　Ｃ．Ｉ．ピグメントブルー１６　　　　　　　　　　　　　４．３部
　Ｃ．Ｉ．ピグメントバイオレット２３　　　　　　　　　　２．９部
　アクリル系顔料分散剤　　　　　　　　　　　　　　　　　４．１部
　分散樹脂（樹脂（Ｂ－Ｘ））　　　　　　　　　　　　　　３．５部
　ジアセトンアルコール　　　　 　　　　　　　　　　　　　６．７部
　プロピレングリコールモノメチルエーテル　　　　　　　　２．０部
　プロピレングリコールモノメチルエーテルアセテート　　７１．７部
を混合し、ビーズミルを用いて顔料を十分に分散させることにより、顔料分散液（Ａ－２）を得た。 Synthesis Example 2: Preparation of Pigment Dispersion (A-2)
C.I. Pigment Blue 15:6 4.8 parts C.I. Pigment Blue 16 4.3 parts C.I. Pigment Violet 23 2.9 parts Acrylic pigment dispersant 4.1 parts Dispersion resin (resin (B-X)) 3.5 parts Diacetone alcohol 6.7 parts Propylene glycol monomethyl ether 2.0 parts Propylene glycol monomethyl ether acetate 71.7 parts were mixed and the pigment was thoroughly dispersed using a bead mill to obtain a pigment dispersion (A-2).
＜合成例３：顔料分散液の調製（Ａ－３）＞
　Ｃ．Ｉ．ピグメントグリーン３６　　　　　　　　　　　　６．６部
　Ｃ．Ｉ．ピグメントイエロー１３９　　　　　　　　　　　２．０部
　Ｃ．Ｉ．ピグメントイエロー１５０　　　　　　　　　　　３．３部
　アクリル系顔料分散剤　　　　　　　　　　　　　　　　　３．９部
　分散樹脂（樹脂（Ｂ－Ｘ））　　　　　　　　　　　　　　４．７部
　エチレングリコールモノブチルエーテル　　　　　　　　　１．６部
　プロピレングリコールモノメチルエーテル　　　　　　　　２．１部
　プロピレングリコールモノメチルエーテルアセテート　　７５．８部
を混合し、ビーズミルを用いて顔料を十分に分散させることにより、顔料分散液（Ａ－３）を得た。 Synthesis Example 3: Preparation of Pigment Dispersion (A-3)
C.I. Pigment Green 36 6.6 parts C.I. Pigment Yellow 139 2.0 parts C.I. Pigment Yellow 150 3.3 parts Acrylic pigment dispersant 3.9 parts Dispersion resin (resin (B-X)) 4.7 parts Ethylene glycol monobutyl ether 1.6 parts Propylene glycol monomethyl ether 2.1 parts Propylene glycol monomethyl ether acetate 75.8 parts were mixed and the pigment was thoroughly dispersed using a bead mill to obtain a pigment dispersion (A-3).
＜合成例４：顔料分散液の調製（Ａ－４）＞
　Ｃ．Ｉ．ピグメントレッド２５４　　　　　　　　　　　　７．８部
　Ｃ．Ｉ．ピグメントイエロー１３９　　　　　　　　　　　４．２部
　アクリル系顔料分散剤　　　　　　　　　　　　　　　　　３．１部
　分散樹脂（樹脂（Ｂ－Ｘ））　　　　　　　　　　　　　　２．２部
　プロピレングリコールモノメチルエーテル　　　　　　　　３．８部
　プロピレングリコールモノメチルエーテルアセテート　　　７８．９部
を混合し、ビーズミルを用いて顔料を十分に分散させることにより、顔料分散液（Ａ－４）を得た。 Synthesis Example 4: Preparation of Pigment Dispersion (A-4)
C.I. Pigment Red 254 7.8 parts C.I. Pigment Yellow 139 4.2 parts Acrylic pigment dispersant 3.1 parts Dispersion resin (resin (B-X)) 2.2 parts Propylene glycol monomethyl ether 3.8 parts Propylene glycol monomethyl ether acetate 78.9 parts were mixed and the pigment was thoroughly dispersed using a bead mill to obtain a pigment dispersion (A-4).
＜合成例５：樹脂（Ｂ－１）の調製＞
　撹拌装置、滴下ロート、コンデンサー、温度計、ガス導入管を備えたフラスコにプロピレングリコールモノメチルエーテルアセテート２７６．８部を取り、窒素置換しながら撹拌し１２０℃に昇温した。次いで、２－エチルヘキシルアクリレート９２．４部、グリシジルメタクリレート１８４．９部及びジシクロペンタニルメタクリレート１２．３部からなるモノマー混合物に、３５．３部のｔ-ブチルパーオキシ－２－エチルヘキサノエート（重合開始剤）を添加したものを滴下ロートから２時間にわたって前記フラスコ中に滴下した。滴下終了後、１２０℃でさらに３０分間撹拌して共重合反応を行い、付加共重合体を生成させた。その後、フラスコ内を空気に置換し、アクリル酸９３．７部、トリフェニルホスフィン（触媒）１．５部およびメトキノン（重合禁止剤）０．８部を上記の付加共重合体溶液中に投入し、１１０℃で１０時間にわたり反応を続け、グリシジルメタクリレート由来のエポキシ基とアクリル酸の反応によりエポキシ基を開裂すると同時にポリマーの側鎖に重合性不飽和結合を導入した。次いで、反応系に無水コハク酸２４．２部を加え、１１０℃で１時間にわたり反応を続け、エポキシ基の開裂により生じたヒドロキシ基と無水コハク酸を反応させて側鎖にカルボキシル基を導入し、ポリマーを得た。最後に反応溶液に、プロピレングリコールモノメチルエーテルアセテート３８３．３部を加え、ポリマー固形分４０％のポリマー（樹脂（Ｂ－１））溶液を得た。生成した共重合体（ポリマー；樹脂（Ｂ－１））の重量平均分子量Ｍｗは６．３×１０３、固形分換算の酸価は３４ｍｇ－ＫＯＨ／ｇであった。樹脂（Ｂ－１）のエチレン性二重結合当量は、３５０ｇ／ｍｏｌであった。 Synthesis Example 5: Preparation of Resin (B-1)
276.8 parts of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 120°C. Next, a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate, and 12.3 parts of dicyclopentanyl methacrylate, to which 35.3 parts of t-butylperoxy-2-ethylhexanoate (polymerization initiator) had been added, was dropped into the flask from the dropping funnel over 2 hours. After the dropwise addition was completed, the mixture was stirred for another 30 minutes at 120°C to carry out a copolymerization reaction, and an addition copolymer was produced. Thereafter, the inside of the flask was replaced with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine (catalyst) and 0.8 parts of methoquinone (polymerization inhibitor) were added to the above addition copolymer solution, and the reaction was continued for 10 hours at 110 ° C., and the epoxy group derived from glycidyl methacrylate was reacted with acrylic acid to cleave the epoxy group, and at the same time, a polymerizable unsaturated bond was introduced into the side chain of the polymer. Next, 24.2 parts of succinic anhydride were added to the reaction system, and the reaction was continued for 1 hour at 110 ° C., and the hydroxyl group generated by the cleavage of the epoxy group was reacted with succinic anhydride to introduce a carboxyl group into the side chain, thereby obtaining a polymer. Finally, 383.3 parts of propylene glycol monomethyl ether acetate were added to the reaction solution, and a polymer (resin (B-1)) solution with a polymer solid content of 40% was obtained. The weight average molecular weight Mw of the produced copolymer (polymer; resin (B-1)) was 6.3 × 10 3 , and the acid value in terms of solid content was 34 mg-KOH / g. The ethylenic double bond equivalent of the resin (B-1) was 350 g/mol.
＜合成例６：樹脂（Ｂ－２）の調製＞
　撹拌機、温度計、還流冷却器及び、滴下ロートを備えたフラスコ内に窒素を０．０２Ｌ／分で流して窒素雰囲気とし、乳酸エチル２６８部を入れ、撹拌しながら７０℃まで加熱した。次いで、アクリル酸５５部、Ｎ－シクロヘキシルマレイミド８１部、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート（下記式（Ｉ－１）で表される化合物及び式（ＩＩ－１）で表される化合物を、モル比で、５０：５０で混合。）２２４部、並びにトリシクロ［５．２．１．０2,6］デセン－８－イルアクリレート（下記式（ｃ－１）で表される化合物及び式（ｃ－２）で表される化合物を、モル比で、５０：５０で混合。）７部を、乳酸エチル１４０部に溶解して溶液を調製し、該溶液を、滴下ロートを用いて４時間かけて、７０℃に保温したフラスコ内に滴下した。一方、重合開始剤２，２’－アゾビス（２，４－ジメチルバレロニトリル）３０部を乳酸エチル２２５部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗは、１１．２×１０３、固形分３６．７％、溶液酸価４４ｍｇ－ＫＯＨ／ｇの共重合体（ポリマー；樹脂（Ｂ－２））溶液を得た。上記の固形分と溶液酸価とから固形分酸価を計算すると、１１９ｍｇ－ＫＯＨ／ｇであった。 Synthesis Example 6: Preparation of Resin (B-2)
A flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel was filled with nitrogen at 0.02 L/min to create a nitrogen atmosphere, and 268 parts of ethyl lactate was added and heated to 70° C. with stirring. Next, 55 parts of acrylic acid, 81 parts of N-cyclohexylmaleimide, 224 parts of 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate (a compound represented by the following formula (I-1) and a compound represented by the following formula (II-1) mixed in a molar ratio of 50:50), and 7 parts of tricyclo[5.2.1.0 2,6 ]decen-8-yl acrylate (a compound represented by the following formula (c-1) and a compound represented by the following formula (c-2) mixed in a molar ratio of 50:50) were dissolved in 140 parts of ethyl lactate to prepare a solution, which was then dropped into a flask kept at 70° C. using a dropping funnel over a period of 4 hours. On the other hand, a solution of 30 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 225 parts of ethyl lactate was dropped into the flask over 4 hours using another dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the temperature was kept at 70°C for 4 hours and then cooled to room temperature to obtain a copolymer (polymer; resin (B-2)) solution having a weight average molecular weight Mw of 11.2 x 10 3 , a solid content of 36.7%, and a solution acid value of 44 mg-KOH/g. The solid content acid value was calculated from the above solid content and solution acid value to be 119 mg-KOH/g.
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000013
＜合成例７：分散樹脂の調製＞
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流し窒素雰囲気に置換し、プロピレングリコールモノメチルエーテルアセテート２８０部を入れ、攪拌しながら８０℃まで加熱した。次いで、アクリル酸３８部、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－９－イルアクリレートの混合物（含有比はモル比で１：１）２８９部、プロピレングリコールモノメチルエーテルアセテート１２５部の混合溶液を５時間かけて滴下した。一方、２，２－アゾビス（２，４－ジメチルバレロニトリル）３３部をプロピレングリコールモノメチルエーテルアセテート２３５部に溶解させた溶液を６時間かけて滴下した。滴下終了後、８０℃で４時間保持した後、室温まで冷却して、固形分３５．１％、Ｂ型粘度計（２３℃）で測定した粘度１２５ｍＰａ・ｓの共重合体（ポリマー；樹脂（Ｂ－Ｘ））溶液を得た。生成した共重合体の重量平均分子量Ｍｗは９．２×１０3、分散度２．０８、固形分換算の酸価は７７ｍｇ－ＫＯＨ／ｇであった。樹脂（Ｂ－Ｘ）は、以下の構造単位を有する。 Synthesis Example 7: Preparation of Dispersion Resin
A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring. Next, a mixed solution of 38 parts of acrylic acid, 289 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl acrylate (content ratio: 1:1 by molar ratio), and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (polymer; resin (B-X)) solution having a solid content of 35.1% and a viscosity of 125 mPa·s measured with a Brookfield viscometer (23°C). The weight average molecular weight Mw of the produced copolymer was 9.2×10 3 , the dispersity was 2.08, and the acid value calculated as solid content was 77 mg-KOH/g. Resin (B-X) has the following structural units.
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000014
樹脂（Ｂ－３）：株式会社レゾナック製の商品名「リポキシ（登録商標)ＳＰＣ－２０００」 Resin (B-3): Lipoxy (registered trademark) SPC-2000, manufactured by Resonac Co., Ltd.
＜合成例９：樹脂（Ｂ－４）の調製＞
　撹拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート２４１部を加え、窒素置換しながら撹拌し、１３０℃に昇温した。
　次いで、２－エチルヘキシルアクリレート７２．６部、グリシジルメタクリレート１４５．３部、およびジシクロペンタニルメタクリレート９．７部からなるモノマー混合物に、３３．５部のｔ－ブチルパーオキシ－２－エチルヘキサノエートを添加したものを、滴下ロートから２時間にわたって前記フラスコ中に滴下した。滴下終了後、さらに３０分撹拌して共重合反応を行った。
　その後、フラスコ内を空気に置換し、アクリル酸７３．７部、トリフェニルホスフィン０．９部およびメトキノン０．９部を投入し、１２０℃で１０時間にわたり反応を続け、次いで、反応系に無水コハク酸６５．２部を加え、さらに１．５時間にわたり反応を続け、ポリマーを得た。最後に、反応溶液に、プロピレングリコールモノメチルエーテルアセテート３００部を加えた後、ポリマー固形分濃度４０％になるようプロピレングリコールモノメチルエーテルアセテートを加え、ポリマー（樹脂（Ｂ－４））溶液を得た。樹脂（Ｂ－４）のエチレン性二重結合当量は、４００ｇ／ｍｏｌであった。 Synthesis Example 9: Preparation of Resin (B-4)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 241 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 130°C.
Next, a monomer mixture consisting of 72.6 parts of 2-ethylhexyl acrylate, 145.3 parts of glycidyl methacrylate, and 9.7 parts of dicyclopentanyl methacrylate, to which 33.5 parts of t-butylperoxy-2-ethylhexanoate had been added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes to carry out a copolymerization reaction.
Thereafter, the flask was replaced with air, 73.7 parts of acrylic acid, 0.9 parts of triphenylphosphine and 0.9 parts of methoquinone were added, and the reaction was continued for 10 hours at 120°C. Then, 65.2 parts of succinic anhydride were added to the reaction system, and the reaction was continued for another 1.5 hours to obtain a polymer. Finally, 300 parts of propylene glycol monomethyl ether acetate was added to the reaction solution, and propylene glycol monomethyl ether acetate was added so that the polymer solid concentration was 40%, to obtain a polymer (resin (B-4)) solution. The ethylenic double bond equivalent of resin (B-4) was 400 g/mol.
＜合成例１０：樹脂（Ｂ－５）の調製＞
　撹拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート２５８部を加え、窒素置換しながら撹拌し、１２０℃に昇温した。
　次いで、２－エチルヘキシルアクリレート８９．５部、グリシジルメタクリレート１８０．０部、およびジシクロペンタニルメタクリレート１１．９部からなるモノマー混合物に、１０．９部のｔ－ブチルパーオキシ－２－エチルヘキサノエートを添加したものを、滴下ロートから２時間にわたって前記フラスコ中に滴下した。滴下終了後、さらに３０分撹拌して共重合反応を行った。
　その後、フラスコ内を空気に置換し、アクリル酸９０．８部、トリフェニルホスフィン１．１部およびメトキノン１．１部を投入し、１２０℃で１０時間にわたり反応を続け、次いで、反応系に無水コハク酸１８．０部を加え、さらに３０分にわたり反応を続け、ポリマーを得た。最後に、反応溶液に、プロピレングリコールモノメチルエーテルアセテート３３０部を加えた後、ポリマー固形分濃度４０％になるようプロピレングリコールモノメチルエーテルアセテートを加え、ポリマー（樹脂（Ｂ－５））溶液を得た。樹脂（Ｂ－５）のエチレン性二重結合当量は、３３０ｇ／ｍｏｌであった。 Synthesis Example 10: Preparation of Resin (B-5)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 258 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 120°C.
Next, a monomer mixture consisting of 89.5 parts of 2-ethylhexyl acrylate, 180.0 parts of glycidyl methacrylate, and 11.9 parts of dicyclopentanyl methacrylate, to which 10.9 parts of t-butylperoxy-2-ethylhexanoate had been added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes to carry out a copolymerization reaction.
Thereafter, the flask was replaced with air, 90.8 parts of acrylic acid, 1.1 parts of triphenylphosphine and 1.1 parts of methoquinone were added, and the reaction was continued for 10 hours at 120°C. Then, 18.0 parts of succinic anhydride were added to the reaction system, and the reaction was continued for another 30 minutes to obtain a polymer. Finally, 330 parts of propylene glycol monomethyl ether acetate was added to the reaction solution, and propylene glycol monomethyl ether acetate was added so that the polymer solid concentration was 40%, to obtain a polymer (resin (B-5)) solution. The ethylenic double bond equivalent of resin (B-5) was 330 g/mol.
＜合成例１１：樹脂（Ｂ－６）の調製＞
　撹拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート２５７部を加え、窒素置換しながら撹拌し、１２０℃に昇温した。
　次いで、２－エチルヘキシルアクリレート９０．５部、グリシジルメタクリレート１８１．１部、およびジシクロペンタニルメタクリレート１２．０部からなるモノマー混合物に、６．８部のｔ－ブチルパーオキシ－２－エチルヘキサノエートを添加したものを、滴下ロートから２時間にわたって前記フラスコ中に滴下した。滴下終了後、さらに３０分撹拌して共重合反応を行った。
　その後、フラスコ内を空気に置換し、アクリル酸９１．８部、トリフェニルホスフィン１．１部およびメトキノン１．１部を投入し、１２０℃で１０時間にわたり反応を続け、次いで、反応系に無水コハク酸１７．９部を加え、さらに３０分にわたり反応を続け、ポリマーを得た。最後に、反応溶液に、プロピレングリコールモノメチルエーテルアセテート３３０部を加えた後、ポリマー固形分濃度４０％になるようプロピレングリコールモノメチルエーテルアセテートを加え、ポリマー（樹脂（Ｂ－６））溶液を得た。樹脂（Ｂ－６）のエチレン性二重結合当量は、３７０ｇ／ｍｏｌであった。 Synthesis Example 11: Preparation of Resin (B-6)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 257 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 120°C.
Next, a monomer mixture consisting of 90.5 parts of 2-ethylhexyl acrylate, 181.1 parts of glycidyl methacrylate, and 12.0 parts of dicyclopentanyl methacrylate, to which 6.8 parts of t-butylperoxy-2-ethylhexanoate had been added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes to carry out a copolymerization reaction.
Thereafter, the atmosphere in the flask was replaced with air, 91.8 parts of acrylic acid, 1.1 parts of triphenylphosphine and 1.1 parts of methoquinone were added, and the reaction was continued for 10 hours at 120°C. Then, 17.9 parts of succinic anhydride were added to the reaction system, and the reaction was continued for another 30 minutes to obtain a polymer. Finally, 330 parts of propylene glycol monomethyl ether acetate was added to the reaction solution, and propylene glycol monomethyl ether acetate was added so that the polymer solid concentration was 40%, to obtain a polymer (resin (B-6)) solution. The ethylenic double bond equivalent of resin (B-6) was 370 g/mol.
＜合成例１２：樹脂（Ｂ－７）の調製＞
　攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート１７８部を加え、窒素置換しながら攪拌し、１００℃に昇温した。
　次いで、２－エチルヘキシルアクリレート１１５．２部、グリシジルメタクリレート８６．０部、メタクリル酸メチル７２．７部およびジシクロペンタニルメタクリレート１３．３部からなるモノマー混合物に、４７．１部のジメチル２，２’－アゾビス（２ーメチルプロピオネート）（重合開始剤）を添加したものを、滴下ロートから２時間にわたって前記フラスコ中に滴下した。滴下終了後、１００℃でさらに３０分撹拌して共重合反応を行った。
　その後、フラスコ内を空気に置換し、アクリル酸４３．８部、トリフェニルホスフィン（触媒）１．０部およびジブチルヒドロキシトルエン（重合禁止剤）１．０部を投１２０℃で１０時間にわたり反応を続け、次いで、反応系に無水コハク酸２２．１部を加え、さらに１．５時間にわたり反応を続け、ポリマーを得た。
　最後に、反応溶液に、プロピレングリコールモノメチルエーテル３３０部を加えた後、ポリマー固形分濃度４０％になるようプロピレングリコールモノメチルエーテルアセテートを加え、ポリマー（樹脂（Ｂ－７））溶液を得た。 Synthesis Example 12: Preparation of Resin (B-7)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 178 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 100°C.
Next, a monomer mixture consisting of 115.2 parts of 2-ethylhexyl acrylate, 86.0 parts of glycidyl methacrylate, 72.7 parts of methyl methacrylate, and 13.3 parts of dicyclopentanyl methacrylate, to which 47.1 parts of dimethyl 2,2'-azobis(2-methylpropionate) (polymerization initiator) was added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred at 100°C for an additional 30 minutes to carry out a copolymerization reaction.
Thereafter, the atmosphere in the flask was replaced with air, and 43.8 parts of acrylic acid, 1.0 part of triphenylphosphine (catalyst) and 1.0 part of dibutylhydroxytoluene (polymerization inhibitor) were added and the reaction was continued for 10 hours at 120°C. Next, 22.1 parts of succinic anhydride was added to the reaction system and the reaction was continued for another 1.5 hours to obtain a polymer.
Finally, 330 parts of propylene glycol monomethyl ether was added to the reaction solution, and then propylene glycol monomethyl ether acetate was added so that the polymer solid concentration became 40%, to obtain a polymer (resin (B-7)) solution.
＜合成例１３：樹脂（Ｂ－８）の調製＞
　撹拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート３４９部を加え、窒素置換しながら撹拌し、１２０℃に昇温した。
　次いで、ベンジルメタクリレート１６９．２部、メタクリル酸１０３．３部、およびジシクロペンタニルメタクリレート５２．９部からなるモノマー混合物に、２３．４部のｔ－ブチルパーオキシ－２－エチルヘキサノエートを添加したものを、滴下ロートから２時間にわたって前記フラスコ中に滴下した。滴下終了後、さらに３０分撹拌して共重合反応を行った。
　その後、フラスコ内を空気に置換し、グリシジルメタクリレート５１．２部、トリフェニルホスフィン１．１部およびメトキノン１．１部を投入し、１２０℃で１０時間にわたり反応を続け、ポリマーを得た。最後に、反応溶液に、ポリマー固形分濃度４０％になるようプロピレングリコールモノメチルエーテルアセテートを加え、ポリマー（樹脂（Ｂ－８））溶液を得た。樹脂（Ｂ－８）のエチレン性二重結合当量は、１１００ｇ／ｍｏｌであった。 Synthesis Example 13: Preparation of Resin (B-8)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 349 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 120°C.
Next, a monomer mixture consisting of 169.2 parts of benzyl methacrylate, 103.3 parts of methacrylic acid, and 52.9 parts of dicyclopentanyl methacrylate, to which 23.4 parts of t-butylperoxy-2-ethylhexanoate had been added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes to carry out a copolymerization reaction.
Thereafter, the atmosphere in the flask was replaced with air, and 51.2 parts of glycidyl methacrylate, 1.1 parts of triphenylphosphine, and 1.1 parts of methoquinone were added, and the reaction was continued for 10 hours at 120° C. to obtain a polymer. Finally, propylene glycol monomethyl ether acetate was added to the reaction solution so that the polymer solid concentration was 40%, to obtain a polymer (resin (B-8)) solution. The ethylenic double bond equivalent of resin (B-8) was 1100 g/mol.
＜合成例１４：樹脂（Ｂ－９）の調製＞
　撹拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート４９２．４部を加え、窒素置換しながら撹拌し、９０℃に昇温した。
　次いで、ビニルトルエン２０８．１部、アクリル酸６２．１部、およびノルボルネン１３．０部からなるモノマー混合物に、３２．６部のジメチル２，２’－アゾビス（２－メチルプロピオネート）、５．７部のチオグリコール酸を添加したものを、滴下ロートから２時間にわたって前記フラスコ中に滴下した。滴下終了後、さらに３０分撹拌して共重合反応を行った。
　その後、フラスコ内を空気に置換し、グリシジルメタクリレート７８．５部、トリフェニルホスフィン１．１部およびメトキノン１．１部を投入し、１２０℃で１０時間にわたり反応を続け、ポリマーを得た。最後に、反応溶液に、ポリマー固形分濃度４０％になるようプロピレングリコールモノメチルエーテルアセテートを加え、ポリマー（樹脂（Ｂ－９））溶液を得た。樹脂（Ｂ－９）のエチレン性二重結合当量は、７３０ｇ／ｍｏｌであった。 Synthesis Example 14: Preparation of Resin (B-9)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 492.4 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 90°C.
Next, a monomer mixture consisting of 208.1 parts of vinyltoluene, 62.1 parts of acrylic acid, and 13.0 parts of norbornene, to which 32.6 parts of dimethyl 2,2'-azobis(2-methylpropionate) and 5.7 parts of thioglycolic acid were added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes to carry out the copolymerization reaction.
Thereafter, the atmosphere in the flask was replaced with air, and 78.5 parts of glycidyl methacrylate, 1.1 parts of triphenylphosphine, and 1.1 parts of methoquinone were added, and the reaction was continued for 10 hours at 120° C. to obtain a polymer. Finally, propylene glycol monomethyl ether acetate was added to the reaction solution so that the polymer solid concentration was 40%, to obtain a polymer (resin (B-9)) solution. The ethylenic double bond equivalent of resin (B-9) was 730 g/mol.
＜合成例１５：樹脂（Ｂ－１０）の調製＞
　撹拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテルアセテート５４７部を加え、窒素置換しながら撹拌し、１２０℃に昇温した。
　次いで、ベンジルメタクリレート２７２．０部、およびメタクリル酸７３．８部からなるモノマー混合物に、４．２部のｔ－ブチルパーオキシ－２－エチルヘキサノエートを添加したものを、滴下ロートから２時間にわたって前記フラスコ中に滴下した。滴下終了後、さらに３０分撹拌して共重合反応を行い、ポリマーを得た。この反応溶液に、ポリマー固形分濃度３５％になるようプロピレングリコールモノメチルエーテルアセテートを加え、ポリマー（樹脂（Ｂ－１０））溶液を得た。 Synthesis Example 15: Preparation of Resin (B-10)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 547 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 120°C.
Next, a monomer mixture consisting of 272.0 parts of benzyl methacrylate and 73.8 parts of methacrylic acid, to which 4.2 parts of t-butylperoxy-2-ethylhexanoate had been added, was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes to carry out a copolymerization reaction, thereby obtaining a polymer. To this reaction solution, propylene glycol monomethyl ether acetate was added so that the polymer solid concentration was 35%, thereby obtaining a polymer (resin (B-10)) solution.
＜合成例１６：樹脂（Ｂ－１１）の調製＞
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流し窒素雰囲気に置換し、プロピレングリコールモノメチルエーテルアセテート３４０部を入れ、攪拌しながら８０℃まで加熱した。次いで、アクリル酸５７部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（含有比はモル比で１：１）５４部、ベンジルメタクリレート２３９部、プロピレングリコールモノメチルエーテルアセテート７３部の混合溶液を５時間かけて滴下した。一方、重合開始剤２，２－アゾビス（２，４－ジメチルバレロニトリル）４０部をプロピレングリコールモノメチルエーテルアセテート１９７部に溶解した溶液を６時間かけて滴下した。開始剤溶液の滴下終了後、８０℃で３時間保持した後、室温まで冷却して、Ｂ型粘度計（２３℃）で測定した粘度１２７ｍＰａｓ、固形分３７．０重量％の共重合体（樹脂（Ｂ－１１））溶液を得た。生成した樹脂（Ｂ－１１）の重量平均分子量Ｍｗは９．４×１０３、分散度は１．８９、固形分換算の酸価は１１４ｍｇ－ＫＯＨ／ｇであった。樹脂（Ｂ－１１）は、以下の構造単位を有する。
Figure JPOXMLDOC01-appb-I000015
 Synthesis Example 16: Preparation of Resin (B-11)
A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 340 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring. Next, a mixed solution of 57 parts of acrylic acid, 54 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl acrylate (content ratio is 1:1 by molar ratio), 239 parts of benzyl methacrylate, and 73 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a solution of 40 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 197 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition of the initiator solution, the mixture was kept at 80°C for 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-11)) solution having a solid content of 37.0% by weight and a viscosity of 127 mPas measured with a Brookfield viscometer (23°C). The weight average molecular weight Mw of the produced resin (B-11) was 9.4 x 10 3 , the dispersity was 1.89, and the acid value calculated as solid content was 114 mg-KOH/g. Resin (B-11) has the following structural units.
Figure JPOXMLDOC01-appb-I000015
＜合成例１７：樹脂（Ｂ－１２）の調製＞
　還流冷却器、滴下ロート及び攪拌機を備えた１Ｌのフラスコ内に窒素を適量流し窒素雰囲気に置換し、プロピレングリコールモノメチルエーテルアセテート２５６部を入れ、攪拌しながら８０℃まで加熱した。次いで、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物４４部、アクリル酸５７部、３－フェノキシベンジルアクリレート２４９部、プロピレングリコールモノメチルエーテルアセテート1５９部の混合溶液を３時間かけて滴下した。
　一方、２，２－アゾビス（２，４－ジメチルバレロニトリル）２５部をプロピレングリコールモノメチルエーテルアセテート２１０部に溶解した混合溶液を５時間かけて滴下した。滴下終了後、４時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）５１ｍＰａｓ、固形分３６．０％の共重合体（樹脂（Ｂ－１２））溶液を得た。生成した共重合体の重量平均分子量Ｍｗは１１０００、分散度１．９８であった。 Synthesis Example 17: Preparation of Resin (B-12)
An appropriate amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 256 parts of propylene glycol monomethyl ether acetate was added and heated to 80° C. with stirring. Next, a mixed solution of 44 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl acrylate, 57 parts of acrylic acid, 249 parts of 3-phenoxybenzyl acrylate, and 159 parts of propylene glycol monomethyl ether acetate was added dropwise over 3 hours.
On the other hand, a mixed solution of 25 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 210 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-12)) solution having a Brookfield viscosity (23°C) of 51 mPas and a solid content of 36.0%. The weight average molecular weight Mw of the produced copolymer was 11,000 and the dispersity was 1.98.
　上記の合成例で得られた樹脂のポリスチレン換算の重量平均分子量Ｍｗ及び数平均分子量Ｍｎの測定については、ＧＰＣ法を用いて、以下の条件で行った。
　　　装置　　　　　　；ＨＬＣ－８１２０ＧＰＣ（東ソー（株）製）
　　　カラム　　　　　；ＴＳＫ－ＧＥＬＧ２０００ＨＸＬ
　　　カラム温度　　　；４０℃
　　　溶媒　　　　　　；テトラヒドロフラン
　　　流速　　　　　　；１．０ｍＬ／ｍｉｎ
　　　被検液固形分濃度；０．００１～０．０１質量％
　　　注入量　　　　　；５０μＬ
　　　検出器　　　　　；ＲＩ
　　　校正用標準物質　；ＴＳＫ　ＳＴＡＮＤＡＲＤ　ＰＯＬＹＳＴＹＲＥＮＥ
　　　　　　　　　　　　Ｆ－４０、Ｆ－４、Ｆ－２８８、Ａ－２５００、Ａ－５００
　　　　　　　　　　　　（東ソー（株）製）
　上記で得られたポリスチレン換算の重量平均分子量及び数平均分子量の比（Ｍｗ／Ｍｎ）を分散度とした。 The polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn of the resins obtained in the above Synthesis Examples were measured using a GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40°C
Solvent: Tetrahydrofuran Flow rate: 1.0 mL/min
Solids concentration of test solution: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and the number average molecular weight (Mw/Mn) calculated in terms of polystyrene obtained above was taken as the dispersity.
＜実施例１及び比較例１＞
　（１）着色硬化性樹脂組成物の調製
　表１に記載の各成分を表１に記載の配合量となるように混合して着色硬化性樹脂組成物を得た。なお、着色硬化性樹脂組成物の調製にあたり、着色硬化性樹脂組成物の固形分が２３.５質量％となるように、プロピレングリコールモノメチルエーテルアセテートを混合した。表１における各成分の配合量の単位は「質量部」であり、着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）、重合開始剤（Ｄ）、シランカップリング剤及びレベリング剤（Ｆ）の各配合量は固形分換算である。 <Example 1 and Comparative Example 1>
(1) Preparation of Colored Curable Resin Composition The components shown in Table 1 were mixed in the amounts shown in Table 1 to obtain colored curable resin compositions. In preparing the colored curable resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 23.5 mass%. The unit of the amount of each component in Table 1 is "parts by mass", and the amounts of the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), silane coupling agent, and leveling agent (F) are calculated as solid content.
　使用した着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）、重合開始剤（Ｄ）、密着促進剤としてのシランカップリング剤、及びレベリング剤（Ｆ）は、次の通りである。 The colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), silane coupling agent as an adhesion promoter, and leveling agent (F) used are as follows:
　着色剤（Ａ）：着色分散液（Ａ－１）（表１には、各顔料の合計量として表す）
　樹脂（Ｂ）：樹脂（Ｂ－１）
　重合性化合物（Ｃ）：重合性化合物（Ｃ－１）（新中村化学工業（株）製、商品名「ＮＫ　エステル　Ａ－ＴＭＰＴ」トリメチロールプロパントリアクリレート） Colorant (A): Colored dispersion (A-1) (Table 1 shows the total amount of each pigment)
Resin (B): Resin (B-1)
Polymerizable compound (C): Polymerizable compound (C-1) (manufactured by Shin-Nakamura Chemical Co., Ltd., product name "NK Ester A-TMPT" trimethylolpropane triacrylate)
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000016
　重合開始剤（Ｄ）：重合開始剤（Ｄ－１）下記式で表される化合物（ＢＡＳＦ（株）製、商品名「イルガキュアＯＸＥ０３」） Polymerization initiator (D): Polymerization initiator (D-1) is a compound represented by the following formula (manufactured by BASF Ltd., product name "Irgacure OXE03")
Figure JPOXMLDOC01-appb-I000017
Figure JPOXMLDOC01-appb-I000017
重合開始剤（Ｄ）：重合開始剤（Ｄ－２）下記式で表される化合物 Polymerization initiator (D): Polymerization initiator (D-2) Compound represented by the following formula
Figure JPOXMLDOC01-appb-I000018
Figure JPOXMLDOC01-appb-I000018
　シランカップリング剤：下記式で表される化合物、３－メタクリロキシプロピルトリメトキシシラン　（信越化学工業（株）製の商品名「ＫＢＭ―５０３」） Silane coupling agent: Compound represented by the following formula, 3-methacryloxypropyltrimethoxysilane (trade name "KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.)
Figure JPOXMLDOC01-appb-I000019
Figure JPOXMLDOC01-appb-I000019
　レベリング剤（Ｆ）：ポリエーテル変性シリコーンオイル（東レ・ダウコーニング（株）製の商品名「トーレシリコーンＳＨ８４００」） Leveling agent (F): Polyether modified silicone oil (product name "Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
（表１のアクリル系顔料分散剤と分散樹脂は着色分散液（Ａ－１）に由来する量として示す。） (The amounts of acrylic pigment dispersant and dispersing resin in Table 1 are those derived from colored dispersion (A-1).)
〔パターンの作製１〕
　４インチのガラスウエハー上に、表１に記載の各着色硬化性樹脂組成物をポストベーク後の膜厚が１．２μｍになるようにスピンコート法で塗布した後、着色組成物層を得た。着色組成物層を形成した基板を露光機（ＮＳＲ－１７５５ｉ７Ａ；ニコン（株）製）を用いて、２００ｍＪ／ｃｍ2の露光量（３６５ｎｍ基準）で光照射した。フォトマスクとして、２．０μｍ四方のドットパターンが形成されたものを使用した。光照射後の着色組成物層を、テトラメチルアンモニウムヒドロキシドを含む水系現像液に２３℃で２０秒間浸漬現像し、水洗後、９０℃で１５分間ポストベークを行うことにより、パターンを得た。得られたパターンについて、膜厚測定装置（ＤＥＫＴＡＫ３；日本真空技術（株）製））を用いて膜厚を測定したところ、１．２μｍであることを確認した。 [Pattern Creation 1]
On a 4-inch glass wafer, each of the colored curable resin compositions shown in Table 1 was applied by spin coating so that the film thickness after post-baking was 1.2 μm, and then a colored composition layer was obtained. The substrate on which the colored composition layer was formed was irradiated with light at an exposure dose of 200 mJ/cm 2 (based on 365 nm) using an exposure machine (NSR-1755i7A; manufactured by Nikon Corporation). As a photomask, one on which a dot pattern of 2.0 μm square was formed was used. The colored composition layer after light irradiation was immersed and developed in an aqueous developer containing tetramethylammonium hydroxide at 23 ° C. for 20 seconds, washed with water, and then post-baked at 90 ° C. for 15 minutes to obtain a pattern. The film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Shinku Gijutsu Co., Ltd.), and it was confirmed to be 1.2 μm.
＜実施例２及び比較例２＞
　（１）着色硬化性樹脂組成物の調製
　表２に記載の各成分を表２に記載の配合量となるように混合して着色硬化性樹脂組成物を得た。なお、着色硬化性樹脂組成物の調製にあたり、着色硬化性樹脂組成物の固形分が１４.０％となるように、プロピレングリコールモノメチルエーテルアセテートを混合した。表２における各成分の配合量の単位は「質量部」であり、着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）、重合開始剤（Ｄ）、及びレベリング剤（Ｆ）の各配合量は固形分換算である。 <Example 2 and Comparative Example 2>
(1) Preparation of Colored Curable Resin Composition The components shown in Table 2 were mixed in the amounts shown in Table 2 to obtain colored curable resin compositions. In preparing the colored curable resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 14.0%. The unit of the amount of each component in Table 2 is "parts by mass", and the amounts of the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), and leveling agent (F) are calculated as solid content.
　使用した着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）、重合開始剤（Ｄ）、及びレベリング剤（Ｆ）は、次の通りである。 The colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), and leveling agent (F) used are as follows:
　着色剤（Ａ）：着色分散液（Ａ－２）（表２には、各顔料の合計量として表す）
　樹脂（Ｂ）：樹脂（Ｂ－２） Colorant (A): Colored dispersion (A-2) (Table 2 shows the total amount of each pigment)
Resin (B): Resin (B-2)
　重合性化合物（Ｃ）：重合性化合物（Ｃ－２）（東亞合成（株）製、商品名「アロニックス（登録商標）Ｍ－９３０」グリセリントリアクリレート） Polymerizable compound (C): Polymerizable compound (C-2) (manufactured by Toagosei Co., Ltd., product name "Aronix (registered trademark) M-930" glycerin triacrylate)
Figure JPOXMLDOC01-appb-I000021
Figure JPOXMLDOC01-appb-I000021
　重合開始剤（Ｄ）：重合開始剤（Ｄ－１）下記式で表される化合物（ＢＡＳＦ（株）製、商品名「イルガキュアＯＸＥ０３」） Polymerization initiator (D): Polymerization initiator (D-1) is a compound represented by the following formula (manufactured by BASF Ltd., product name "Irgacure OXE03")
Figure JPOXMLDOC01-appb-I000022
Figure JPOXMLDOC01-appb-I000022
重合開始剤（Ｄ）：重合開始剤（Ｄ－２）下記式で表される化合物 Polymerization initiator (D): Polymerization initiator (D-2) is a compound represented by the following formula
Figure JPOXMLDOC01-appb-I000023
Figure JPOXMLDOC01-appb-I000023
　レベリング剤（Ｆ）：ポリエーテル変性シリコーンオイル（東レ・ダウコーニング（株）製の商品名「トーレシリコーンＳＨ８４００」） Leveling agent (F): Polyether modified silicone oil (product name "Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
（表２のアクリル系顔料分散剤と分散樹脂は着色分散液（Ａ－２）に由来する量として示す。） (The amounts of acrylic pigment dispersant and dispersing resin in Table 2 are those derived from colored dispersion (A-2).)
〔パターンの作製２〕
　２インチ角のガラス基板（イーグルＸＧ；コーニング社製）上に、表２に記載の各着色硬化性樹脂組成物を、ポストベーク後の膜厚が２．０μｍになるように、スピンコート法で塗布した後、７０℃で２分間プリベークして組成物層を形成した。冷却後、組成物層を形成した基板と石英ガラス製フォトマスクとの間隔を５０μｍとして、露光機（ＴＭＥ－１５０ＲＳＫ；トプコン（株）製）を用いて、大気雰囲気下、１００ｍＪ／ｃｍ2の露光量（３６５ｎｍ基準）で光照射した。尚、フォトマスクとしては、１０μｍのラインアンドスペースパターンが形成されたものを使用した。光照射後の組成物層を、非イオン系界面活性剤０．１２％と水酸化カリウム０．０４％とを含む水溶液に２５℃で６０秒間浸漬させて現像し、水洗後、オーブン中、８５℃で３０分間ポストベークを行うことにより、パターンを得た。得られたパターンについて、膜厚測定装置（ＤＥＫＴＡＫ３；日本真空技術（株）製））を用いて膜厚を測定したところ、２．０μｍであることを確認した。 [Pattern Creation 2]
On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), each colored curable resin composition described in Table 2 was applied by spin coating so that the film thickness after post-baking was 2.0 μm, and then pre-baked at 70 ° C. for 2 minutes to form a composition layer. After cooling, the substrate on which the composition layer was formed and a quartz glass photomask were spaced apart from each other by 50 μm, and the substrate was irradiated with light at an exposure dose of 100 mJ / cm 2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Note that a photomask on which a 10 μm line and space pattern was formed was used. The composition layer after light irradiation was developed by immersing it in an aqueous solution containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, washed with water, and then post-baked in an oven at 85 ° C. for 30 minutes to obtain a pattern. The film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Shinku Gijutsu Co., Ltd.) and was confirmed to be 2.0 μm.
〔耐溶剤性の評価〕
　パターン作製１、作製２により得られたパターンを、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）あるいはプロピレングリコールモノメチルエーテル（ＰＧＭＥ）に温度２３℃で５分間浸漬し、流水にて１０秒リンスして耐溶剤試験を行った。測色機（ＯＳＰ－ＳＰ－２００；オリンパス（株）製）を用いて分光を測定し、色差による評価と耐溶剤性試験前後の膜厚保持率（膜厚変化）の測定を行った。なお、膜厚保持率（膜厚変化）とは、浸漬前の膜厚に対する浸漬後の膜厚の割合を表す。結果を表３～４に示す。 [Evaluation of Solvent Resistance]
The patterns obtained by Pattern Preparation 1 and Pattern Preparation 2 were immersed in propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) at 23° C. for 5 minutes and rinsed with running water for 10 seconds to conduct a solvent resistance test. Spectroscopic measurements were performed using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and evaluation was performed based on color difference and the film thickness retention (film thickness change) before and after the solvent resistance test was measured. The film thickness retention (film thickness change) refers to the ratio of the film thickness after immersion to the film thickness before immersion. The results are shown in Tables 3 and 4.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
＜実施例３及び比較例３＞
　（１）着色硬化性樹脂組成物の調製
　表５に記載の配合量となるように各成分を混合して着色硬化性樹脂組成物を得た。なお、着色硬化性樹脂組成物の調製にあたり、着色硬化性樹脂組成物の固形分が１４.０％となるように、プロピレングリコールモノメチルエーテルアセテートを混合した。表５における各成分の配合量の単位は「質量部」であり、着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）、重合開始剤（Ｄ）、及びレベリング剤（Ｆ）の各配合量は固形分換算である。 <Example 3 and Comparative Example 3>
(1) Preparation of Colored Curable Resin Compositions Colored curable resin compositions were obtained by mixing the components in the amounts shown in Table 5. In preparing the colored curable resin compositions, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 14.0%. The unit of the amount of each component in Table 5 is "parts by mass", and the amounts of the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), and leveling agent (F) are calculated as solid content.
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　各成分の（Ａ－３）、（Ｂ－Ｘ）、（Ｂ－１）、（Ｃ－１）、（Ｄ－１）、（Ｄ－２）は、前記と同様であり、レベリング剤（Ｆ）は、ポリエーテル変性シリコーンオイル（東レ・ダウコーニング（株）製の商品名「トーレシリコーンＳＨ８４００」）を使用した。
（表５のアクリル系顔料分散剤と分散樹脂は着色分散液（Ａ－３）に由来する量として示す。） The components (A-3), (B-X), (B-1), (C-1), (D-1), and (D-2) were the same as those described above, and the leveling agent (F) used was a polyether-modified silicone oil (manufactured by Dow Corning Toray Co., Ltd. under the trade name "Toray Silicone SH8400").
(The amounts of the acrylic pigment dispersant and dispersing resin in Table 5 are shown as amounts derived from the colored dispersion (A-3).)
〔パターンの作製３〕
　２インチ角のガラス基板（イーグルＸＧ；コーニング社製）上に、表５に記載の各着色硬化性樹脂組成物を、ポストベーク後の膜厚が２．０μｍになるように、スピンコート法で塗布した後、７０℃で２分間プリベークして組成物層を形成した。冷却後、組成物層を形成した基板と石英ガラス製フォトマスクとの間隔を５０μｍとして、露光機（ＴＭＥ－１５０ＲＳＫ；トプコン（株）製）を用いて、大気雰囲気下、１００ｍＪ／ｃｍ2の露光量（３６５ｎｍ基準）で光照射した。尚、フォトマスクとしては、１０μｍのラインアンドスペースパターンが形成されたものを使用した。光照射後の組成物層を、非イオン系界面活性剤０．１２％と水酸化カリウム０．０４％とを含む水溶液に２５℃で６０秒間浸漬させて現像し、水洗後、オーブン中、８５℃で３０分間ポストベークを行うことにより、パターンを得た。得られたパターンについて、膜厚測定装置（ＤＥＫＴＡＫ３；日本真空技術（株）製））を用いて膜厚を測定したところ、２．０μｍであることを確認した。 [Pattern Creation 3]
On a 2-inch square glass substrate (Eagle XG; Corning), each colored curable resin composition described in Table 5 was applied by spin coating so that the film thickness after post-baking was 2.0 μm, and then pre-baked at 70 ° C. for 2 minutes to form a composition layer. After cooling, the substrate on which the composition layer was formed and a quartz glass photomask were spaced apart from each other by 50 μm, and the substrate was irradiated with light at an exposure dose of 100 mJ / cm 2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; Topcon Corporation). Note that a photomask on which a 10 μm line and space pattern was formed was used. The composition layer after light irradiation was developed by immersing it in an aqueous solution containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, washed with water, and then post-baked in an oven at 85 ° C. for 30 minutes to obtain a pattern. The film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Shinku Gijutsu Co., Ltd.) and was confirmed to be 2.0 μm.
〔耐溶剤性の評価〕
　パターン作製３により得られたパターンを、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）あるいはプロピレングリコールモノメチルエーテル（ＰＧＭＥ）に温度２３℃で５分間浸漬し、流水にて１０秒リンスして耐溶剤試験を行った。測色機（ＯＳＰ－ＳＰ－２００；オリンパス（株）製）を用いて分光を測定し、色差による評価と耐溶剤性試験前後の膜厚保持率（膜厚変化）の測定を行った。なお、膜厚保持率（膜厚変化）とは、浸漬前の膜厚に対する浸漬後の膜厚の割合を表す。結果を表６に示す。 [Evaluation of Solvent Resistance]
The pattern obtained by pattern preparation 3 was immersed in propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) at 23° C. for 5 minutes and rinsed with running water for 10 seconds to carry out a solvent resistance test. Spectroscopic measurements were performed using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and evaluation was performed based on color difference and the film thickness retention (film thickness change) before and after the solvent resistance test was measured. The film thickness retention (film thickness change) refers to the ratio of the film thickness after immersion to the film thickness before immersion. The results are shown in Table 6.
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
＜試験例１～１１＞
　（１）着色硬化性樹脂組成物の調製
　表７に記載の配合量となるように各成分を混合して着色硬化性樹脂組成物を得た。なお、着色硬化性樹脂組成物の調製にあたり、着色硬化性樹脂組成物の固形分が１４.０％となるように、プロピレングリコールモノメチルエーテルアセテートを混合した。表７における各成分の配合量の単位は「質量部」であり、着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）、重合開始剤（Ｄ）、及びレベリング剤（Ｆ）の各配合量は固形分換算である。 <Test Examples 1 to 11>
(1) Preparation of Colored Curable Resin Compositions Colored curable resin compositions were obtained by mixing the components in the amounts shown in Table 7. In preparing the colored curable resin compositions, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 14.0%. The unit of the amount of each component in Table 7 is "parts by mass", and the amounts of the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), and leveling agent (F) are calculated as solid content.
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
　各成分の（Ａ－４）、（Ｂ－Ｘ）、（Ｂ－１）、（Ｂ－３）～（Ｂ－１２）、（Ｃ－１）、（Ｄ－２）は、前記と同様であり、レベリング剤（Ｆ）は、ポリエーテル変性シリコーンオイル（東レ・ダウコーニング（株）製の商品名「トーレシリコーンＳＨ８４００」）を使用した。
（表７のアクリル系顔料分散剤と分散樹脂は着色分散液（Ａ－４）に由来する量として示す。） The components (A-4), (B-X), (B-1), (B-3) to (B-12), (C-1), and (D-2) were the same as those described above, and the leveling agent (F) used was a polyether-modified silicone oil (manufactured by Dow Corning Toray Co., Ltd. under the trade name "Toray Silicone SH8400").
(The amounts of the acrylic pigment dispersant and dispersing resin in Table 7 are shown as amounts derived from the colored dispersion (A-4).)
〔パターンの作製４〕
　２インチ角のガラス基板（イーグルＸＧ；コーニング社製）上に、表７に記載の各着色硬化性樹脂組成物を、ポストベーク後の膜厚が２．０μｍになるように、スピンコート法で塗布した後、７０℃で２分間プリベークして組成物層を形成した。冷却後、組成物層を形成した基板と石英ガラス製フォトマスクとの間隔を５０μｍとして、露光機（ＴＭＥ－１５０ＲＳＫ；トプコン（株）製）を用いて、大気雰囲気下、１００ｍＪ／ｃｍ2の露光量（３６５ｎｍ基準）で光照射した。尚、フォトマスクとしては、１０μｍのラインアンドスペースパターンが形成されたものを使用した。光照射後の組成物層を、非イオン系界面活性剤０．１２％と水酸化カリウム０．０４％とを含む水溶液に２５℃で６０秒間浸漬させて現像し、水洗後、オーブン中、８５℃で３０分間ポストベークを行うことにより、パターンを得た。得られたパターンについて、膜厚測定装置（ＤＥＫＴＡＫ３；日本真空技術（株）製））を用いて膜厚を測定したところ、２．０μｍであることを確認した。 [Pattern Creation 4]
On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), each colored curable resin composition described in Table 7 was applied by spin coating so that the film thickness after post-baking was 2.0 μm, and then pre-baked at 70 ° C. for 2 minutes to form a composition layer. After cooling, the substrate on which the composition layer was formed and a quartz glass photomask were spaced apart from each other by 50 μm, and the substrate was irradiated with light at an exposure dose of 100 mJ / cm 2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Note that a photomask on which a 10 μm line and space pattern was formed was used. The composition layer after light irradiation was developed by immersing it in an aqueous solution containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, washed with water, and then post-baked in an oven at 85 ° C. for 30 minutes to obtain a pattern. The film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Shinku Gijutsu Co., Ltd.) and was confirmed to be 2.0 μm.
〔耐溶剤性の評価〕
　パターン作製４により得られたパターンを、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）あるいはプロピレングリコールモノメチルエーテル（ＰＧＭＥ）に温度２３℃で５分間浸漬し、流水にて１０秒リンスして耐溶剤試験を行った。測色機（ＯＳＰ－ＳＰ－２００；オリンパス（株）製）を用いて分光を測定し、色差による評価と耐溶剤性試験前後の膜厚保持率（膜厚変化）の測定を行った。なお、膜厚保持率（膜厚変化）とは、浸漬前の膜厚に対する浸漬後の膜厚の割合を表す。結果を表８に示す。 [Evaluation of Solvent Resistance]
The pattern obtained by pattern preparation 4 was immersed in propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) at 23° C. for 5 minutes and rinsed with running water for 10 seconds to carry out a solvent resistance test. Spectroscopic measurements were taken using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and evaluation was performed based on color difference and the film thickness retention (film thickness change) before and after the solvent resistance test was measured. The film thickness retention (film thickness change) refers to the ratio of the film thickness after immersion to the film thickness before immersion. The results are shown in Table 8.
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030

Claims (13)

  1. 　着色剤、樹脂、重合性化合物、及び重合開始剤を含み、
    　前記重合開始剤が、式（Ｉ）で表される化合物を含む着色硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5は、それぞれ独立して、置換基を有していてもよい炭化水素基を表す。
    　ｎは０～４のいずれかの整数を表す。
    　前記炭化水素基に含まれる－ＣＨ2－は－Ｏ－、－Ｓ－、－ＣＯ－、又は－ＯＣＯ－に置き換わっていてもよい。）     The composition includes a colorant, a resin, a polymerizable compound, and a polymerization initiator,
    The colored curable resin composition, wherein the polymerization initiator comprises a compound represented by formula (I).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a hydrocarbon group which may have a substituent.
    n represents an integer of 0 to 4.
    The --CH 2 -- contained in the hydrocarbon group may be replaced with --O--, --S--, --CO--, or --OCO--.
  2. 　前記樹脂が、下記樹脂［Ｋ１］から［Ｋ６］から選ばれる少なくとも１つである、請求項１に記載の着色硬化性樹脂組成物。
    　樹脂［Ｋ１］；不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種の単量体（ａ）に由来する構造単位と、炭素数２～４の環状エーテル構造とエチレン性不飽和結合とを有する単量体（ｂ）に由来する構造単位とを有する共重合体；
    　樹脂［Ｋ２］；前記（ａ）に由来する構造単位と前記（ｂ）に由来する構造単位と、前記（ａ）と共重合可能な単量体（ｃ）に由来する構造単位とを有する共重合体；
    　樹脂［Ｋ３］；前記（ａ）に由来する構造単位と前記（ｃ）に由来する構造単位とを有する共重合体；
    　樹脂［Ｋ４］；前記（ａ）に由来する構造単位に前記（ｂ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体；
    　樹脂［Ｋ５］；前記（ｂ）に由来する構造単位に前記（ａ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体；
    　樹脂［Ｋ５’］；前記（ａ）に由来する構造単位に前記（ｂ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体；
    　樹脂［Ｋ６］；前記（ｂ）に由来する構造単位に前記（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体。     The colored curable resin composition according to claim 1, wherein the resin is at least one selected from the following resins [K1] to [K6].
    Resin [K1]: a copolymer having a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
    Resin [K2]: a copolymer having a structural unit derived from the (a), a structural unit derived from the (b), and a structural unit derived from a monomer (c) copolymerizable with the (a);
    Resin [K3]: a copolymer having a structural unit derived from the (a) and a structural unit derived from the (c);
    Resin [K4]: a copolymer having a structural unit derived from the (a) and a structural unit derived from the (b) by addition, and a structural unit derived from the (c);
    Resin [K5]: a copolymer having a structural unit derived from the (b) to which the (a) has been added, and a structural unit derived from the (c);
    Resin [K5']: a copolymer having a structural unit derived from the (a) and a structural unit derived from the (b) by addition, and a structural unit derived from the (c);
    Resin [K6]: A copolymer having a structural unit obtained by adding the (a) to a structural unit derived from the (b) and further adding a carboxylic acid anhydride, and a structural unit derived from the (c).
  3. 　前記樹脂が樹脂［Ｋ１］及び／又は樹脂［Ｋ２］である請求項２に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to claim 2, wherein the resin is resin [K1] and/or resin [K2].
  4. 　前記樹脂が樹脂[Ｋ２］～［Ｋ６］のいずれかであって前記単量体（ｃ）として直鎖又は分岐鎖の脂肪族不飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状不飽和脂肪族炭化水素基を有する（メタ）アクリル酸エステル類、不飽和脂肪族炭化水素環を有するビニルモノマー、不飽和複素環を有するビニルモノマー、及び芳香族環を有するビニルモノマーから選ばれる少なくとも１種を含有する樹脂である請求項２に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to claim 2, wherein the resin is any one of resins [K2] to [K6] and contains, as the monomer (c), at least one selected from (meth)acrylic acid esters having a linear or branched aliphatic unsaturated hydrocarbon group, (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, vinyl monomers having an unsaturated aliphatic hydrocarbon ring, vinyl monomers having an unsaturated heterocycle, and vinyl monomers having an aromatic ring.
  5. 　前記樹脂が樹脂［Ｋ４］～［Ｋ６］のいずれかである請求項２に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to claim 2, wherein the resin is any one of resins [K4] to [K6].
  6. 　前記樹脂がエチレン性二重結合を有し、前記樹脂のエチレン性二重結合当量が１００～２０００ｇ／ｍｏｌである請求項２に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to claim 2, wherein the resin has an ethylenic double bond and the ethylenic double bond equivalent of the resin is 100 to 2000 g/mol.
  7. 　前記樹脂が樹脂［Ｋ２］～［Ｋ４］のいずれかであって、前記単量体（ｃ）として芳香族環を有する（メタ）アクリル酸エステル類を含み、全構造単位１００モル％中、芳香族環を有する（メタ）アクリル酸エステル類由来の構造単位と前記（ａ）に由来する構造単位の合計が６０モル％以上である請求項２に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to claim 2, wherein the resin is any one of resins [K2] to [K4], the monomer (c) contains a (meth)acrylic acid ester having an aromatic ring, and the total of the structural units derived from the (meth)acrylic acid ester having an aromatic ring and the structural units derived from the (a) is 60 mol % or more out of 100 mol % of all structural units.
  8. 　着色剤が、緑色顔料及び黄色顔料を含み、
    　前記緑色顔料は、Ｃ．Ｉ．ピグメントグリーン７、Ｃ．Ｉ．ピグメントグリーン３６、Ｃ．Ｉ．ピグメントグリーン５８、Ｃ．Ｉ．ピグメントグリーン５９、Ｃ．Ｉ．ピグメントグリーン６２、及びＣ．Ｉ．ピグメントグリーン６３からなる群から選ばれる少なくとも１種を含み、
    　前記黄色顔料は、Ｃ．Ｉ．ピグメントイエロー１３８、Ｃ．Ｉ．ピグメントイエロー１３９、Ｃ．Ｉ．ピグメントイエロー１５０、Ｃ．Ｉ．ピグメントイエロー１８５、Ｃ．Ｉ．ピグメントイエロー２３１、及びＣ．Ｉ．ピグメントイエロー２３３からなる群から選ばれる少なくとも１種を含む請求項２に記載の着色硬化性樹脂組成物。     the colorant comprises a green pigment and a yellow pigment;
    The green pigment includes at least one selected from the group consisting of C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62, and C.I. Pigment Green 63;
    The yellow pigment comprises at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 231, and C.I. Pigment Yellow 233. The colored curable resin composition according to claim 2, comprising at least one pigment selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 231, and C.I. Pigment Yellow 233.
  9. 　着色剤が、赤色顔料及び黄色顔料を含み、
    　前記赤色顔料は、Ｃ．Ｉ．ピグメントレッド１２２、Ｃ．Ｉ．ピグメントレッド１７７、Ｃ．Ｉ．ピグメントレッド２５４、Ｃ．Ｉ．ピグメントレッド２５５、Ｃ．Ｉ．ピグメントレッド２６４、Ｃ．Ｉ．ピグメントレッド２６９、Ｃ．Ｉ．ピグメントレッド２７２、及びＣ．Ｉ．ピグメントレッド２９１からなる群から選ばれる少なくとも１種を含み、
    　前記黄色顔料は、Ｃ．Ｉ．ピグメントイエロー１３８、Ｃ．Ｉ．ピグメントイエロー１３９、Ｃ．Ｉ．ピグメントイエロー１５０、Ｃ．Ｉ．ピグメントイエロー１８５、Ｃ．Ｉ．ピグメントイエロー２３１、及びＣ．Ｉ．ピグメントイエロー２３３からなる群から選ばれる少なくとも１種を含む請求項２に記載の着色硬化性樹脂組成物。     the colorant comprises a red pigment and a yellow pigment;
    The red pigment includes at least one selected from the group consisting of C.I. Pigment Red 122, C.I. Pigment Red 177, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Red 269, C.I. Pigment Red 272, and C.I. Pigment Red 291;
    The yellow pigment comprises at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 231, and C.I. Pigment Yellow 233. The colored curable resin composition according to claim 2, comprising at least one pigment selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 231, and C.I. Pigment Yellow 233.
  10. 　着色剤が、青色顔料及び紫色顔料を含み、
    　前記青色顔料は、Ｃ．Ｉ．ピグメントブルー１５、１５：３、１５：４、１５：６、１６からなる群より選ばれる少なくとも１種を含み、
    　前記紫色顔料は、Ｃ．Ｉ．ピグメントバイオレット１９、２３、２９からなる群より選ばれる少なくとも１種を含む請求項２に記載の着色硬化性樹脂組成物。     The colorant includes a blue pigment and a purple pigment;
    The blue pigment includes at least one selected from the group consisting of C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 16;
    The colored curable resin composition according to claim 2, wherein the purple pigment comprises at least one selected from the group consisting of C. I. Pigment Violet 19, 23, and 29.
  11. 　請求項１～１０のいずれかに記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。 A color filter formed from the colored curable resin composition according to any one of claims 1 to 10.
  12. 　請求項１１に記載のカラーフィルタを含む表示装置。 A display device including the color filter according to claim 11.
  13. 　請求項１１に記載のカラーフィルタを含む固体撮像素子。 A solid-state imaging device including the color filter according to claim 11.
PCT/JP2023/039215 2022-11-09 2023-10-31 Colored curable resin composition, color filter, display device, and solid-state imaging element WO2024101219A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021175855A1 (en) * 2020-03-04 2021-09-10 Basf Se Oxime ester photoinitiators
CN114380937A (en) * 2021-12-16 2022-04-22 江苏博砚电子科技有限公司 Adamantane-containing photosensitive resin for black matrix photoresist, preparation method thereof, resin composition and application method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021175855A1 (en) * 2020-03-04 2021-09-10 Basf Se Oxime ester photoinitiators
CN114380937A (en) * 2021-12-16 2022-04-22 江苏博砚电子科技有限公司 Adamantane-containing photosensitive resin for black matrix photoresist, preparation method thereof, resin composition and application method thereof

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