WO2021039491A1 - Composition de résine colorée - Google Patents

Composition de résine colorée Download PDF

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Publication number
WO2021039491A1
WO2021039491A1 PCT/JP2020/031072 JP2020031072W WO2021039491A1 WO 2021039491 A1 WO2021039491 A1 WO 2021039491A1 JP 2020031072 W JP2020031072 W JP 2020031072W WO 2021039491 A1 WO2021039491 A1 WO 2021039491A1
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Prior art keywords
group
mass
resin composition
colored resin
meth
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PCT/JP2020/031072
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English (en)
Japanese (ja)
Inventor
森本　純平
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住友化学株式会社
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Priority to KR1020227010330A priority Critical patent/KR20220056212A/ko
Priority to CN202080059185.7A priority patent/CN114303095A/zh
Publication of WO2021039491A1 publication Critical patent/WO2021039491A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C09B45/22—Monoazo compounds containing other metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/04—Isoindoline dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • the present invention relates to a colored resin composition containing a cyclic ether structure-containing component and a green colorant.
  • green colorants are known to cause deterioration of electrical characteristics (for example, dielectric loss tangent) and resulting display defects (for example, screen flicker) in display devices, and green colorants, resins, and polymerizations. It is desired to improve the electrical characteristics and display defects in the green photosensitive resin composition (Patent Document 1) containing a sex compound, a polymerization initiator and a solvent.
  • an object of the present invention is to provide a colored resin composition or the like that satisfies the conditions of high color reproducibility and a thin film and can provide a color filter having a reduced dielectric loss tangent.
  • the colored resin composition, the color filter, the display device, and the solid-state image sensor according to the present invention have the following points.
  • a colored resin composition containing at least a colorant and a resin wherein the colored resin composition contains a cyclic ether structure-containing component, the colorant contains at least a green colorant, and the content of the total colorant.
  • the colored resin composition is characterized in that it is 45.5% by mass or more with respect to the solid content of the colored resin composition.
  • the colored resin composition according to [1] wherein the resin contains a resin having a solid acid value of 85 mg-KOH / g or more.
  • the present invention it is possible to provide a colored resin composition that provides a color filter having a reduced dielectric loss tangent while satisfying the conditions of high color reproducibility and a thin film.
  • the colored resin composition of the present invention contains a colorant (hereinafter, may be referred to as a colorant (A)) and a resin (hereinafter, may be referred to as a resin (B)).
  • the colored resin composition of the present invention includes a polymerizable compound (hereinafter, may be referred to as a polymerizable compound (C)), a polymerization initiator (hereinafter, may be referred to as a polymerization initiator (D)), and a solvent (hereinafter, may be referred to as a polymerization initiator (D)).
  • the solvent (E) may be included), and the polymerization initiator (hereinafter, may be referred to as the polymerization initiator (D1)) may be contained.
  • the colored resin composition of the present invention may contain a leveling agent (hereinafter, may be referred to as a leveling agent (F)).
  • the colored resin composition contains a cyclic ether structure-containing component, the colorant contains at least a green colorant, and the content of the total colorant is the color resin composition. It is characterized in that it is 45.5% by mass or more with respect to the solid content.
  • the colored resin composition contains a cyclic ether structure-containing component.
  • the cyclic ether structure-containing component may be a resin (copolymer) containing a cyclic ether structure, or a compound containing a cyclic ether structure.
  • the cyclic ether structure-containing component preferably has a cyclic ether structure having 2 to 4 carbon atoms (for example, an oxylan ring (epoxide ring), an oxetane ring, and a tetrahydrofuran ring (oxolan ring)), and preferably has an oxylan ring or an oxetane ring. Is more preferable.
  • the cyclic ether structure-containing component examples include the resin having a cyclic ether structure described in the resin (B) and the polymerizable compound (C) described later, and a compound capable of ring-opening polymerization (a compound having a cyclic ether structure). ) And so on.
  • the resin having a cyclic ether structure means a resin having a repeating structural unit in the molecule and having a weight average molecular weight of 3000 or more.
  • the compound capable of ring-opening polymerization is a compound other than a resin having a cyclic ether structure, and means a compound containing a monomer and an oligomer.
  • the compounds exemplified as each component in the present specification may be used alone or in combination of two or more.
  • the content of the cyclic ether structure-containing component (one or both of the resin containing the cyclic ether structure and the compound containing the cyclic ether structure) is reduced in the solid content of 100% by mass of the colored resin composition.
  • it is preferably 0.1% by mass or more and 50% by mass or less, and from the viewpoint of reduced dielectric normal contact and coating film processability, it is more preferably 0.1% by mass or more and 40% by mass or less. More preferably, it is 0.5% by mass or more and 38% by mass or less, and even more preferably 1% by mass or more and 35% by mass or less.
  • the colored resin composition according to the present invention contains a colorant (A), and the colorant (A) contains at least a green colorant.
  • the green colorant may be either a pigment or a dye, but is preferably a pigment, more preferably zinc phthalocyanine, further preferably polyhalogenated zinc phthalocyanine, and polychlorinated zinc phthalocyanine. , Polybrominated zinc phthalocyanine is even more preferred.
  • green is 0 ⁇ x ⁇ 0.40, 0.40 ⁇ y ⁇ 0.85 (preferably 0 ⁇ x ⁇ 0.30, 0.50 ⁇ y ⁇ 0.85) in the XYZ color system. , More preferably 0 ⁇ x ⁇ 0.20, 0.55 ⁇ y ⁇ 0.70).
  • the green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) is treated with rosin, surface-treated with a pigment derivative having an acidic group or a basic group introduced, or a polymer compound, if necessary.
  • the pigment surface is grafted with, etc., atomized by sulfuric acid atomization method, etc., washed with organic solvent or water to remove impurities, removed by ion exchange method of ionic impurities, etc. May be.
  • the green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) is preferably used in the form of a dispersion uniformly dispersed in a solvent, and the dispersion is a green colorant (preferably). It can be obtained by mixing zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) in a solvent. If necessary, the dispersant may be mixed.
  • the dispersant may be any of a cationic, anionic, nonionic and amphoteric dispersant, and examples thereof include polyester-based, polyamine-based and acrylic-based dispersants. These dispersants may be used alone or in combination of two or more. Dispersants are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solspers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF), and Ajinomoto Fine-Techno. (Manufactured by Co., Ltd.), Disperbyk (manufactured by Big Chemie), and the like.
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Floren manufactured by Kyoeisha Chemical Co., Ltd.
  • Solspers manufactured by Zeneca Co., Ltd.
  • EFKA manufactured by BASF
  • the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the pigment.
  • the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solvent tends to be obtained.
  • the solvent is not particularly limited, and examples thereof include the same solvent as the solvent (E) in the colored resin composition of the present invention. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol.
  • 4-Hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, etc. More preferably, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like.
  • the amount of the solvent used is not particularly limited, but it is preferable to use the solvent so that the solid content concentration in the pigment dispersion can be adjusted to 3 to 30% by mass, more preferably 5 to 25% by mass.
  • the colorant (A) is a pigment such as a yellow colorant, a blue colorant, which is a second colorant other than a green colorant (preferably zinc phthalocyanine, more preferably a polyhalogenated zinc phthalocyanine) and / or. It may contain a dye.
  • the colorant (A) preferably further contains a yellow colorant.
  • Examples of the pigments include organic pigments and inorganic pigments, and examples thereof include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colorists).
  • Examples of organic pigments include C.I. I. Pigment Yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 185, 194, 214; C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments; C. I. Pigment Green 7, 36 and other green pigments other than polyhalogenated zinc phthalocyanine; And so on.
  • the pigment preferably contains at least one selected from the group consisting of green pigments other than zinc phthalocyanine, yellow pigments, and blue pigments, and the blue pigments are preferably contained together with the yellow pigments.
  • Green pigments, yellow pigments and blue pigments other than zinc phthalocyanine are described in C.I. I. Pigment Yellow 138, 139, 150, 185, C.I. I. Pigment Blue 15: 3, 15: 6, C.I. I. Pigment Greens 7 and 36 are preferred. Two or more of these pigments may be used.
  • the pigment is treated with a rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a pigment dispersant, or the like, a graft treatment on the pigment surface with a polymer compound or the like, and sulfuric acid atomization, if necessary.
  • a micronization treatment by a method or the like, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment of ionic impurities by an ion exchange method or the like may be performed.
  • the pigment preferably has a uniform particle size.
  • the pigment dispersant a commercially available surfactant can be used, and the surface activity of silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric, polyester-based, polyamine-based, acrylic-based, etc. Agents and the like can be mentioned.
  • the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines and the like.
  • KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solpers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Azispar (registered trademark) (Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by Big Chemie) and the like can be mentioned. These can be used alone or in combination of two or more.
  • the amount used is preferably 100% by mass or less, more preferably 5 to 50% by mass, based on the pigment.
  • the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.
  • the dye is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes.
  • dyes include compounds classified by the Color Index (published by The Society of Dyers and Colorists) as having hues other than pigments, and known dyes described in dyeing notes (color dyeing company). Be done. According to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squaarylium dye, acrydin dye, styryl dye. , Kumarin dyes, quinoline dyes, nitro dyes and the like. Of these, organic solvent-soluble dyes are preferred.
  • the content of the total colorant is 45.5% by mass or more, preferably 46.0% by mass or more, and more preferably 46.5% by mass with respect to the solid content of the colored resin composition. It is 5% by mass or more, preferably 65% by mass or less, more preferably 63% by mass or less, and further preferably 61% by mass or less.
  • the content of the green colorant can be appropriately adjusted so as to have a desired chromaticity. From the viewpoint of high color reproducibility, it is preferably 35% by mass or more and 99.9% by mass or less with respect to the solid content of the total colorant.
  • the lower limit of the content of the green colorant is more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more.
  • the upper limit of the content of the green colorant is more preferably 98% by mass or less, further preferably 95% by mass or less, and particularly preferably 90% by mass or less.
  • the content of the green colorant is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 55% by mass or less, based on the solid content of the colored resin composition. It is even more preferably 15% by mass or more and 50% by mass or less, and even more preferably 20% by mass or more and 45% by mass or less.
  • the colorant is C.I. I. Pigment Green 59 and C.I. I.
  • the content of CI Pigment Green 59: the content of CI Pigment Green 58 is represented by C.I. I. Pigment Green 59 and C.I. I.
  • the content ratio of Pigment Green 58 may be in the range of 0.1 to 99.9: 99.9 to 0.1, preferably 1 to 99: 99 to 1. These content ratios can be appropriately adjusted according to the desired color.
  • the amount of the green pigment other than zinc phthalocyanine used is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 1 part by mass or more with respect to 100 parts by mass of zinc phthalocyanine. It is preferably 10 parts by mass or more, preferably 2000 parts by mass or less, more preferably 300 parts by mass or less, and further preferably 100 parts by mass or less.
  • the yellow colorant may be either a yellow pigment or a yellow dye, and is preferably a yellow pigment.
  • the content of the total yellow pigment is preferably 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass, based on the solid content of the total colorant. It is mass% or more.
  • the content of the total yellow pigment is preferably 1% by mass or more and 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, based on the solid content of the total colored resin composition.
  • the blue colorant may be either a blue pigment or a blue dye, and is preferably a blue pigment.
  • the content of the total blue pigment is preferably 0.1% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 25% by mass or less, and further preferably 3% by mass or more, based on the solid content of the total colorant. It is 20% by mass or less.
  • the content of the total blue pigment is preferably 1% by mass or more and 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less with respect to the solid content of the total colored resin composition.
  • the total amount of the colorant (A) is preferably 25 to 65% by mass, more preferably 30 to 60% by mass, still more preferably 35 to 55% by mass, based on 100% by mass of the solid content of the colored resin composition. is there.
  • the resin containing a cyclic ether structure may be a copolymer containing a structural unit derived from a monomer having an oxylanyl group and an ethylenically unsaturated bond (preferably (b1) and (b2) described later). preferable. Further, the resin may be a copolymer containing a structural unit derived from a monomer that does not contain a cyclic ether structure, in which case the colored resin composition will contain a compound having a cyclic ether structure. ..
  • the resin (B) used in the present invention may be an alkali-soluble resin.
  • the resin (B) include the following resins [K1] to [K6].
  • Resin [K1] At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (a) (hereinafter sometimes referred to as "(a)") and a cyclic ether structure having 2 to 4 carbon atoms.
  • a copolymer of and a monomer (b) having an ethylenically unsaturated bond hereinafter, may be referred to as "(b)").
  • Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c).
  • Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c).
  • Resin [K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.
  • (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexendicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-e
  • Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as monosuccinate [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] kind;
  • Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as ⁇ - (hydroxymethyl) acrylic acid.
  • acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerizability and solubility in an alkaline aqueous solution.
  • (B) is a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring (epoxide ring), an oxetane ring and a tetrahydrofuran ring (oxolan ring)) and an ethylenically unsaturated bond.
  • (B) is a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
  • (b) in addition to the monomer (b1) having the epoxy group and the ethylenically unsaturated bond, the monomer (b2) having the oxetanyl group and the ethylenically unsaturated bond (hereinafter, "(b2)).
  • a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond hereinafter, may be referred to as “(b3)” and the like.
  • (meth) acrylic acid represents at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.
  • (B1) is a monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, may be referred to as “(b1-1)”), and an unsaturated alicyclic hydrocarbon is epoxy. Examples thereof include a monomer (b1-2) having a modified structure (hereinafter, may be referred to as “(b1-2)”).
  • Examples of (b1-1) include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, ⁇ -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p.
  • Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy4-vinylcyclohexane (for example, celloxide 2000; manufactured by Daicel Co., Ltd.), and 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclos).
  • Ma A400 manufactured by Daicel Co., Ltd.
  • 3,4-epoxycyclohexylmethyl (meth) acrylate for example, Cyclomer M100; manufactured by Daicel Co., Ltd.
  • Ra and R b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. It may be replaced with.
  • X 1 and X 2 are each independently a single bond, * - R c -, * - R c -O -, * - represents the R c -S- or * -R c -NH-.
  • R c represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with 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, a tert-butyl group and the like.
  • Alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy.
  • R a and R b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.
  • the alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-.
  • Examples include 1,6-diyl group.
  • Examples of X 1 and X 2 include preferably a single bond, a methylene group, an ethylene group, a * -CH 2- O- group, and * -CH 2 CH 2- O- group, and more preferably a single bond, *-. CH 2 CH 2- O-group can be mentioned. * Represents a bond with O.
  • Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15).
  • the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), the formulas (I-11) to the formulas (I-15). Can be mentioned. More preferably, the formula (I-1), the formula (I-7), the formula (I-9), and the formula (I-15) can be mentioned.
  • Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15).
  • formulas (II-1), formulas (II-7), formulas (II-9), and formulas (II-15) can be mentioned.
  • the compound represented by the formula (I) and the compound represented by the formula (II) can be used independently. Also, they can be mixed in any ratio. When mixed, the mixing ratio is a molar ratio, preferably in formula (I): formula (II), 5:95 to 95: 5, more preferably 10:90 to 90:10, still more preferably 20:80. ⁇ 80:20.
  • the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable.
  • Examples of (b2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3-acryloyloxymethyloxetane.
  • the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.
  • Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscort V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.
  • Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
  • Decane-8-yl (meth) acrylate In the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate” and may also be referred to as “tricyclodecyl (meth) acrylate”.
  • Tricyclo [5.2.1.0 2,6 ] decene-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate"), Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) ) (Meta) acrylic acid esters such as acrylate; Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid; Bi
  • benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2. 2.1] Hept-2-ene and the like are preferable. Further, benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferable because they are excellent in developability at the time of pattern formation.
  • the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
  • Structural units derived from (b), particularly structural units derived from (b1); 50-98 mol% (more preferably 55-90 mol%) When the ratio of the structural units of the resin [K1] is within the above range, the storage stability, developability, and solvent resistance of the obtained pattern tend to be excellent.
  • the resin [K1] is described in the method described in the document "Experimental method for polymer synthesis” (written by Takayuki Otsu, published by Kagaku-Dojin Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the document. It can be manufactured with reference to the cited references.
  • the polymerization initiator, solvent, and the like used here are not particularly limited, and any of those usually used in the art can be used.
  • the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.).
  • the solvent may be any solvent that dissolves each monomer, and the solvent (E) described later can be used as the solvent for the colored resin composition.
  • the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the copolymer is taken out as a solid (powder) by a method such as reprecipitation. You may use the one.
  • the solvent (E) described later as the solvent in this polymerization the solution after the reaction can be used as it is, and the production process can be simplified.
  • the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K2].
  • the resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1]. Specifically, predetermined amounts of (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent are charged in the reaction vessel, and stirred, heated and kept warm in a deoxidized atmosphere. There is a way to do it. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation or the like. You may use it.
  • the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K3].
  • the resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1].
  • the resin [K4] obtains a copolymer of (a) and (c), and (a) has a cyclic ether having 2 to 4 carbon atoms of (b), particularly an oxylane ring of (b1). It can be produced by adding it to a carboxylic acid and / or a carboxylic acid anhydride.
  • the copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1].
  • the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
  • a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer contains a cyclic ether having 2 to 4 carbon atoms of (b), particularly an oxylane contained in (b1). React the ring.
  • the atmosphere in the flask was replaced with air from nitrogen, and (b) (particularly (b1)), carboxylic acid or carboxylic acid anhydride and cyclic ether were added.
  • a reaction catalyst for example, tris (dimethylaminomethyl) phenol, etc.
  • a polymerization inhibitor for example, hydroquinone, etc.
  • the amount of (b) used, particularly the amount of (b1) used, is preferably 5 to 80 mol, more preferably 10 to 75 mol, based on 100 mol of (a). Within this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good.
  • the amount of the reaction catalyst used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) (particularly (b1)) and (c).
  • the amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c).
  • the reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the calorific value due to polymerization and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
  • the resin [K5] obtains a copolymer of (b) (particularly (b1)) and (c) in the same manner as in the method for producing the resin [K1] described above.
  • the obtained copolymer may be a solution after the reaction as it is, a concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation. You may use the one taken out as.
  • the ratio of the structural units derived from (b) (particularly (b1)) and (c) is preferably in the following range with respect to the total number of moles of all the structural units constituting the copolymer.
  • (a) is contained in the cyclic ether derived from (b) contained in the copolymer of (b) (particularly (b1)) and (c).
  • the resin [K5] can be obtained by reacting with a carboxylic acid or a carboxylic acid anhydride.
  • the amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol with respect to 100 mol of (b) (particularly (b1)). Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K5], and (b1-1) is further preferable.
  • the resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride.
  • the carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride.
  • carboxylic acid anhydride examples include maleic anhydride, citraconic anhydride, itaconic acid anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride) and the like. Be done. Of the resins [K1] to [K6], the preferred resin is the resin [K1] or [K2].
  • resin (B) preferably a resin containing a cyclic ether structure
  • resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [.
  • Resin [K1] such as 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 ] decylacrylate / (meth) acrylic acid / N-cyclohexyl maleimide Resin such as a polymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid A resin obtained by adding glycidyl (meth) acrylate to a copolymer, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid.
  • Resins with glycidyl (meth) acrylate added to copolymers resins with tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylate copolymers with glycidyl (meth) acrylate added, etc.
  • Resin such as a resin obtained by reacting a copolymer with (meth) acrylic acid [K5]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid
  • a resin [K6] such as a resin obtained by reacting a tetrahydrophthalic acid anhydride can be mentioned, and the resin [K1] is preferable.
  • the resin (B) other than the above specifically, a resin such as 3-methyl-3- (meth) acrylic loyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth). Resins such as acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3] And so on. These resins may be used alone or in combination of two or more.
  • 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. ..
  • the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
  • the solid acid value of the resin (B) is preferably 85 mg-KOH / g or more, more preferably 100 mg-KOH / g or more, and further preferably 110 mg-KOH / g or more.
  • the solid acid value is preferably 200 mg-KOH / g or less, more preferably 180 mg-KOH / g or less, and further preferably 160 mg-KOH / g or less.
  • the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titrating with an aqueous potassium hydroxide solution.
  • the content of the resin (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 30% by mass, based on 100% by mass of the solid content of the colored resin composition. Is. When the content of the resin (B) is within the above range, the unexposed portion tends to have high solubility in the developing solution.
  • the polymerizable compound (C) is not particularly limited as long as it is a compound having a group capable of polymerizing, and examples thereof include a compound capable of ring-opening polymerization and a compound capable of addition polymerization.
  • Examples of the compound capable of ring-opening polymerization include compounds having a cyclic ether structure having about 2 to 4 carbon atoms (for example, an oxylane ring (also referred to as an epoxy ring), an oxetane ring and a tetrahydrofuran ring (also referred to as an oxolane ring)).
  • the compound capable of ring-opening polymerization is more preferably a compound having an oxylan ring or an oxetane ring, and further preferably a compound containing an epoxy group.
  • the compound containing an epoxy group may be a compound having one or more oxylanyl groups.
  • the epoxy compound is different from the resin (B).
  • the film thickness of the colored coating film can be reduced and the dielectric loss tangent can be reduced even if the total colorant content is high.
  • the number of oxylanyl groups contained in the epoxy compound may be one or more, may be two or more, or may be three or more.
  • the acid value of the epoxy compound is preferably less than 30 mg-KOH / g, more preferably 20 mg-KOH / g or less, still more preferably 10 mg-KOH / g or less, and particularly preferably 0 mg-KOH / g. g.
  • the epoxy compound examples include an epoxy compound having no ring such as an epoxy compound of an isoprene (co) polymer and an epoxy compound of an alkandien (co) polymer such as an epoxy compound of a butadiene (co) polymer; a ring.
  • the ring include an alicyclic hydrocarbon ring and an aromatic hydrocarbon ring. These may be heterocycles, but are preferably hydrocarbon rings.
  • Examples of the alicyclic hydrocarbon ring include a cycloalkane ring having 3 to 10 carbon atoms such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptan ring, and a cyclooctane ring; a cyclopentene ring, a cyclohexene ring, and a cycloheptene ring.
  • a cycloalkane ring having 3 to 10 carbon atoms such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptan ring, and a cyclooctane ring
  • a cyclopentene ring a cyclohexene ring
  • Cycloalkene ring with 5 to 10 carbon atoms such as cyclooctane ring; bicyclo [2.2.1] heptane ring (norbornane ring), 1,7,7-trimethylbicyclo [2.2.1] heptane ring (isobornane) Ring), bicyclo [2.2.2] octane ring, tricyclo [5.2.1.0 2,6 ] decane ring, tricyclo [3.3.1.1 3,7 ] decane ring (adamantan ring), etc. Examples thereof include a polycyclic alicyclic hydrocarbon ring having 7 to 15 carbon atoms.
  • the alicyclic hydrocarbon ring is preferably a cycloalkane ring having 4 to 9 carbon atoms, and more preferably a cycloalkane ring having 5 to 8 carbon atoms. Of these, cyclohexane is more preferable.
  • aromatic hydrocarbon ring examples include a benzene ring, a naphthalene ring, an anthracene ring and the like.
  • the epoxy compound having a ring a compound having one or more rings and two or more oxylanyl groups is preferable, and an epoxy compound having two or more rings and two or more oxylanyl groups is more preferable.
  • the number of oxylanyl groups with respect to the number 1 of the ring is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.
  • Examples of the epoxy compound having an alicyclic hydrocarbon ring and two or more oxylanyl groups include 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol. And so on.
  • As the epoxy compound 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (celloxide 2021P, manufactured by Daicel Corporation), ⁇ -caprolactone modified 3', 4'-epoxycyclohexylmethyl 3,4 -Epoxycyclohexanecarboxylate (celloxide 2081, manufactured by Daicel Corporation) and the like can also be mentioned.
  • Examples of the epoxy compound having an aromatic hydrocarbon ring and two or more oxylanyl groups include bisphenol type epoxy compounds, bisphenol F type epoxy compounds, brominated bisphenol A type epoxy compounds and brominated bisphenol F type epoxy compounds.
  • bisphenol A type epoxy compounds and orthocresol novolac type epoxy compounds are particularly preferable.
  • the (weight) average molecular weight of the epoxy compound is preferably less than 3000, more preferably 2900 or less, preferably 50 or more, more preferably 200 or more, still more preferably 350 or more.
  • the epoxy equivalent of the epoxy compound is preferably 30 g / equivalent or more and 400 g / equivalent or less, more preferably 50 g / equivalent or more and 350 g / equivalent or less, still more preferably 100 g / equivalent or more and 300 g / equivalent or less, and particularly preferably 150 g. / Equivalent or more and 250 g / equivalent or less.
  • Epoxy equivalents can be measured by the methods defined in JIS K7236.
  • the content of the compound capable of ring-opening polymerization is preferably 0.01% by mass or more and 10% by mass or less, and 0.1% by mass or more and 5% by mass or less, based on 100% by mass of the colored resin composition (solid content). It is more preferable that it is 0.2% by mass or more and 5% by mass or less.
  • the compound capable of addition polymerization (hereinafter, also referred to as a polymerizable compound (C1)) is particularly limited as long as it is a compound that can be polymerized by an active radical or the like generated from the polymerization initiator (D) by being irradiated with light. Examples thereof include compounds having a polymerizable ethylenically unsaturated bond.
  • the weight average molecular weight of the polymerizable compound (C1) is preferably 3,000 or less.
  • the polymerizable compound (C1) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and is preferably trimethylpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol.
  • Tetra (meth) acrylate dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate , Tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified Examples thereof include pentaerythritol tetra (meth) acrylate, propylene glycol
  • the content of the polymerizable compound (C1) is preferably 20 to 150 parts by mass, and more preferably 80 to 120 parts by mass with respect to 100 parts by mass of the resin (B) in the colored resin composition.
  • the polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light and heat, and a known polymerization initiator can be used.
  • Examples of the polymerization initiator (D) include an O-acyloxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, an acylphosphine oxide compound and the like.
  • the polymerization initiator (D) only one type may be used, or two or more types may be used.
  • a preferred polymerization initiator (D) is an O-acyloxime compound.
  • the O-acyloxime compound is a compound having a structure represented by the formula (d).
  • * represents a bond.
  • O-acyloxime compound examples include a compound represented by the following formula (d1) (hereinafter, may be referred to as compound (d1)) and a compound represented by the formula (d2) (hereinafter, compound (d2). ), And at least one selected from the group consisting of the compound represented by the formula (d3) (hereinafter, may be referred to as compound (d3)) is preferable.
  • R d1 has an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, and a substituent.
  • the contained methylene group (-CH 2- ) may be replaced with -O-, -CO-, -S-, -SO 2- or -NR d5-.
  • R d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
  • R d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.
  • R d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, and the fat.
  • the methylene group (-CH 2- ) contained in the group hydrocarbon group may be replaced with -O-, -CO- or -S-, and the methine group (-CH ⁇ " contained in the aliphatic hydrocarbon group. ) May be replaced with ⁇ PO 3 ⁇ , and the hydrogen atom contained in the aliphatic hydrocarbon group may be replaced with an OH group.
  • R d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (-CH 2- ) contained in the alkyl group may be replaced with -O- or -CO-.
  • the number of carbon atoms of the aromatic hydrocarbon group represented by R d1 is preferably 6 to 15, more preferably 6 to 12, and even more preferably 6 to 10.
  • the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group, and a phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.
  • the aromatic hydrocarbon group represented by R d1 may have 1 or 2 or more substituents.
  • the substituent is preferably substituted at the ⁇ -position or the ⁇ -position of the aromatic hydrocarbon group, and more preferably substituted at the ⁇ -position.
  • the substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group and a pentadecyl group.
  • the alkyl group as the substituent preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms.
  • the alkyl group as the substituent may be linear, branched, or cyclic, or may be a combination of a chain group and a cyclic group.
  • the methylene group (-CH 2- ) contained in the alkyl group as the substituent may be replaced with -O- or -S-.
  • the hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, and is preferably substituted with a fluorine atom.
  • a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, and is preferably substituted with a fluorine atom.
  • alkyl group as a substituent of the aromatic hydrocarbon group represented by R d1 examples include a group represented by the following formula. In the formula, * represents a bond.
  • Examples of the aromatic hydrocarbon group which may have a substituent represented by R d1 include a group represented by the following formula. In the formula, * represents a bond.
  • aromatic hydrocarbon group which may have a substituent represented by R d1 , a group represented by the following formula is preferable.
  • R d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and the hydrogen atom contained in R d6 may be substituted with a halogen atom.
  • m2 represents an integer from 1 to 5.
  • Examples of the alkyl group represented by R d6 include groups similar to the alkyl group exemplified as the substituent of the aromatic hydrocarbon group represented by R d1.
  • the carbon number of R d6 is preferably 2 to 7, and more preferably 2 to 5.
  • the alkyl group represented by R d6 may be linear, branched chain, or cyclic, and is preferably chain (linear or branched).
  • Examples of the halogen atom in which the hydrogen atom contained in R d6 may be substituted include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, and a fluorine atom is particularly preferable.
  • R d6 2 or more and 10 or less hydrogen atoms contained in R d6 are substituted with halogen atoms, and 3 or more and 6 or less are preferably substituted with halogen atoms.
  • the substitution position of the R d6 O-group is preferably the ortho-position or the para-position, and the para-position is particularly preferable.
  • m2 is preferably 1 to 2, and particularly preferably 1.
  • the number of carbon atoms of the heterocyclic group represented by R d1 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5.
  • the heterocyclic group include a pyrrolyl group, a frill group, a thienyl group, an indolyl group, a benzofuryl group and a carbazolyl group.
  • the heterocyclic group represented by R d1 may have 1 or 2 or more substituents. Examples of the substituent include groups similar to those exemplified as the substituents that the aromatic hydrocarbon group represented by R d1 may have.
  • the alkyl group represented by R d1 preferably has 1 to 12 carbon atoms.
  • Examples of the alkyl group represented by R d1 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and tridecyl group. Examples thereof include a tetradecyl group and a pentadecyl group.
  • These alkyl groups may be linear, branched, or cyclic, or may be a combination of a chain (linear or branched) group and a cyclic group. ..
  • the methylene group (-CH 2- ) may be replaced with -O-, -CO-, -S-, -SO 2- or -NR d5-.
  • the hydrogen atom may be substituted with an OH group or an SH group.
  • R d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group may be chain-like (linear or branched-chain), cyclic, linear, branched-chain, or cyclic, and is a chain-like group. And a cyclic group may be combined.
  • the methylene group (-CH 2- ) may be replaced with -O- or -CO-.
  • alkyl group which may have a substituent represented by R d1 include a group represented by the following formula. * Represents a bond.
  • the number of carbon atoms of the group formed by combining an alkanediyl group derived from an alkyl group represented by an aromatic hydrocarbon group and the R d1 is preferably from 7 to 33 and more It is preferably 7 to 18, and more preferably 7 to 12.
  • the combined group may have one or more substituents, and the substituents are the same as those exemplified as the aromatic hydrocarbon group and the substituent which the alkyl group may have. The basis of is mentioned.
  • R d1 Represented by the R d1, as the group which is a combination of an alkanediyl group derived from an alkyl group represented by an aromatic hydrocarbon group and the R d1, an aralkyl group, specifically, the following formula
  • the groups represented by can be mentioned.
  • * represents a bond.
  • R d1 an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent is preferable, and an aromatic hydrocarbon group which may have a substituent may be used. Is more preferable.
  • the number of carbon atoms of the aromatic hydrocarbon group represented by R d2 is preferably 6 to 15, more preferably 6 to 12, and even more preferably 6 to 10.
  • the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group.
  • the number of carbon atoms of the heterocyclic group represented by R d2 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5.
  • the heterocyclic group include a pyrrolyl group, a frill group, a thienyl group, an indolyl group, a benzofuryl group and a carbazolyl group.
  • the alkyl group represented by R d2 preferably has 1 to 7 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably 1 to 3 carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
  • the alkyl group may be linear, branched, or cyclic, or may be a combination of a chain group and a cyclic group.
  • the R d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, still more preferably a chain alkyl group having 1 to 3 carbon atoms, and a methyl group. Especially preferable.
  • the number of carbon atoms of the aromatic hydrocarbon group represented by R d3 is preferably 6 to 15, more preferably 6 to 12, and even more preferably 6 to 10.
  • the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group, and a phenyl group and a naphthyl group are more preferable.
  • the aromatic hydrocarbon group represented by R d3 may have one or more substituents. The substituent is preferably substituted at the ⁇ -position or the ⁇ -position of the aromatic hydrocarbon group.
  • an aliphatic hydrocarbon group having 1 to 15 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group.
  • Alkyl groups having 1 to 15 carbon atoms such as groups and decyl groups; alkenyl groups having 1 to 15 carbon atoms such as ethenyl groups, propenyl groups, butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, nonenyl groups and decenyl groups; etc.
  • the aliphatic hydrocarbon group represented by R d3 may have more preferably 1 to 7 carbon atoms, and the aliphatic hydrocarbon group is linear or branched. It may be either chain-like or cyclic, or it may be a group in which a chain-like group and a cyclic group are combined. Further, the methylene group (-CH 2- ) contained in the aliphatic hydrocarbon group may be replaced with -O-, -CO- or -S-, and the methine group (-CH ⁇ ) is -N. It may be replaced with ⁇ .
  • Examples of the aliphatic hydrocarbon group that the aromatic hydrocarbon group represented by R d3 may have include a group represented by the following formula. In the formula, * represents a bond.
  • Examples of the aromatic hydrocarbon group which may have a substituent represented by R d3 include a group represented by the following formula. In the formula, * represents a bond.
  • the number of carbon atoms of the heterocyclic group represented by R d3 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5.
  • the heterocyclic group include a pyrrolyl group, a frill group, a thienyl group, an indolyl group, a benzofuryl group and a carbazolyl group.
  • the heterocyclic group represented by R d3 may have one or more substituents, and the substituent includes an aromatic hydrocarbon group represented by R d1. Examples of the preferred substituent include groups similar to those exemplified.
  • R d3 is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms), and is substituted.
  • the number of groups is preferably 2 or more and 5 or less.
  • the number of carbon atoms of the aromatic hydrocarbon group represented by R d4 is preferably 6 to 15, more preferably 6 to 12, and even more preferably 6 to 10.
  • the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group, and a phenyl group and a naphthyl group are more preferable, and a phenyl group is further preferable.
  • the aromatic hydrocarbon group represented by R d4 may have one or more substituents. Examples of the substituent include a group similar to the substituent that the aromatic hydrocarbon group of R d1 may have.
  • the number of carbon atoms of the aliphatic hydrocarbon group represented by R d4 is preferably 1 to 13, more preferably 2 to 10, and even more preferably 4 to 9.
  • Examples of the aliphatic hydrocarbon group represented by R d4 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group.
  • Alkyl groups such as tridecyl group, tetradecyl group and pentadecyl group; ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, butadesenyl group.
  • Alkenyl groups such as groups and pentadecenyl groups; and the like.
  • aliphatic hydrocarbon groups may be chain-like (linear or branched-chain), cyclic, or may be a combination of a chain-like group and a cyclic group.
  • the methylene group (-CH 2- ) may be replaced with -O-, -CO- or -S-, and the methine group (-CH ⁇ ) is-. It may be replaced with PO 3 ⁇ , and the hydrogen atom contained in the aliphatic hydrocarbon group may be replaced with an OH group.
  • Examples of the aliphatic hydrocarbon group which may have a substituent represented by R d4 include a group represented by the following formula. In the formula, * represents a bond.
  • R d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group which does not have a substituent, and further preferably a branch which does not have a substituent. It is a chain alkyl group.
  • Examples of the compound (d1) include a compound represented by the formula (d1), specifically, a compound represented by the formula (d1-1) to a compound represented by the formula (d1-67).
  • * represents a bond.
  • the compound represented by the formula (d1-3) to the compound represented by the formula (d1-6), the compound represented by the formula (d1-18) to the compound represented by the formula (d1-52), A compound represented by the formula (d1-55), a compound represented by the formula (d1-56), a compound represented by the formula (d1-60), and a compound represented by the formula (d1-61) are preferable. More preferably, the compound represented by the formula (d1-3) to the compound represented by the formula (d1-6), the compound represented by the formula (d1-18) to the compound represented by the formula (d1-41).
  • Compound (d1) can be produced by the production method described in JP-A-2014-500852.
  • Compound (d2) is An alkyl group having 1 to 15 carbon atoms, in which R d1 may have a substituent, R d2 is an alkyl group having 1 to 10 carbon atoms, An aromatic hydrocarbon group having 6 to 18 carbon atoms, in which R d3 may have a substituent, A compound in which R d4 is an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent is preferable. More preferably, R d1 represents a methyl group, an ethyl group or a propyl group.
  • R d2 represents a methyl group, an ethyl group or a propyl group
  • R d3 represents a phenyl group substituted with a methyl group.
  • the compound (d3) is preferably a compound in which R d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent and R d2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms. More preferably, it is a compound in which R d1 is a hexyl group and R d2 is a phenyl group.
  • O-acyloxym compounds examples include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane.
  • the alkylphenone compound is a compound having a partial structure represented by the formula (d4) or a partial structure represented by the formula (d5).
  • the benzene ring may have a substituent.
  • Examples of the compound having a structure represented by the formula (d4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl).
  • ) 2--Benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one, etc. Be done.
  • Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF) may be used.
  • Examples of the compound having a structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy). ) Phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, ⁇ , ⁇ -diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal.
  • the alkylphenone compound is preferably a compound having a structure represented by the formula (d4).
  • biimidazole compound examples include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4.
  • triazine compounds examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl).
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoin compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthlenquinone, Kinone compounds such as 2-ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, titanosen compounds and the like. These are preferably used in combination with the polymerization initiation aid (D1) (particularly amine
  • the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 5 to 25 parts, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C1). It is by mass, more preferably 10 to 20 parts by mass.
  • the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.
  • the polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is used in combination with the polymerization initiator (D).
  • the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds. Of these, thioxanthone compounds are preferred. Two or more kinds of polymerization initiation aids (D1) may be contained.
  • Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( Ethylmethylamino) benzophenone and the like can be mentioned, with 4,4′-bis (diethylamino) benzophenone being preferred.
  • Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.
  • alkoxyanthracene compound examples include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Examples thereof include anthracene and 2-ethyl-9,10-dibutoxyanthracene.
  • thioxanthone compound examples include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.
  • carboxylic acid compound examples include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, and N.
  • -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.
  • the content of the polymerization initiation aid (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C1). It is a department. When the amount of the polymerization initiation aid (D1) is within this range, a coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.
  • the colored resin composition of the present invention preferably contains a solvent (E).
  • the solvent (E) include an ester solvent (solvent containing -COO-), an ether solvent other than the ester solvent (solvent containing -O-), an ether ester solvent (solvent containing -COO- and -O-), and the like.
  • examples thereof include a ketone solvent (solvent containing ⁇ CO—) other than the ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.
  • ester solvent examples include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, ⁇ -butyrolactone and the like.
  • ether solvent examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.
  • ether ester solvent examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy.
  • Ethyl propionate methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.
  • Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. And so on.
  • Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
  • Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.
  • Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
  • Two or more kinds of the solvent (E) may be used in combination.
  • an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable.
  • propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol.
  • the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the colored resin composition.
  • the solid content of the colored resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass.
  • Leveling agent (F) examples include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
  • silicone-based surfactant examples include surfactants having a siloxane bond in the molecule.
  • Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like. ..
  • fluorine-based surfactant examples include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554.
  • R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).
  • silicone-based surfactant having a fluorine atom examples include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include MegaFvck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).
  • the content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass, based on the total amount of the colored resin composition. Hereinafter, it is more preferably 0.005% by mass or more and 0.05% by mass or less.
  • the content of the pigment dispersant is not included in this content.
  • the colored resin composition of the present invention contains a colorant (A) and a resin (B), and contains a polymerizable compound (C1), a polymerization initiator (D), and if necessary, a solvent (E) and a leveling agent ( It can be prepared by mixing F), a polymerization initiator (D1), and other components.
  • Examples of the method for producing a colored pattern from the colored resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Above all, the photolithography method is preferable.
  • the photolithography method is a method in which the colored resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask.
  • a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask at the time of exposure and / or not developing.
  • the colored pattern or colored coating film thus formed is the color filter of the present invention.
  • the substrate examples include a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and the substrate. Acrylic, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit, etc. may be formed on these substrates. Further, a substrate obtained by subjecting the silicon substrate to HMDS (1,1,1,3,3,3-hexamethyldisilazane) treatment may be used.
  • HMDS 1,1,1,3,3,3-hexamethyldisilazane
  • each color pixel by the photolithography method can be performed by a known or conventional device or condition.
  • it can be produced as follows.
  • the colored resin composition is applied onto a substrate and dried by heating and drying (pre-baking) and / or under reduced pressure to remove volatile components such as a solvent to obtain a smooth colored composition layer.
  • the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
  • the temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C.
  • the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes.
  • the film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.
  • the coloring composition layer is then exposed via a photomask to form the desired coloring pattern.
  • the pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
  • a light source used for exposure a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it.
  • Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp and the like.
  • a mask aligner proximity exposure machine
  • a stepper repetition
  • an exposure apparatus such as a projection exposure machine
  • a coloring pattern is formed on the substrate by developing the coloring composition layer after exposure in contact with a developing solution.
  • the unexposed portion of the coloring composition layer is dissolved in a developing solution and removed.
  • an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable.
  • the concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.
  • the developer may contain a surfactant.
  • the developing method may be any of a paddle method, a dipping method, a spray method and the like.
  • the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water. Further, it is preferable to post-bake the obtained coloring pattern.
  • the post-bake temperature is preferably 80 to 250 ° C, more preferably 100 to 250 ° C, even more preferably 150 to 250 ° C, and even more preferably 160 to 235 ° C.
  • the post-baking time is preferably 1 to 120 minutes, more preferably 2 to 120 minutes, even more preferably 10 to 60 minutes, even more preferably 10 to 30 minutes.
  • the coating film is as thin as possible. Especially when the film is thick, the light from the light source may leak through the pixels of two or more colors when the liquid crystal panel is manufactured, and the colors are vivid when the panel is viewed from an angle. May be lost.
  • the coating film after post-baking is, for example, preferably 4 ⁇ m or less or 3 ⁇ m or less, more preferably 2.8 ⁇ m or less, still more preferably 2.5 ⁇ m or less, and even more preferably 2.3 ⁇ m or less.
  • the lower limit of the coating film is not particularly limited, but is usually 0.1 ⁇ m or more, preferably 0.2 ⁇ m or more, 0.5 ⁇ m or more, or 1 ⁇ m or more, and may be 1.5 ⁇ m or more.
  • the thickness of the colored coating film after post-baking at a temperature of 230 ° C. for 30 minutes is 1 to 4 ⁇ m (preferably 1 to 3 ⁇ m, more preferably 2.8 ⁇ m or less, still more preferably 2.5 ⁇ m or less, still more preferably 2). .3 ⁇ m is formed so as to become less), when illuminated with illumination of which 2.8 ⁇ 10 5 lux (lx), dielectric loss tangent tan ⁇ at the frequency 20Hz is preferable to exhibit 0.20 or less.
  • the tan ⁇ of the colored coating film more preferably 0.18 or less, and further preferably 0.15 or less. The closer the value of tan ⁇ is to 0, the more preferable it is.
  • the tan ⁇ of the colored coating film is preferably measured on the surface opposite to the irradiation surface while irradiating the coating film with a light, and an appropriate commercially available product may be used as the light. Further, the irradiation of the colored coating film can be performed, for example, in the range of illuminance 1.5 ⁇ 10 5 to 3.0 ⁇ 10 5 lux (lx), and the brightness and irradiation distance of the light so that the illuminance is in this range. Should be adjusted. In the examples below, it is measured by the illuminance 2.8 ⁇ 10 5 lux (lx).
  • tan ⁇ By irradiating the colored coating film, it is possible to measure tan ⁇ in the same environment as when the colored coating film (color filter) is actually applied to the display device. Without irradiation of the colored coating film, the value of tan ⁇ tends to be measured as small as, for example, less than 0.04, so it is not possible to evaluate or predict screen display defects that occur when the colored coating film is applied to a display device. It tends to be difficult to do.
  • the colored coating film (color filter) satisfies tan ⁇ in the above range, screen flicker tends to be suppressed, so that it can be suitably used for, for example, a mobile liquid crystal screen.
  • the colored coating film satisfies the above-mentioned dielectric loss tangent and film thickness, and in the XYZ color system, 0 ⁇ x ⁇ 0.40, 0.40 ⁇ y ⁇ 0.85 (preferably 0 ⁇ x ⁇ 0.35, It is preferable to satisfy 0.50 ⁇ y ⁇ 0.85, more preferably 0 ⁇ x ⁇ 0.30, 0.55 ⁇ y ⁇ 0.70).
  • the colored resin composition of the present invention By using the colored resin composition of the present invention, it is possible to manufacture a color filter in which dielectric loss tangent is particularly reduced.
  • the color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.
  • Synthesis example 1 340 parts of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and the atmosphere inside the flask was changed from air to nitrogen and then heated to 80 ° C. Then, a mixed solution of 30 parts of acrylic acid, 60 parts of benzyl methacrylate, 10 parts of tricyclodecanyl methacrylate, and 73 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours.
  • Synthesis example 2 An appropriate amount of nitrogen was poured into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 362 parts by mass of propylene glycol monomethyl ether acetate was placed therein, and the mixture was heated to 80 ° C. with stirring.
  • a mixed solution prepared by dissolving 27 parts by mass of 2,2-azobis (2,4-dimethylvaleronitrile) in 210 parts by mass of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropping, the mixture was kept at the same temperature for 5.5 hours, cooled to room temperature, and had a B-type viscosity (23 ° C.) of 43 mPas, a solid content of 29.8% by mass, and a solid content acid value of 148 mg-KOH / g.
  • a coalesced (resin B2) solution was obtained (hereinafter, may be referred to as a resin solution (B2)).
  • the weight average molecular weight Mw of the produced copolymer was 1.09 ⁇ 10 4 , and the dispersity (molecular weight distribution) was 2.25.
  • Synthesis example 3 An appropriate amount of nitrogen was poured into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 280 parts by mass of propylene glycol monomethyl ether acetate was placed therein, and the mixture was heated to 80 ° C. with stirring. Then, 38 parts by mass of acrylic acid , 289 parts by mass of a mixture of 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane-8 and / or 9-ylacrylate, 125 parts by mass of propylene glycol monomethyl ether acetate. The mixed solution of the part was added dropwise over 5 hours.
  • a mixed solution prepared by dissolving 33 parts by mass of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts by mass of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropping, the copolymer was kept at the same temperature for 4 hours, cooled to room temperature, and had a B-type viscosity (23 ° C.) of 125 mPas, a solid content of 37.0% by mass, and a solid content acid value of 77 mg-KOH / g.
  • a resin B3) solution was obtained (hereinafter, may be referred to as a resin solution (B3)).
  • the weight average molecular weight Mw of the produced copolymer was 9200, and the dispersity (molecular weight distribution) was 2.08.
  • the obtained copolymer solution showed almost no absorption at 500 to 600 nm.
  • the polystyrene-equivalent weight average molecular weight Mw and the number average molecular weight Mn of the resin obtained in the above synthesis example were measured by using the GPC method under the following conditions.
  • the dispersion liquids (A-1) to (A-8) were prepared by mixing the following components and sufficiently dispersing the pigment using a bead mill.
  • the resins (B1) to (B3) the above resin solutions (B1) to (B3) were used.
  • Dispersions (A-1) to (A-8) Dispersion prepared above Resin (B1): Copolymer solution obtained in Synthesis Example 1
  • a colored resin composition was applied onto a 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with this colored resin composition and the quartz glass photomask having a pattern is set to 100 ⁇ m, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used under an air atmosphere of 150 mJ. Light was irradiated with an exposure amount of / cm 2 (based on 365 nm). As the photomask, a mask having a 50 ⁇ m line and space pattern formed was used.
  • the coating film is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and then in an oven at 230 ° C. After 30 minutes of post-baking, a pattern was obtained.
  • the film thickness FT ( ⁇ m) of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).
  • the x and y values of the XYZ color system were 0.270 and 0.638, respectively, and the patterns obtained in Example 5 were obtained.
  • the x and y values of the XYZ color system are 0.214 and 0.638, respectively, and in the pattern obtained in Example 6, the x and y values of the XYZ color system are 0.270 and 0.270, respectively. It was 0.638.
  • Table 8 The results are shown in Table 8.
  • the dielectric loss tangent was measured by the following method. First, a colored resin composition was applied to a glass substrate (resistance: 10 ⁇ ) on which a transparent conductive film (ITO film) was formed by a spin coating method, and prebaked at 100 ° C. for 3 minutes. After cooling, the glass substrate coated with this colored resin composition is irradiated with light at an exposure amount of 80 mJ / cm 2 (365 nm standard) under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). , Post-baked at 230 ° C. for 30 minutes.
  • a transparent conductive film ITO film
  • a Pd / Pt-based vapor deposition material was deposited on the coating film so as to have a diameter of 1.5 cm to prepare an electrode portion.
  • a drop of a silver-based conductive coating material (TreeBond 3350C) was dropped onto the center of the electrode portion, and then dried at 100 ° C. for 3 minutes to obtain a measurement substrate.
  • the colored resin composition of the present invention can be suitably used for manufacturing a color filter, a display device, and a solid-state image sensor.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Une composition de résine colorée comprenant, au moins, un ou plusieurs colorants et une résine, est caractérisée en ce que : la composition de résine colorée comprend un composant contenant une structure éther cyclique; le ou les colorants comprennent au moins un colorant vert ; et la teneur en tous les colorants n'est pas inférieure à 45,5 % en masse par rapport à la teneur en solides de la composition de résine colorée.
PCT/JP2020/031072 2019-08-30 2020-08-18 Composition de résine colorée WO2021039491A1 (fr)

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KR20240140976A (ko) 2022-03-17 2024-09-24 후지필름 가부시키가이샤 착색 조성물, 막, 광학 필터, 고체 촬상 소자 및 화상 표시 장치

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016224447A (ja) * 2015-06-01 2016-12-28 株式会社Ｄｎｐファインケミカル カラーフィルタ用色材分散液、カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、液晶表示装置、及び有機発光表示装置
JP2017145321A (ja) * 2016-02-17 2017-08-24 住友化学株式会社 着色硬化性樹脂組成物、カラーフィルタ及びそれを含む表示装置
WO2019155923A1 (fr) * 2018-02-06 2019-08-15 住友化学株式会社 Composition de résine photosensible colorée

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JP6731703B2 (ja) 2015-03-30 2020-07-29 住友化学株式会社 着色感光性樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016224447A (ja) * 2015-06-01 2016-12-28 株式会社Ｄｎｐファインケミカル カラーフィルタ用色材分散液、カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、液晶表示装置、及び有機発光表示装置
JP2017145321A (ja) * 2016-02-17 2017-08-24 住友化学株式会社 着色硬化性樹脂組成物、カラーフィルタ及びそれを含む表示装置
WO2019155923A1 (fr) * 2018-02-06 2019-08-15 住友化学株式会社 Composition de résine photosensible colorée

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240140976A (ko) 2022-03-17 2024-09-24 후지필름 가부시키가이샤 착색 조성물, 막, 광학 필터, 고체 촬상 소자 및 화상 표시 장치

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