WO2023119898A1 - Pigment dispersion composition, photosensitive colored composition, and color filter - Google Patents

Pigment dispersion composition, photosensitive colored composition, and color filter Download PDF

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Publication number
WO2023119898A1
WO2023119898A1 PCT/JP2022/040986 JP2022040986W WO2023119898A1 WO 2023119898 A1 WO2023119898 A1 WO 2023119898A1 JP 2022040986 W JP2022040986 W JP 2022040986W WO 2023119898 A1 WO2023119898 A1 WO 2023119898A1
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Prior art keywords
group
functional group
pigment
binder resin
pigment dispersion
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PCT/JP2022/040986
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French (fr)
Japanese (ja)
Inventor
健太 大竹
優介 青木
真之介 西村
健宏 木下
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株式会社レゾナック
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Publication of WO2023119898A1 publication Critical patent/WO2023119898A1/en

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    • 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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • 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
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a pigment dispersion composition, a photosensitive coloring composition and a color filter.
  • This application claims priority based on Japanese Patent Application No. 2021-209989 filed in Japan on December 23, 2021, the content of which is incorporated herein.
  • photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams are widely used in various fields such as coatings, printing, paints, and adhesives.
  • active energy rays such as ultraviolet rays and electron beams
  • photosensitive resin compositions are used in solder resists for printed wiring boards and the like, color filter resists for displays such as liquid crystal displays and organic EL displays, and the like.
  • Color filters are generally formed on a transparent substrate such as a glass substrate, red, green and blue pixels formed on the transparent substrate, a black matrix formed at the boundaries of the pixels, and the pixels and the black matrix. and a protective film.
  • a color filter having such a structure is usually manufactured by sequentially forming a colored pattern such as a black matrix and pixels and a pattern such as a protective film on a transparent substrate.
  • Various methods have been proposed as methods for forming various patterns. Among them, a color filter manufactured by a photolithography method, which uses a photosensitive resin composition in which pigments/dyes are dispersed as a resist, and repeats coating, exposure, development, and baking, has excellent durability and is free from pinholes. To give a coloring pattern with few defects. Therefore, the photolithography method is currently the mainstream.
  • a photosensitive resin composition used in photolithography contains an alkali-soluble binder resin, a reactive diluent, a photopolymerization initiator, a pigment/dye (also referred to as a coloring agent) and a solvent.
  • a pattern of black matrix, red, green, and blue is repeatedly formed. It is required to have resistance to various solvents used.
  • organic EL light-emitting layers often use members that are vulnerable to heat, and there is a demand for color filters that cure at low curing temperatures.
  • Dispersants generally have a site that adsorbs to pigments and a site that has high affinity with solvents and other resin compositions.
  • the optimal structure of the site to be adsorbed on the pigment changes according to the surface condition of the pigment.
  • a dispersant having a basic adsorption site is used for a pigment having a biased acid surface, and in many cases, an amino group is used for the basic adsorption site as in Patent Document 1.
  • Patent Documents 1 to 3 a dispersant with excellent solvent resistance that is photocurable by introducing an ethylenically unsaturated group, which is a photosensitive group, into the dispersant and imparting a curing function has also been developed. being developed.
  • the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a pigment dispersion composition having good pigment dispersibility and storage stability. Another object of the present invention is to provide a photosensitive colored composition which, when the present pigment dispersion composition is used, cures at a low temperature to give a cured product having excellent solvent resistance and good developability. An object of the present invention is to provide a color filter having a cured product thereof, and an image display device having the same.
  • the present invention includes the following aspects.
  • the polymeric dispersant (C) is a reaction product of an amino group-containing polymeric compound (c-1) and a halogen compound (c-2) having the functional group (Y) [1 ].
  • the functional group (X) of the binder resin (A-1) is one or more selected from a hydroxy group and a mercapto group;
  • the functional group (X) possessed by the binder resin (A-1) is a carboxy group, and the functional group (Y) possessed by the polymer dispersant (C) is selected from an epoxy group and an oxetanyl group.
  • the functional group (X) of the binder resin (A-1) is one or more selected from a group having a blocked isocyanato group and an alkyl ester;
  • the functional group (X) of the binder resin (A-1) is one or more selected from an epoxy group and an oxetanyl group;
  • the present invention it is possible to provide a pigment dispersion composition with good pigment dispersibility and storage stability. Further, by using the pigment dispersion composition in a photosensitive coloring composition, curing proceeds at a low temperature, and a cured product having excellent solvent resistance and good developability can be obtained. Further, it is possible to provide a color filter having a cured product of the photosensitive coloring composition, and an image display device having the same.
  • (meth)acryloyloxy group represents one or more selected from a methacryloyloxy group and an acryloyloxy group.
  • (meth)acrylic acid represents one or more selected from a methacryloyloxy group and an acryloyloxy group.
  • the pigment dispersion composition of this embodiment contains a binder resin (A-1), a pigment (B), a polymeric dispersant (C), and a solvent (D-1).
  • the binder resin (A-1) of this embodiment does not have an amino group or a quaternary ammonium structure and has a functional group (X).
  • the functional group (X) is crosslinked with the functional group (Y) having reactivity with the functional group (X) of the polymer dispersant (C) described later. Therefore, it exhibits excellent low-temperature curability when used as a photosensitive coloring composition. Moreover, even when cured at a low temperature, the obtained resin cured film exhibits excellent solvent resistance.
  • the functional group (X) possessed by the binder resin (A-1) does not have an amino group or a quaternary ammonium structure, and the functional group (Y) possessed by the polymer dispersant (C) described later, and is not particularly limited as long as it is a group that can be crosslinked by Examples of the functional group (X) include a hydroxy group, a carboxy group, a blocked isocyanato group, an epoxy group, an oxetanyl group, an alkyl ester group (preferably an alkyl ester group having 1 to 3 carbon atoms), a mercapto group, and the like. Among these, a hydroxy group and a blocked isocyanato group are preferable from the viewpoint of stability when used in a millbase because of their high reactivity.
  • These functional groups (X) may contain one type alone or may contain two or more types.
  • the type of binder resin (A-1) is not particularly limited as long as it is a binder resin commonly used for negative resists.
  • examples thereof include (meth)acrylic resins and vinyl ester resins.
  • a (meth)acrylic resin is preferable because it has excellent developability as a photosensitive coloring composition.
  • the (meth)acrylic resin is preferably a copolymer of an ethylenically unsaturated group-containing compound having a functional group (X) and a (meth)acrylate monomer.
  • An ethylenically unsaturated group-containing compound having a functional group (X) is a compound having a functional group (X) and an ethylenically unsaturated group. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, and (meth)acryloyl groups.
  • examples of ethylenically unsaturated group-containing compounds having the functional group (X) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1 , 6-hexanediol (meth)acrylate, 3-methylpentanediol (meth)acrylate, and other ethylenically unsaturated group-containing compounds having a hydroxyl group.
  • examples of ethylenically unsaturated group-containing compounds having the functional group (X) include (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, 2-(meth ) Acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, ⁇ -bromo (meth) acrylic acid, ⁇ -furyl (meth) acrylic acid, croton unsaturated monobasic acids such as acid, propiolic acid, cinnamic acid, ⁇ -cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconate, monomethyl maleate, monoethyl maleate, Unsaturated dibasic acid monoesters
  • examples of ethylenically unsaturated group-containing compounds having the functional group (X) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth) ) acrylate, 3-isocyanatopropyl (meth) acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyanatocyclohexyl (meth) acrylate , a compound obtained by blocking the isocyanate group in an isocyanate compound such as methacryloyl isocyanate with a blocking agent, and an ethylenically unsaturated group-containing compound having a blocked isocyanato group.
  • examples of the ethylenically unsaturated group-containing compound having the functional group (X) include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, lipid (Meth)acrylates having a cyclic epoxy group and their lactone adducts, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylates, epoxidized dicyclopentenyl (meth)acrylates, and dicyclopentenyl Ethylenically unsaturated group-containing compounds having an epoxy group, such as epoxy group-containing (meth)acrylates such as epoxidized oxyethyl (meth)acrylate, can be mentioned.
  • examples of ethylenically unsaturated group-containing compounds having the functional group (X) include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-[ 3-(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy) ) Ethylenically unsaturated group-containing compounds having an oxetanyl group such as pentyloxy]styrene and 2-vinyl-2-methyloxetane.
  • the ethylenically unsaturated group-containing compound having the functional group (X) includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, diethyl citraconate, maleic acid
  • Ethylenically unsaturated group-containing compounds having an alkyl ester group of 1 to 3 carbon atoms such as diethyl, diethyl fumarate, diethyl itaconate, and the like can be mentioned.
  • examples of ethylenically unsaturated group-containing compounds having the functional group (X) include 2-sulfanylethyl (meth)acrylate, 3-sulfanylpropyl (meth)acrylate, or Ethylenically unsaturated group-containing compounds having a mercapto group such as 4-sulfanylbutyl (meth)acrylate, 2-vinylbenzenethiol, 11-bromo-1-undecanethiol, and the like can be mentioned.
  • Examples of the blocking agent that blocks the isocyanate compound include lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, and ⁇ -propiolactam; methanol, ethanol, propanol, butanol, ethylene glycol, methyl Alcohols such as cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; Phenolics such as tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid ester, thymol, p-naphthol, p-nitrophenol, p-chlorophenol; dimethyl malonate, diethyl malonate, methyl acetoacetate, active methylene compounds such as ethyl acetoacetate and acet
  • An ethylenically unsaturated group-containing compound having an isocyanato group and an ethylenically unsaturated group-containing compound having an epoxy group are preferable; hydroxyalkyl (meth)acrylate, (meth)acrylic acid, blocked isocyanato group-containing (meth)acrylate , epoxy group-containing (meth)acrylates; more preferred are blocked isocyanato group-containing (meth)acrylates.
  • These compounds may be used individually by 1 type, or may use 2 or more types.
  • the (meth)acrylate monomer that is copolymerized with the ethylenically unsaturated group-containing compound having the functional group (X) to give the binder resin (A-1) does not have the functional group (X).
  • Examples of the (meth)acrylate monomers include alkyl (meth)acrylates having 4 or more carbon atoms, alicyclic alkyl (meth)acrylates, and aromatic-containing (meth)acrylates.
  • alkyl (meth)acrylate having 4 or more carbon atoms examples include tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isoamyl (meth)acrylate. , dodecyl (meth)acrylate and the like.
  • Examples of the alicyclic alkyl (meth)acrylates include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl ( meth)acrylate, adamantyl (meth)acrylate and the like.
  • Examples of the aromatic-containing (meth)acrylates include benzyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, naphthalene (meth)acrylate, and anthracene (meth)acrylate.
  • alkyl (meth)acrylates having 6 or more carbon atoms for example, 2-ethylhexyl (meth)acrylate), dicyclopentanyl (meth)acrylate, benzyl ( Meth)acrylates are preferred. These compounds may be used individually by 1 type, or may use 2 or more types.
  • binder resin (A-1) is a (meth)acrylic resin
  • other ethylenically unsaturated group-containing monomers may be copolymerized.
  • Other ethylenically unsaturated group-containing monomers include styrene, styrenes such as ⁇ -, o-, m-, and p-alkyl derivatives of styrene, and norbornene (bicyclo[2.2.1]hept-2-ene).
  • a vinyl ester resin is used as the binder resin (A-1), in the process of synthesizing the vinyl ester resin by reacting the epoxy resin and (meth)acrylic acid, the epoxy group is ring-opened to form a hydroxy group. , a hydroxy group is introduced as the functional group (X).
  • a carboxy group is further introduced as the functional group (X)
  • the carboxy group is added by adding a polybasic acid anhydride such as succinic anhydride or maleic anhydride to the hydroxy group of the vinyl ester resin. should be introduced.
  • an epoxy group is introduced as the functional group (X)
  • part of the epoxy group of the raw material epoxy resin may be left unreacted in the process of synthesizing the vinyl ester resin.
  • a blocked isocyanato group, an alkyl ester group, a mercapto group, an oxetanyl group, or the like as the functional group (X), for example, a compound having these functional groups and a carboxy group is added to the hydroxy group of the vinyl ester resin. Examples include a method of adding and introducing.
  • the binder resin (A-1) is introduced with an ethylenically unsaturated group from the viewpoint of excellent developability during exposure and development of the photosensitive coloring composition and improved adhesion of the cured resin film to the substrate.
  • the binder resin (A-1) may be For example, by adding a compound having a functional group (Y) reactive with the functional group (X) and an ethylenically unsaturated group to part of the functional group (X) of the binder resin (A-1) , the binder resin (A-1) can be imparted with a single curing function.
  • the binder resin (A-1) having one or more selected from a hydroxy group and a mercapto group as the functional group (X) block Compounds having an ethylenically unsaturated group and at least one selected from groups having an isocyanato group and an alkyl ester are exemplified. Further, for the binder resin (A-1) having a carboxyl group as the functional group (X), compounds having one or more selected from an epoxy group and an oxetanyl group and an ethylenically unsaturated group can be mentioned.
  • binder resin (A-1) having at least one selected from groups having a blocked isocyanato group and an alkyl ester as the functional group (X), at least one selected from a hydroxy group and a mercapto group at least one selected from a hydroxy group and a mercapto group
  • a compound having an ethylenically unsaturated group can be mentioned.
  • the binder resin (A-1) having one or more selected from an epoxy group and an oxetanyl group as the functional group (X) a compound having a carboxy group and an ethylenically unsaturated group can be mentioned.
  • the binder resin (A-1) described above is a (meth)acrylic resin
  • the ethylenically unsaturated group-containing compound having a functional group (X) and the same as those listed as specific examples A compound can be selected appropriately.
  • the solid content acid value of the binder resin (A-1) is preferably from 10 to 300 mgKOH/g, preferably from 20 to 200 mgKOH/g, from the viewpoint of improving developability during exposure and development of the photosensitive coloring composition. is more preferably 30 to 150 mgKOH/g.
  • the acid value is 10 or more, the effect of improving the developability of the photosensitive coloring composition is sufficiently exhibited.
  • the acid value is 300 or less, the stability as a pigment dispersion composition is good.
  • the acid value of the binder resin (A-1) is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3.
  • the acid value of the binder resin (A-1) means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the binder resin (A-1).
  • the acid value of the binder resin (A-1) is determined by the ethylenically unsaturated group having a carboxyl group as the ethylenically unsaturated group-containing compound having the functional group (X) during the copolymerization of the binder resin (A-1). A contained compound is used and can be adjusted by this compounding amount. Further, when the binder resin (A-1) has a hydroxy group, the acid value can be adjusted by adding a polybasic acid anhydride to introduce a carboxy group.
  • Polybasic acid anhydrides include 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, acid anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, octenylsuccinic anhydride and the like.
  • Method (1) A method of using an ethylenically unsaturated group-containing compound having a hydroxy group as the ethylenically unsaturated group-containing compound having a functional group (X) and copolymerizing the binder resin (A-1).
  • Method (2) Using an ethylenically unsaturated group-containing compound having a carboxy group as the ethylenically unsaturated group-containing compound having a functional group (X), and copolymerizing a precursor of the binder resin (A-1).
  • an ethylenically unsaturated group-containing compound having an epoxy group is added to the carboxy group of the precursor to introduce an ethylenically unsaturated group;
  • a method of introducing a hydroxy group by ring-opening of an epoxy group is Using an ethylenically unsaturated group-containing compound having an epoxy group as the ethylenically unsaturated group-containing compound having a functional group (X), and copolymerizing a precursor of the binder resin (A-1).
  • an ethylenically unsaturated group-containing compound having a carboxy group is added to the epoxy group of the precursor to introduce an ethylenically unsaturated group;
  • a method of introducing a hydroxy group by ring-opening of an epoxy group is also included.
  • the weight average molecular weight of the binder resin (A-1) is preferably 1,000 to 50,000, more preferably 3,000 to 30,000, even more preferably 5,000 to 20,000. When the weight average molecular weight is 5,000 or more and 20,000 or less, good dispersion stability can be obtained when used as a mill base.
  • the amount of the functional group (X) contained in 1 g of the binder resin (A-1) solid is preferably 100 to 3000 ⁇ mol/g, more preferably 300 to 2500 ⁇ mol/g, and more preferably 500 to 2000 ⁇ mol/g. is more preferable.
  • the amount of the functional group (X) is 100 ⁇ mol/g or more, it is possible to produce a millbase having good solvent resistance when formed into a coating film.
  • the amount of the functional group (X) is 3000 ⁇ mol/g or less, good dispersion stability can be obtained when mill base is formed.
  • composition ratio of binder resin (A-1) When the binder resin (A-1) is a (meth)acrylic resin, the content of the ethylenically unsaturated group-containing compound having a functional group (X) is 10 to 75 mol% based on 100 mol% of the copolymerizable monomer. is preferred, 20 to 80 mol% is more preferred, and 30 to 70 mol% is even more preferred. When the content is 10 mol% or more, a sufficient amount of crosslinking with the functional group (Y) of the polymer dispersant (C) described later can be ensured, and the low-temperature curability of the photosensitive coloring composition is good. you get something. When the content is 75 mol% or less, the pigment dispersion composition has good storage stability.
  • the addition rate is , preferably 10 to 80 mol %, more preferably 20 to 70 mol %, relative to the total number of moles of the functional group (X).
  • the addition rate is 10 mol % or more, the solvent resistance is improved when the mill base is made into a coating film, and when the addition rate is 80 mol % or less, good dispersion stability is obtained when the mill base is made.
  • the content of the (meth)acrylate monomer is preferably 25 to 90 mol%, preferably 30 to 70 mol%, and preferably 35 to 60 mol%, based on 100 mol% of the copolymerized monomer.
  • the binder resin (A-1) is a (meth)acrylic resin
  • it can be produced, for example, using the production method shown below. That is, a raw material monomer comprising an ethylenically unsaturated group-containing compound having a functional group (X), a (meth)acrylate monomer, and optionally another ethylenically unsaturated group-containing monomer, and a polymerization solvent , and a polymerization initiator, and radically polymerized under a nitrogen atmosphere, usually at 70° C. to 130° C., to obtain a (meth)acrylic resin as the binder resin (A-1).
  • the solvent for polymerization is not particularly limited as long as it is inert to the copolymerization reaction of the raw material monomers. It may be partially or wholly different from the solvent contained in the solvent (D-1) described below. When the solvent for polymerization is partially or entirely the same as the solvent contained in the solvent (D-1) contained in the pigment dispersion composition, the solvent for polymerization is separated from the reaction solution after completion of the copolymerization reaction, It can be used as part of the solvent (D-1) without removal, which is preferable.
  • Examples of the solvent for polymerization include the same solvents as those exemplified as solvents that may be contained in the solvent (D-1) described later. Among these, from the viewpoint of handling, it is preferable to use (poly)alkylene glycol monoalkyl ether acetates, and it is particularly preferable to use propylene glycol monomethyl ether acetate.
  • the amount of the polymerization solvent used is not particularly limited, but is preferably 30 to 1,000 parts by mass, more preferably 50 to 800 parts by mass, relative to 100 parts by mass of the raw material monomer.
  • the amount of the polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the raw material monomers can be stably carried out, and coloration and gelation of the functional group-containing resin precursor (a) can be prevented.
  • the amount of the polymerization solvent used is 1000 parts by mass or less, the decrease in the molecular weight of the functional group-containing resin precursor (a) due to the chain transfer effect can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.
  • the polymerization initiator that can be used in the copolymerization reaction of the raw material monomers is not particularly limited. valeronitrile), 2,2′-azobis(isobutyrate)dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and the like. These polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 16 parts by mass with respect to 100 parts by mass of the raw material monomer. .
  • a polymerization inhibitor or catalyst is added as necessary, and a compound having a functional group (Y) and an ethylenically unsaturated group is added. , 50 to 150° C. for 1 to 10 hours.
  • the pigment (B) in the present embodiment is not particularly limited as long as it can be uniformly dispersed with other compositions to form pixels of a color filter.
  • Pigments of each color can be used, including pigments of the three primary colors of light such as red, green, and blue, pigments such as yellow, orange, and purple that can be used as complementary colors, and pigments such as black and brown that are used in the black matrix. can.
  • the chemical structure of the pigment (B) includes isoindolinone, isoindoline, azomethine, anthraquinone, anthrone, xanthene, diketopyrrolopyrrole, perylene, perinone, quinacridone, indigoid, dioxazine, indigoid, phthalocyanine, anthocyanin, azo and inorganic pigments such as carbon black, titanium black and titanium dioxide.
  • the pigment (B) in the present embodiment preferably contains a green pigment having a halogenated phthalocyanine skeleton represented by the following formula (1).
  • M represents a divalent or tetravalent metal atom. From the viewpoint of color reproducibility, zinc or copper is preferred, and zinc is particularly preferred.
  • X represents any one of a hydrogen atom, a chlorine atom and a bromine atom, and contains at least one chlorine atom or a bromine atom.
  • the addition ratio of chlorine atoms and bromine atoms changes depending on the brightness and color reproducibility. The more chlorine atoms and fewer bromine atoms, the higher the brightness. Conversely, the more bromine atoms and fewer chlorine atoms, the better the color reproducibility. be.
  • the number of chlorine atoms is preferably 1 or more and 10 or less, more preferably 1.5 or more and 8 or less.
  • the number of bromine atoms is preferably 5 or more and 15 or less, more preferably 7 or more and 14 or less.
  • a green pigment having a halogenated phthalocyanine skeleton and the polymer dispersant (C) By using a green pigment having a halogenated phthalocyanine skeleton and the polymer dispersant (C), sufficient pigment dispersibility and storage stability of the pigment dispersion composition are obtained, and a color filter with high brightness and a wide color reproduction range can be provided, and the heat resistance, solvent resistance, and pattern adhesion of the colored pattern can be imparted.
  • halogenated phthalocyanine pigment a commercially available product may be used, or one may be prepared by oneself.
  • An example of a commercially available product is C.I. I. Pigment Green 7, 36, 58, 59, etc., among which C.I. I. The use of Pigment Greens 58, 59 is preferred.
  • a well-known manufacturing method is utilized.
  • a method of forming a phthalocyanine skeleton in the presence of a catalyst such as ammonium molybdate using phthaloic acid, phthalonitrile, or the like in which some or all of the hydrogen atoms in the aromatic ring are substituted with halogen atoms as a starting material or a method of forming a phthalocyanine skeleton in the presence of chlorine gas or the like.
  • a catalyst such as ammonium molybdate using phthaloic acid, phthalonitrile, or the like in which some or all of the hydrogen atoms in the aromatic ring are substituted with halogen atoms as a starting material
  • a method of forming a phthalocyanine skeleton in the presence of chlorine gas or the like or a method of forming a phthalocyanine skeleton in the presence of chlorine gas or the like.
  • a method of halogenation with bromine gas is mentioned.
  • a desired green pigment can be obtained by dry-grinding the crude
  • the green pigment having a halogenated phthalocyanine skeleton may be used alone, or two or more of them may be used in combination.
  • other pigments other than green pigments having a halogenated phthalocyanine skeleton may be used in combination.
  • Specific examples of other 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, 147, 148, 150, 153, 154, 166, 173, 194, 214; I.
  • C.I. I. red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
  • C. I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60;
  • C.I. I. purple pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. I. Pigment Brown 23, 25 and other brown pigments;
  • These pigments may be used alone or in combination of two or more, depending on the desired pixel color.
  • the pigment (B) in this embodiment not only the pigment but also the dye may be used in combination.
  • a dye when used in combination, higher brightness, an expanded color reproduction range, and better developability can be expected than when a pigment is used.
  • the heat resistance is superior to that of the dye, and the color change after formation of the colored pattern is small.
  • a dye and a pigment may be used in combination depending on the required performance and the desired pixel color.
  • the dye from the viewpoint of solubility in the solvent (D) and alkaline developer, interaction with other components in the resin composition, heat resistance, etc., acid dyes having an acidic group such as a carboxy group, acid dyes, etc. Salts with nitrogen compounds, sulfonamides of acid dyes, and the like are preferably used.
  • dyes include acid alizarin violet N; acid black 1,2,24,48; acid blue 1,7,9,25,29,40,45,62,70,74,80,83,90 , 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; , 56, 63, 74, 95; 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42 , 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and derivatives thereof
  • azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes are preferred. These dyes may be used alone or in combination of two or more. When a dye is used, it is preferably 20 to 80 parts by weight per 100 parts by weight of the pigment (B).
  • the polymeric dispersant (C) of the present embodiment has one or more selected from amino groups and quaternary ammonium cationic groups, and is reactive with the functional group (X) of the binder resin (A-1). It is not particularly limited as long as it has a functional group (Y). Polymeric dispersants having at least one substituent selected from the group consisting of tertiary amino groups and quaternary ammonium cationic groups are more preferred. Since the polymer dispersant (C) has the functional group (Y), it can react with the functional group (X) of the binder resin (A-1) to be crosslinked.
  • a quaternary ammonium cationic group refers to a group having four carbon atoms bonded to a nitrogen atom, excluding amide and urea bonds.
  • the functional group (Y) reactive with the functional group (X) is not particularly limited as long as it is a functional group reactive with the functional group (X) contained in the binder resin (A).
  • the functional group (Y) may be a blocked isocyanato group, an alkyl ester group, an epoxy group, or oxetanyl. group, hydroxy group, mercapto group, carboxy group and the like.
  • the amino groups that the polymeric dispersant (C) may have include primary, secondary and tertiary amino groups.
  • a primary amino group is a group having one carbon atom attached to the nitrogen atom
  • a secondary amino group is a group having two carbon atoms attached to the nitrogen atom
  • a tertiary amino group is a group having three carbon atoms attached to the nitrogen atom, respectively. Refers to a group to which a carbon atom is attached.
  • the amino group and the quaternary ammonium cationic group it is preferable to include at least a tertiary amino group from the viewpoint of the dispersibility and storage stability of the pigment dispersion composition.
  • the polymeric dispersant (C) is preferably a reaction product of the amino group-containing polymeric compound (c-1) and the halogen compound (c-2) having the functional group (Y).
  • a halogen compound means an organic chemical substance to which a halogen atom such as chlorine, bromine or iodine is attached.
  • an amino group-containing polymer compound (c-1) containing a tertiary amino group is reacted with a halogen compound (c-2) having the functional group (Y) to convert the tertiary amino group to a quaternary
  • a polymeric dispersant (C) having an ammonium cationic group is preferred.
  • amino group-containing polymer compound (c-1) examples include polyamines obtained by homopolymerizing a monomer having an amino group and an ethylenically unsaturated group or copolymerizing it with another monomer having an ethylenically unsaturated group.
  • Such polymer compounds include, for example, polyamines that are polymers of vinylamine or polymers of allylamine; or polyamines obtained by copolymerizing vinylamine or allylamine with other monomers having ethylenically unsaturated groups; Polymers obtained by ring-opening polymerization of aziridines, 2-oxazoline and the like; polyalkyleneimines obtained by polycondensation of polyfunctional amine compounds such as ethylenediamine and hexamethylenediamine with haloalkanes and the like.
  • the polymer compound (c-1) may contain amide, imide, urea, urethane, etc. within a range that does not impair the effect, and these have the functional group (Y).
  • halogen compound (c-2) it is the amine structure that greatly contributes to the dispersibility of the pigment, so it is preferred that the amide, imide, urea, and urethane bonds are substantially absent.
  • polyamine obtained by block polymerization of a monomer having an amino group and an ethylenically unsaturated group and a monomer having another ethylenically unsaturated group is preferable, and a monomer having a tertiary amino group and an ethylenically unsaturated group and other ethylene
  • a polyamine obtained by block polymerization with a monomer having a polyunsaturated group is more preferred.
  • the polymeric dispersant (C) By using a block-polymerized polyamine as the polymeric dispersant (C), amino groups are unevenly distributed in one end region, and the affinity with the pigment (B) is improved.
  • the other one end region has an increased affinity with another pigment dispersion composition, specifically a binder resin (A-1) or a solvent (D-1) described later, thereby improving pigment dispersibility and The storage stability of the pigment dispersion composition can be dramatically improved.
  • monomers having an amino group and an ethylenically unsaturated group include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl.
  • a monomer having a tertiary amino group and an ethylenically unsaturated group is preferred, and dimethylaminoethyl (meth)acrylate is more preferred, since it greatly contributes to improving the dispersibility and storage stability of the pigment dispersion composition.
  • a monomer having a tertiary amino group and an ethylenically unsaturated group is used to obtain an amino group-containing polymer compound (c-1) having a tertiary amino group, and the functional group is added to a part of the tertiary amino group.
  • the halogen compound (c-2) having (Y) is reacted to form a quaternary ammonium cationic group, the hydrophilicity is improved and the developability as a photosensitive coloring composition is improved.
  • Examples of monomers having other ethylenically unsaturated groups include alkyl groups, aryl groups, aralkyl groups, cycloalkyl groups, (meth)acrylates having a (poly)oxyalkylene skeleton, etc.
  • Other pigments There is no particular limitation as long as it does not impair the affinity with the dispersion composition.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (Meth)acrylates such as (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or
  • styrenes such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate.
  • vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether
  • fatty acid vinyls such as vinyl acetate or vinyl propionate.
  • amino group-containing polymer compound (c-1) a commercially available product may be used, or it may be prepared by oneself.
  • suitable amino group-containing polymer compounds (c-1) include the DISPERBYK series manufactured by BYK-Chemie, the Solspers series manufactured by Lubrizol, and the EFKA-PX series manufactured by BASF. mentioned.
  • a known polymer production method is used. These amino group-containing polymer compounds (c-1) may be used alone or in combination of two or more, as required.
  • Halogen compound (c-2) The halogen compound (c-2) is not particularly limited as long as it is a monohalogen compound having the functional group (Y).
  • the number of functional groups (Y) is not particularly limited.
  • Specific examples include 2-bromoethanol and epibromohydrin. These compounds may be used alone, or two or more of them may be used. Among them, bromides are preferred from the viewpoint of reactivity.
  • the addition rate of the halogen compound (c-2) to the total amount of amino groups possessed by the amino group-containing polymer compound (c-1) is preferably 5 to 80%, more preferably 10 to 60%. It is preferably 15 to 40%, more preferably 15 to 40%.
  • a sufficient amount of the functional group (Y) is introduced into the polymeric dispersant (C). Therefore, a sufficient amount of cross-linking with the functional group (X) of the binder resin (A-1) can be ensured. As a result, a cured resin film having good low-temperature curability as a photosensitive coloring composition and excellent solvent resistance can be obtained.
  • the polymer dispersant (C) can be easily produced without gelation during synthesis, and good dispersion stability is obtained when mill bases are used. maintains sexuality.
  • the amino group possessed by the amino group-containing polymer compound (c-1) is a tertiary amino group
  • the addition rate of the halogen compound (c-2) is 80% or less, the residual tertiary amino A sufficient base amount can be secured. Therefore, the dispersibility and storage stability of the pigment dispersion composition are sufficient.
  • the amine content (the total amount of primary amine, secondary amine, and tertiary amine) is The amount can be determined quantitatively by measuring the amine value (the value measured according to the standards shown in JIS K7237, etc.).
  • the amine content of the polymer compound (c-1) of the present embodiment is not particularly limited, but is preferably 10 mgKOH/g to 400 mgKOH/g, more preferably 20 mgKOH/g to 200 mgKOH/g, still more preferably 30 mgKOH/g to 100 mg KOH/g.
  • the amine value is 10 mgKOH/g or more, sufficient dispersibility and storage stability of the pigment dispersion composition can be obtained.
  • the tertiary amino group has a particularly large contribution to improving the dispersibility and storage stability of the pigment dispersion composition. Therefore, it is preferable to ensure a sufficient tertiary amine content in the polymeric dispersant (C).
  • the tertiary amine value of the polymer dispersant (C) is preferably 10 mgKOH/g to 400 mgKOH/g, more preferably 30 mgKOH/g to 200 mgKOH/g, still more preferably 40 mgKOH/g to 100 mgKOH/g. is g.
  • the tertiary amine value is a value calculated based on the amount of amino group-containing monomer and halogen compound (c-2) used, based on the amine value V 0 (value measured in accordance with standards such as JIS K7237). be.
  • the amount of the functional group (Y) contained in 1 g of solid polymer dispersant (C) is preferably 50 to 5000 ⁇ mol/g, more preferably 100 to 3000 ⁇ mol/g, and more preferably 150 to 1000 ⁇ mol/g. is more preferable.
  • the amount of the functional group (X) is 50 ⁇ mol/g or more, a cured resin film having excellent developability and low-temperature curability as a photosensitive coloring composition and good solvent resistance can be obtained.
  • the amount of the functional group (X) is 5000 ⁇ mol/g or less, good dispersion stability can be obtained when mill base is formed.
  • the weight-average molecular weight of the polymeric dispersant (C) of the present embodiment is preferably 1,000 to 40,000, more preferably 1,000 to 30,000. Furthermore, the molecular weight distribution of the polymeric dispersant (C) (the value obtained by dividing the polystyrene equivalent weight average molecular weight by the number average molecular weight) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. is within the range of When the molecular weight and molecular weight distribution of the polymeric dispersant (C) are within the above ranges, the viscosity of the pigment dispersion composition can be controlled within an appropriate range. As a result, sufficient pigment dispersibility and storage stability of the pigment dispersion composition can be obtained, and excellent heat resistance, solvent resistance, pattern adhesion, developability, etc. can be ensured.
  • a preferred combination of the functional group (X) possessed by the binder resin (A-1) and the functional group (Y) possessed by the polymer dispersant (C) is from the viewpoint of improving the low-temperature curability of the photosensitive coloring composition.
  • Combination (1) A combination of one or more groups selected from hydroxy groups and mercapto groups as functional groups (X) and one or more groups selected from groups having blocked isocyanato groups and alkyl esters as functional groups (Y).
  • Combination (3) A combination of one or more selected from blocked isocyanato groups and alkyl ester-containing groups as functional groups (X) and one or more selected from hydroxy groups and mercapto groups as functional groups (Y).
  • Combination (4) A combination of one or more types selected from an epoxy group and an oxetanyl group as the functional group (X) and a carboxy group as the functional group (Y).
  • a carboxy group is preferably used in combination in any combination from the viewpoint of improving developability as a photosensitive coloring composition.
  • the polymeric dispersant (C) can be produced, for example, by the following method. That is, it can be produced by adding the halogen compound (c-2) having the functional group (Y) to the amino group of the amino group-containing polymer compound (c-1). As a method for adding the halogen compound (c-2) having the functional group (Y) to the amino group of the polymer compound (c-1), it is preferable to use a bromochlorination reaction. Specifically, the polymer compound (c-1), the halogen compound (c-2) having the functional group (Y), and the solution are mixed in an arbitrary ratio, and the temperature is from room temperature to 150° C., preferably from 30° C. A polymer dispersant (C), which is a reaction product of the polymer compound (c-1) and the halogen compound (c-2) having the functional group (Y), is obtained by reacting at 130°C. .
  • the solvent (D-1) is not particularly limited as long as it does not react with each component contained in the pigment dispersion composition or the photosensitive coloring composition of the present embodiment and is capable of dissolving or dispersing them.
  • the solvent (D-1) the same solvent as used in producing the binder resin (A-1) or the polymer dispersant (C) can be used, and the solvent contained after the reaction can be used as it is. can be used, and more can be added. Moreover, when adding another component, it may coexist there.
  • the solvent (D-1) examples include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate and the like. These may be used alone or in combination of two or more. Among these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, which are preferably used when manufacturing color filters, are preferred.
  • the pigment dispersion composition of the present embodiment is obtained by weighing predetermined amounts of the binder resin (A-1), the polymer dispersant (C), the pigment (B), and the solvent (C-1), and using a known dispersion treatment process. to make the pigment (B) finer and dispersed. Apparatuses such as paint shakers, bead mills, ball mills, roll mills, stone mills, jet mills, homogenizers, planetary mixers, and rotation/revolution mixers are often used in this dispersion treatment process. In addition, in this dispersing treatment step, if beads having a diameter of 0.01 to 10 mm are used, the pigment (B) can be uniformly finely divided efficiently.
  • the material of the beads is not limited, glass beads and zirconia beads are preferably used in consideration of hardness, contamination of the pigment dispersion composition, and the like. Appropriate time, temperature, diameter of beads and usage amount of the dispersion treatment may be adjusted as appropriate, since appropriate conditions vary depending on the composition of the pigment dispersion composition, the size of the apparatus, and the like. Finally, for the purpose of removing fine dust, coarse particles and aggregates of the pigment (B) from the pigment dispersion composition, it is preferable to filter the pigment dispersion composition with a glass filter or the like.
  • the content of the binder resin (A-1) is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass, and 20 to 40 parts by mass with respect to 100 parts by mass of the pigment (B). Part is more preferred.
  • the content of the binder resin (A-1) is 10 parts by mass or more, sufficient developability can be obtained.
  • the content of the binder resin (A-1) is 80 parts by mass or less, good dispersion stability can be obtained when used as a mill base.
  • the content of the polymeric dispersant (C) is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass, and 20 to 40 parts by mass, relative to 100 parts by mass of the pigment (B). Part is more preferred.
  • the content of the polymeric dispersant (C) is 10 parts by mass or more, good dispersion stability can be obtained when mill bases are formed. Sufficient developability is obtained as content of a polymeric dispersing agent (C) is 80 mass parts or less.
  • the amount of the solvent (D-1) is preferably 100 to 900 parts, more preferably 120 to 600 parts when the total of the components of the pigment dispersion composition excluding the solvent (D-1) is 100 parts by mass. , more preferably 150 to 400 parts. If the content of the solvent (D-1) is within the above range, the pigment dispersion composition will have an appropriate viscosity.
  • the content of the polymeric dispersant (C) is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass, and 20 to 40 parts by mass, relative to 100 parts by mass of the pigment (B). Part is more preferred.
  • the photosensitive coloring composition of the present embodiment contains the pigment dispersion composition, a binder resin (A-2), a reactive diluent (E), and a photopolymerization initiator (F).
  • the photosensitive coloring composition of the present embodiment may contain a solvent (D-2).
  • the total binder resin (A) of the binder resin (A-1) and (A-2) is 50 to 280 parts by mass with respect to 100 parts by mass of the pigment (B). , 10 to 80 parts by mass of the polymer dispersant (C), 40 to 200 parts by mass of the reactive diluent (E), and 0.1 to 10 parts by mass of the photopolymerization initiator (F). is preferred.
  • the solvent (D-2) the same solvent as the solvent (D-1) contained in the pigment dispersion composition may be used, or a different solvent may be added.
  • Binder resin (A-2) As the binder resin (A-2), a conventionally known resin that can be used as a photosensitive coloring composition can be used without particular limitation, and the binder resin (A-1) contained in the pigment dispersion composition , may be used in common, or different ones may be used. Alternatively, the binder resin (A-1) may be used as (A-2) without newly adding it as the binder resin (A-2).
  • the total binder resin (A) content of the binder resins (A-1) and (A-2) is preferably 50 to 280 parts by mass with respect to 100 parts by mass of the pigment (B). It is more preferably from 100 to 200 parts by mass, more preferably from 100 to 200 parts by mass.
  • the reactive diluent (E) is not particularly limited as long as it is a low-molecular-weight compound containing an ethylenically unsaturated double bond such as a vinyl group or (meth)acryloyloxy group.
  • the reactive diluent (C) include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; Polycarboxylic acid monomers such as vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ⁇ -hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate , ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, (Metth)
  • compounds having a plurality of (meth)acryloyloxy groups are preferable, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl)isocyanurate
  • a compound having 3 or more (meth)acryloyloxy groups such as tri(meth)acrylate of is more preferable.
  • the content of the reactive diluent (E) is preferably 40 to 200 parts by mass, more preferably 60 to 180 parts by mass, and 80 to 160 parts by mass with respect to 100 parts by mass of the pigment (B). Part is more preferred.
  • the photopolymerization initiator (F) is preferably a photoradical generator, and specific examples include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenones such as acetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone Anthraquinones such as; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and other ketals; acetophenone dimethyl ketal, benzyl ethers such as benzoin, be
  • the content of the photopolymerization initiator (F) is preferably 0.1 to 10 parts by mass, more preferably 1 to 9 parts by mass, based on 100 parts by mass of the pigment (B). It is more preferably 8 parts by mass.
  • the photosensitive coloring composition of the present embodiment contains known additives such as photoacid generators, photobase generators, coupling agents, leveling agents, etc., and fillers to impart predetermined properties. etc. may be added.
  • the blending amount of these components is not particularly limited as long as it does not impair the effects of the present invention.
  • the photosensitive coloring composition of the present embodiment can be produced by mixing the components described above using a known mixing device. For example, it can be produced by first preparing a pigment dispersion composition and then sequentially mixing a binder resin (A-2), a reactive diluent (E), a photopolymerization initiator (F), and the like. Further, if necessary, a solvent (D-2) may be added in addition to the solvent (D-1) contained in the pigment dispersion composition. In that case, the solvent (D) contained in the photosensitive coloring composition contains the solvent (D-1) and the solvent (D-2). The solvent (D-2) may be the same as the solvent (D-1), or may be different.
  • the photosensitive coloring composition obtained as described above has sufficient pigment dispersibility and storage stability of the pigment dispersion composition, can achieve high brightness, and suppresses bleeding out of the dispersant and coloring agent. It is possible to express various resist properties such as excellent heat resistance, solvent resistance, pattern adhesion and developability. As a result, a highly reliable colored pattern can be formed. That is, by using the photosensitive coloring composition, a highly reliable color filter can be provided.
  • the cured resin film of this embodiment can be produced, for example, by the following method. After coating the photosensitive coloring composition of the present embodiment on a substrate such as glass so that the average thickness of the final cured coating film becomes a predetermined value according to the purpose, for 1 to 50 minutes to volatilize the solvent. Next, the entire surface of the coating film is exposed (for example, USH-250BY manufactured by Ushio Inc. is used as a lamp, the exposure amount is 40 mJ/cm 2 ), and further, for example, baking is performed at 50 to 200° C. for 10 to 180 minutes. to obtain a cured coating film. Further, by exposing the coating film through a photomask and developing it with an alkaline developer, a cured coating film having a predetermined color pattern can be obtained.
  • a photomask and developing it with an alkaline developer a cured coating film having a predetermined color pattern can be obtained.
  • the color filter of the present invention has a colored pattern formed using the above photosensitive coloring composition.
  • a color filter is generally composed of a substrate, RGB pixels formed thereon, a black matrix formed at the boundaries of each pixel, and a protective film formed over the pixels and the black matrix. In this configuration, except that the pixels and the black matrix (coloring pattern) are formed using the above-mentioned photosensitive coloring composition, other known configurations can be adopted.
  • a colored pattern is formed on a substrate.
  • a black matrix and RGB pixels are sequentially formed on the substrate.
  • the material of the substrate is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamideimide substrates, polyimide substrates, aluminum substrates, printed wiring substrates, array substrates, etc. can be used as appropriate. can.
  • the colored pattern can be formed by photolithography. Specifically, after coating the photosensitive coloring composition on a substrate to form a coating film, the coating film is exposed through a photomask having a predetermined pattern to photo-cure the exposed portion. By developing the unexposed portion with an alkaline aqueous solution and then baking, a predetermined colored pattern can be formed.
  • the method for applying the photosensitive coloring composition is not particularly limited, but screen printing, roll coating, curtain coating, spray coating, spin coating, and the like can be used.
  • the solvent (D) may be volatilized by heating using a heating means such as a circulating oven, an infrared heater, or a hot plate.
  • the heating conditions are not particularly limited, and may be appropriately set according to the type of photosensitive coloring composition to be used. In general, heating may be performed at a temperature of 50° C. to 120° C. for 30 seconds to 30 minutes.
  • the formed coating film is partially exposed by irradiating it with active energy rays such as ultraviolet rays and excimer laser light through a negative mask.
  • active energy rays such as ultraviolet rays and excimer laser light through a negative mask.
  • the energy dose to be irradiated may be appropriately selected according to the composition of the photosensitive coloring composition, and is preferably, for example, 30 to 2000 mJ/cm2.
  • the light source used for exposure is not particularly limited, but low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, and the like can be used.
  • the alkaline aqueous solution used for development is not particularly limited, but aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; amino groups such as ethylamino group, diethylamino group, and dimethylethanolamino group Aqueous solutions of compounds; tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino -N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates, etc. can be used.
  • the baking conditions are not particularly limited, and heat treatment may be performed according to the type of photosensitive coloring composition to be used. Generally, heating at 80 to 250° C. for 10 to 60 minutes is sufficient.
  • a desired coloring pattern is obtained by successively repeating the coating, exposure, development and baking as described above using a photosensitive coloring composition for black matrix and photosensitive coloring compositions for red, green and blue pixels. can be formed. After that, a protective film is formed on the colored pattern (RGB pixels and black matrix).
  • the color filter produced in this way has excellent pigment dispersibility by achieving uniform fineness of the pigment, achieves high brightness, and has excellent heat resistance, solvent resistance, and adhesion. Suppression of bleeding out of dispersants and coloring agents can be expected.
  • the image display device of the present embodiment is an image display device having the color filter described above, and specific examples thereof include a liquid crystal display device, an organic EL display device, a solid-state imaging device such as a CCD device and a CMOS device, and the like. .
  • the image display device of this embodiment may be manufactured according to a conventional method, except for using the color filter described above. For example, when manufacturing a liquid crystal display device, the above color filter is formed on a substrate, and then electrodes, spacers and the like are sequentially formed. Then, an electrode or the like is formed on another substrate, the two substrates are pasted together, a predetermined amount of liquid crystal is injected, and the substrate is sealed.
  • the amount of the functional group (X)-containing compound is the amount (mol %) of the functional group (X)-containing compound used with respect to 100 mol % of all monomers as raw materials for the binder resin (A-1). It is a calculated value calculated based on the amount of all the monomers and the amount of the functional group (X)-containing compound that are contained in the raw material of the actual binder resin (A-1).
  • the amount of unreacted functional group (X) is the amount after removing the amount of functional group (X) consumed in the addition reaction from the amount of the functional group (X)-containing compound. It is a calculated value calculated based on the calculated amount of the compound containing the functional group (X) and the actual amount of the monomer added for the addition reaction to the binder resin (A-1).
  • the weight average molecular weight and number average molecular weight mean the standard polystyrene conversion weight average molecular weight and number average molecular weight measured under the following conditions using gel permeation chromatography (GPC).
  • halogen compound (c-2) with respect to total amount of amino groups possessed by amino group-containing polymer compound (c-1)
  • the addition rate of the halogen compound (c-2) with respect to the total amount of amino groups possessed by the amino group-containing polymer compound (c-1) is the actual polymer compound (c-1) and the functional group (Y).
  • Amount of halogen compound (c-2) used, amount of functional group (Y) of polymeric dispersant (C), amine value of polymeric dispersant (C), tertiary amine value of polymeric dispersant (C) It is a calculated value calculated based on
  • Y ⁇ Functional Group (Y) Amount of Polymer Dispersant (C)> It is the number of moles of the functional group (Y) per mass of the polymer dispersant (C), and is the actual polymer compound (c-1) and the halogen compound (c-2) having the functional group (Y). It is a calculated value calculated based on the usage amount.
  • a production example of the binder resin (A-1) is shown below.
  • HEMA ethylene glycol methacrylate
  • a polymerization initiator 15.5 g of ethylene glycol methacrylate (HEMA) as a polymerization initiator was added to a monomer mixture consisting of 27.5 g of tricyclodecanyl methacrylate, 66.0 g of benzyl methacrylate and 45.0 g of acrylic acid, 16.3 g of ethylene glycol methacrylate (HEMA).
  • 5 g of t-butyl peroxy-2-ethylhexanoate was added dropwise into the flask from the dropping funnel. After completion of dropping, the mixture was stirred at 120° C. for 2 hours to carry out a copolymerization reaction.
  • TCDMA tricyclodecanyl methacrylate
  • BZMA benzyl methacrylate
  • 2EHA 2-ethylhexyl acrylate
  • HEMA hydroxyethyl methacrylate
  • HBA 4-hydroxybutyl acrylate
  • MAA methacrylic acid AA: acrylic acid
  • MOI-DEM malonic acid-2-[[[2 -methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester
  • MOI-BP 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate
  • MOI-BM 2 -[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate
  • GMA glycidyl methacrylate
  • 3EOXMA (3-ethyloxetan-3-y
  • a production example of the polymer dispersant (C) is shown below.
  • the solution was sampled again, the non-volatile content was measured, converted into the non-volatile content, and after confirming that the polymerization conversion rate was 98% or more, the solution was cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40.0%, and bPD1 (amine value 70 mgKOH/g, weight An average molecular weight of 5500) was obtained.
  • a polymeric dispersant (PD1) was obtained as a reaction product of the compound (c-1) and the halogen compound (c-2) having the functional group (Y).
  • a production example of the photosensitive coloring composition (CR) is shown below.
  • the blending amount of each component for 100 parts by mass of the pigment (B) is 128 parts by mass of the binder resin (A-2), 128 parts by mass of the reactive diluent (E), and 6 parts by mass of the photopolymerization initiator (F). .4 parts by mass.
  • Tables 4A and 4B show the parts used for various materials.
  • the developability test evaluated development speed. Regarding the development speed, in the development step of the green color resist (2), the time required for the pattern to finish being visible during development with a 0.2% by mass potassium hydroxide aqueous solution was measured, and the rate was 1 to 5 according to the following criteria. , and 3 or more was regarded as a pass.
  • the evaluation results are shown in Tables 4A and 4B. "5": less than 40 seconds "4": 40 seconds to less than 50 seconds "3": 50 seconds to less than 60 seconds "2": 60 seconds to less than 70 seconds "1": 70 seconds or more
  • Comparative Examples a'4 and Comparative Examples b'4 the pigment dispersibility of the pigment dispersion composition was significantly poor, and it was difficult to use it as a pigment dispersion composition, and when it was made into a photosensitive coloring composition, Curability was insufficient and solvent resistance was poor, making it difficult to use as a photosensitive coloring composition.
  • Comparative Examples a'1, a'5, a'6, and Comparative Examples b'1, b'5, b'6, the pigment dispersibility and storage stability of the pigment dispersion composition the photosensitive coloring composition While the developability of the photosensitive coloring composition was good, the solvent resistance of the photosensitive coloring composition was poor.
  • the present invention includes a pigment dispersion composition having excellent pigment dispersibility and storage stability, and a photosensitive coloring composition containing the pigment dispersion composition, and the photosensitive coloring composition, solvent resistance, It is possible to provide a color filter that is excellent in developability and is expected to suppress elution and bleeding out of dispersants and pigments.
  • the present invention it is possible to provide a pigment dispersion composition with good pigment dispersibility and storage stability.
  • the pigment dispersion composition it is possible to provide a photosensitive coloring composition from which a cured product having excellent solvent resistance and developability can be obtained. Further, it is possible to provide a color filter having a cured product of the photosensitive coloring composition, and an image display device having the same.

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Abstract

Provided is a pigment dispersion composition satisfactory in terms of pigment dispersibility and storage stability. A photosensitive colored composition comprising the pigment dispersion composition cures at low temperatures to give cured objects having excellent solvent resistance and satisfactory developability. Also provided are: a color filter including a cured object obtained from the photosensitive colored composition; and an image display element equipped with the color filter. This pigment dispersion composition comprises a binder resin (A-1), a pigment (B), a polymeric dispersant (C), and a solvent (D-1). The binder resin (A-1) has a functional group (X), and the polymeric dispersant (C) has a functional group (Y) reactive with the functional group (X).

Description

顔料分散組成物、感光性着色組成物及びカラーフィルターPigment dispersion composition, photosensitive coloring composition and color filter
　本発明は、顔料分散組成物、感光性着色組成物及びカラーフィルターに関する。
　本願は、２０２１年１２月２３日に、日本に出願された特願２０２１－２０９９８９号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a pigment dispersion composition, a photosensitive coloring composition and a color filter.
This application claims priority based on Japanese Patent Application No. 2021-209989 filed in Japan on December 23, 2021, the content of which is incorporated herein.
　現在、省資源および省エネルギーの観点から、各種コーティング、印刷、塗料、接着剤などの分野において、紫外線、電子線などの活性エネルギー線により硬化可能な感光性樹脂組成物が広く使用されている。感光性樹脂組成物は、電子材料の分野において、プリント配線基板などのソルダーレジスト、液晶や有機ＥＬ等のディスプレイのカラーフィルター用レジストなどに使用されている。 Currently, from the perspective of saving resources and energy, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams are widely used in various fields such as coatings, printing, paints, and adhesives. BACKGROUND ART In the field of electronic materials, photosensitive resin compositions are used in solder resists for printed wiring boards and the like, color filter resists for displays such as liquid crystal displays and organic EL displays, and the like.
　カラーフィルターは、一般に、ガラス基板などの透明基板と、透明基板上に形成された赤、緑及び青の画素と、画素の境界に形成されるブラックマトリックスと、画素及びブラックマトリックス上に形成される保護膜とから構成される。このような構成を有するカラーフィルターは、通常、透明基板上にブラックマトリックスや画素といった着色パターンや、保護膜といったパターンを順次形成することによって製造される。各種パターンの形成方法としては、様々な方法が提案されている。その中で、顔料／染料が分散された感光性樹脂組成物をレジストとして用い、塗布、露光、現像及びベーキングを繰り返すフォトリソグラフィ工法で作製されたカラーフィルターは、耐久性に優れ、ピンホールなどの欠陥が少ない着色パターンを与える。そのため、フォトリソグラフィ工法が、現在の主流となっている。 Color filters are generally formed on a transparent substrate such as a glass substrate, red, green and blue pixels formed on the transparent substrate, a black matrix formed at the boundaries of the pixels, and the pixels and the black matrix. and a protective film. A color filter having such a structure is usually manufactured by sequentially forming a colored pattern such as a black matrix and pixels and a pattern such as a protective film on a transparent substrate. Various methods have been proposed as methods for forming various patterns. Among them, a color filter manufactured by a photolithography method, which uses a photosensitive resin composition in which pigments/dyes are dispersed as a resist, and repeats coating, exposure, development, and baking, has excellent durability and is free from pinholes. To give a coloring pattern with few defects. Therefore, the photolithography method is currently the mainstream.
　一般に、フォトリソグラフィ工法に用いられる感光性樹脂組成物は、アルカリ可溶性のあるバインダー樹脂、反応性希釈剤、光重合開始剤、顔料／染料（着色剤ともいう）及び溶剤を含有する。この感光性樹脂組成物を用いたカラーフィルターを作製する方法では、ブラックマトリックス、赤、緑、青のパターンを繰り返し形成することから、感光性樹脂組成物の硬化物には、製造工程中に曝される各種溶剤に対する耐性が求められる。
　加えて、有機ＥＬの発光層は、熱に弱い部材を使用していることが多く、低い硬化温度で硬化するカラーフィルターが求められるようになっている。 In general, a photosensitive resin composition used in photolithography contains an alkali-soluble binder resin, a reactive diluent, a photopolymerization initiator, a pigment/dye (also referred to as a coloring agent) and a solvent. In the method of producing a color filter using this photosensitive resin composition, a pattern of black matrix, red, green, and blue is repeatedly formed. It is required to have resistance to various solvents used.
In addition, organic EL light-emitting layers often use members that are vulnerable to heat, and there is a demand for color filters that cure at low curing temperatures.
　近年、液晶や有機ＥＬ等のディスプレイには高画質化、高精細化が求められており、カラーフィルターに対しても高輝度化、および色再現範囲の拡大を達成する設計が求められている。高輝度化や色再現範囲拡大を実現するため、着色剤として染料のみを用いる例も見られるが、染料は顔料に比べ耐熱性や溶剤耐性が劣り、使用割合や種類が限定されるため、多くの場合は色材に顔料を含有している。顔料を用いてカラーフィルターを形成する場合、顔料の均一な微細化が不可欠である。顔料を微細化することにより、カラーフィルターを透過する光の顔料粒子による散乱が低減され、透過率への寄与が高く、高輝度化が達成される。
　しかし、微細化された顔料粒子は凝集しやすく、顔料の分散性や顔料分散組成物の保存安定性が低下しやすい問題があった。顔料分散組成物において微細化された顔料の分散性を向上する方法として、顔料と分散剤を併用することが有効である。 In recent years, displays such as liquid crystal and organic EL are required to have higher image quality and higher definition, and color filters are also required to be designed to achieve higher brightness and an expanded color reproduction range. In some cases, only dyes are used as coloring agents in order to achieve high brightness and widen the color reproduction range, but dyes are inferior to pigments in heat resistance and solvent resistance, and the proportion and type of use of dyes are limited. In the case of , the coloring material contains a pigment. When forming a color filter using a pigment, it is essential to make the pigment uniformly fine. By miniaturizing the pigment, the scattering of light transmitted through the color filter by the pigment particles is reduced, the contribution to the transmittance is high, and high brightness is achieved.
However, there is a problem that the finely divided pigment particles tend to agglomerate, and the dispersibility of the pigment and the storage stability of the pigment dispersion composition tend to deteriorate. As a method for improving the dispersibility of a finely divided pigment in a pigment dispersion composition, it is effective to use a pigment and a dispersant together.
　さらに、色再現範囲を拡大するために、着色剤を高濃度配合する取組も行われている。着色剤の高濃度化に伴い、分散剤の濃度や他の組成物の濃度が相対的に低減するため、より少量の分散剤であっても、顔料分散性や顔料分散組成物の保存安定性、耐熱性、耐溶剤性、パターン密着性等の各種レジスト特性を発現することが求められる。 In addition, in order to expand the color reproduction range, efforts are also being made to blend colorants at high concentrations. As the concentration of the colorant increases, the concentration of the dispersant and the concentration of other compositions relatively decrease. , heat resistance, solvent resistance, and pattern adhesion.
　一般的に分散剤は、顔料に吸着する部位と、溶剤や他の樹脂組成物と親和性の高い部位とを持ち合わせている。顔料に吸着する部位は、顔料の表面状態に合わせて最適構造が変化する。例えば、酸性に偏った表面を有する顔料には、塩基性の吸着部位を有する分散剤が用いられ、多くの場合、特許文献１のように塩基性の吸着部位にはアミノ基が用いられる。
　また、近年では、特許文献１～３ように、分散剤に感光性基であるエチレン性不飽和基を導入し、硬化機能を付与し、よりよく光硬化する耐溶剤性に優れた分散剤も開発されている。 Dispersants generally have a site that adsorbs to pigments and a site that has high affinity with solvents and other resin compositions. The optimal structure of the site to be adsorbed on the pigment changes according to the surface condition of the pigment. For example, a dispersant having a basic adsorption site is used for a pigment having a biased acid surface, and in many cases, an amino group is used for the basic adsorption site as in Patent Document 1.
In recent years, as in Patent Documents 1 to 3, a dispersant with excellent solvent resistance that is photocurable by introducing an ethylenically unsaturated group, which is a photosensitive group, into the dispersant and imparting a curing function has also been developed. being developed.
特表２００８－５４２５２３号公報Japanese Patent Publication No. 2008-542523 国際公開第２００６／０７５７５４号WO2006/075754 国際公開第２０１３／１７５９７８号WO2013/175978
　しかし、特許文献１～３に開示される分散剤を使用した場合、耐溶剤性が良好な硬化物が得られるが、顔料分散性が不十分で単独での使用が困難である場合や、顔料分散組成物の保存安定性も改善が必要であった。また、導入されている硬化性基がエチレン性不飽和基であるため、高い硬化温度が必要となり、熱に弱い材料などと併用することができず、改善が求められていた。 However, when the dispersants disclosed in Patent Documents 1 to 3 are used, a cured product having good solvent resistance can be obtained, but the pigment dispersibility is insufficient and it is difficult to use the pigment alone. The storage stability of dispersion compositions also needed improvement. In addition, since the curable group introduced is an ethylenically unsaturated group, a high curing temperature is required, and it cannot be used together with heat-sensitive materials.
　本発明は、上記のような課題を解決するためになされたものであり、顔料分散性や保存安定性が良好な顔料分散組成物を提供することを目的とする。また、本発明は、本顔料分散組成物を使用した場合、低温で硬化し、優れた耐溶剤性を有する、現像性が良好な硬化物が得られる感光性着色組成物を提供することを目的とし、その硬化物を有するカラーフィルター、これを具備する画像表示素子を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a pigment dispersion composition having good pigment dispersibility and storage stability. Another object of the present invention is to provide a photosensitive colored composition which, when the present pigment dispersion composition is used, cures at a low temperature to give a cured product having excellent solvent resistance and good developability. An object of the present invention is to provide a color filter having a cured product thereof, and an image display device having the same.
本発明は以下の態様を含む。
〔１〕　バインダー樹脂（Ａ－１）と、
　顔料（Ｂ）と、
　高分子分散剤（Ｃ）と、
　溶剤（Ｄ－１）と、
を含有する顔料分散組成物であって、
　前記バインダー樹脂（Ａ－１）が、アミノ基および４級アンモニウムカチオン基から選択される一種以上を有し、官能基（Ｘ）を有し、
　前記高分子分散剤（Ｃ）が、前記官能基（Ｘ）と反応性を有する官能基（Ｙ）を有することを特徴とする顔料分散組成物。
〔２〕　前記高分子分散剤（Ｃ）が、アミノ基含有高分子化合物（ｃ－１）と、前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）と、の反応物である〔１〕に記載の顔料分散組成物。
〔３〕　前記アミノ基含有高分子化合物（ｃ－１）のアミノ基が３級アミノ基である〔２〕に記載の顔料分散組成物。
〔４〕　前記バインダー樹脂（Ａ－１）の有する官能基（Ｘ）が、ヒドロキシ基及びメルカプト基から選択される一種以上であり、
　前記高分子分散剤（Ｃ）の有する官能基（Ｙ）が、ブロックイソシアナト基及びアルキルエステルを有する基から選択される一種以上である〔１〕～〔３〕のいずれかに記載の顔料分散組成物。
〔５〕　前記バインダー樹脂（Ａ－１）の有する官能基（Ｘ）が、カルボキシ基であり、　前記高分子分散剤（Ｃ）の有する官能基（Ｙ）が、エポキシ基及びオキセタニル基から選択される一種以上である〔１〕～〔３〕のいずれかに記載の顔料分散組成物。
〔６〕　前記バインダー樹脂（Ａ－１）の有する官能基（Ｘ）が、ブロックイソシアナト基及びアルキルエステルを有する基から選択される一種以上であり、
　前記高分子分散剤（Ｃ）の有する官能基（Ｙ）が、ヒドロキシ基及びメルカプト基から選択される一種以上である〔１〕～〔３〕のいずれかに記載の顔料分散組成物。
〔７〕　前記バインダー樹脂（Ａ－１）の有する官能基（Ｘ）が、エポキシ基及びオキセタニル基から選択される一種以上であり、
　前記高分子分散剤（Ｃ）の有する官能基（Ｙ）が、カルボキシ基である〔１〕～〔３〕のいずれかに記載の顔料分散組成物。
〔８〕　前記顔料（Ｂ）が、ハロゲン化フタロシアニン骨格を有する顔料を含む〔１〕～〔７〕のいずれかに記載の顔料分散組成物。
〔９〕　前記顔料（Ｂ）１００質量部に対して、
　前記バインダー樹脂（Ａ－１）を１０～８０質量部を含有し、
　前記高分子分散剤（Ｃ）を１０～８０質量部を含有する〔１〕～〔８〕のいずれかに記載の顔料分散組成物。
〔１０〕　〔１〕～〔９〕のいずれかに記載の顔料分散組成物と、
　バインダー樹脂（Ａ－２）と、
　反応性希釈剤（Ｅ）と、
　光重合開始剤（Ｆ）と
を含有することを特徴とする感光性着色組成物。
〔１１〕　前記顔料（Ｂ）１００質量部に対して、
　前記バインダー樹脂（Ａ－１）を１０～８０質量部を含有し、
　前記高分子分散剤（Ｃ）を１０～８０質量部を含有し、
　前記バインダー樹脂（Ａ－２）を５０～２８０質量部含有し、
　前記反応性希釈剤（Ｅ）を４０～２００質量部含有し、
　前記光重合開始剤（Ｆ）を０．１～１０質量部含有する
〔１０〕に記載の感光性着色組成物。
〔１２〕　〔１０〕又は〔１１〕に記載の感光性着色組成物を硬化させてなる樹脂硬化膜。
〔１３〕　〔１０〕又は〔１１〕に記載の感光性着色組成物の硬化物を有するカラーフィルター。
〔１４〕　請求項１３に記載のカラーフィルターを具備する画像表示素子。 The present invention includes the following aspects.
[1] a binder resin (A-1);
a pigment (B);
a polymeric dispersant (C);
a solvent (D-1);
A pigment dispersion composition containing
The binder resin (A-1) has one or more selected from amino groups and quaternary ammonium cationic groups and has a functional group (X),
A pigment dispersion composition, wherein the polymer dispersant (C) has a functional group (Y) reactive with the functional group (X).
[2] The polymeric dispersant (C) is a reaction product of an amino group-containing polymeric compound (c-1) and a halogen compound (c-2) having the functional group (Y) [1 ].
[3] The pigment dispersion composition according to [2], wherein the amino group of the amino group-containing polymer compound (c-1) is a tertiary amino group.
[4] the functional group (X) of the binder resin (A-1) is one or more selected from a hydroxy group and a mercapto group;
The pigment dispersion according to any one of [1] to [3], wherein the functional group (Y) possessed by the polymeric dispersant (C) is one or more selected from a group having a blocked isocyanato group and an alkyl ester. Composition.
[5] The functional group (X) possessed by the binder resin (A-1) is a carboxy group, and the functional group (Y) possessed by the polymer dispersant (C) is selected from an epoxy group and an oxetanyl group. The pigment dispersion composition according to any one of [1] to [3], which is one or more kinds of pigments.
[6] the functional group (X) of the binder resin (A-1) is one or more selected from a group having a blocked isocyanato group and an alkyl ester;
The pigment dispersion composition according to any one of [1] to [3], wherein the functional group (Y) possessed by the polymeric dispersant (C) is one or more selected from hydroxy groups and mercapto groups.
[7] the functional group (X) of the binder resin (A-1) is one or more selected from an epoxy group and an oxetanyl group;
The pigment dispersion composition according to any one of [1] to [3], wherein the functional group (Y) possessed by the polymer dispersant (C) is a carboxy group.
[8] The pigment dispersion composition according to any one of [1] to [7], wherein the pigment (B) contains a pigment having a halogenated phthalocyanine skeleton.
[9] For 100 parts by mass of the pigment (B),
Containing 10 to 80 parts by mass of the binder resin (A-1),
The pigment dispersion composition according to any one of [1] to [8], containing 10 to 80 parts by mass of the polymer dispersant (C).
[10] the pigment dispersion composition according to any one of [1] to [9];
a binder resin (A-2);
a reactive diluent (E);
A photosensitive coloring composition comprising a photopolymerization initiator (F).
[11] With respect to 100 parts by mass of the pigment (B),
Containing 10 to 80 parts by mass of the binder resin (A-1),
Containing 10 to 80 parts by mass of the polymer dispersant (C),
Containing 50 to 280 parts by mass of the binder resin (A-2),
Containing 40 to 200 parts by mass of the reactive diluent (E),
The photosensitive coloring composition according to [10] containing 0.1 to 10 parts by mass of the photopolymerization initiator (F).
[12] A cured resin film obtained by curing the photosensitive coloring composition of [10] or [11].
[13] A color filter comprising a cured product of the photosensitive coloring composition of [10] or [11].
[14] An image display device comprising the color filter according to [13].
　本発明によれば、顔料分散性や保存安定性が良好な顔料分散組成物を提供することができる。また、当該顔料分散組成物を感光性着色組成物に用いることにより、低温で硬化が進行し、優れた耐溶剤性を有し、現像性が良好な硬化物が得られる。さらに、当該感光性着色組成物の硬化物を有するカラーフィルター、これを具備する画像表示素子を提供することができる。 According to the present invention, it is possible to provide a pigment dispersion composition with good pigment dispersibility and storage stability. Further, by using the pigment dispersion composition in a photosensitive coloring composition, curing proceeds at a low temperature, and a cured product having excellent solvent resistance and good developability can be obtained. Further, it is possible to provide a color filter having a cured product of the photosensitive coloring composition, and an image display device having the same.
　以下、本発明の実施形態について詳細に説明する。ただし、本発明は、以下に示す実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below.
　以下、本発明の実施形態について詳細に説明する。ただし、本発明は、以下に示す実施形態に限定されるものではない。なお、本明細書において「（メタ）アクリロイルオキシ基」とは、メタクリロイルオキシ基およびアクリロイルオキシ基から選択される一種以上を表す。「（メタ）アクリル酸」も同様である。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below. In addition, in this specification, "(meth)acryloyloxy group" represents one or more selected from a methacryloyloxy group and an acryloyloxy group. The same applies to "(meth)acrylic acid".
＜顔料分散組成物＞
　本実施形態の顔料分散組成物は、バインダー樹脂（Ａ－１）と、顔料（Ｂ）と、高分子分散剤（Ｃ）と、溶剤（Ｄ－１）と、を含有する。 <Pigment dispersion composition>
The pigment dispersion composition of this embodiment contains a binder resin (A-1), a pigment (B), a polymeric dispersant (C), and a solvent (D-1).
〔バインダー樹脂（Ａ－１）〕
　本実施形態のバインダー樹脂（Ａ－１）は、アミノ基や４級アンモニウム構造を有さず、官能基（Ｘ）を有する。バインダー樹脂（Ａ－１）を使用することにより、官能基（Ｘ）が、後述する高分子分散剤（Ｃ）が有する前記官能基（Ｘ）と反応性を有する官能基（Ｙ）と架橋するため、感光性着色組成物として使用した際に優れた低温硬化性を発現する。また、低温で硬化させた場合でも得られた樹脂硬化膜は優れた耐溶剤性を発現する。 [Binder resin (A-1)]
The binder resin (A-1) of this embodiment does not have an amino group or a quaternary ammonium structure and has a functional group (X). By using the binder resin (A-1), the functional group (X) is crosslinked with the functional group (Y) having reactivity with the functional group (X) of the polymer dispersant (C) described later. Therefore, it exhibits excellent low-temperature curability when used as a photosensitive coloring composition. Moreover, even when cured at a low temperature, the obtained resin cured film exhibits excellent solvent resistance.
　バインダー樹脂（Ａ－１）が有する官能基（Ｘ）としては、アミノ基や４級アンモニウム構造を有さず、後述する高分子分散剤（Ｃ）が有する、前記官能基（Ｙ）と、加熱により架橋できる基であれば特に限定されない。官能基（Ｘ）として例えば、ヒドロキシ基、カルボキシ基、ブロックイソシアナト基、エポキシ基、オキセタニル基、アルキルエステル基（好ましくは、炭素数１～３のアルキルエステル基）、メルカプト基等が挙げられる。これらの中でも、高い反応性を有し、ミルベースに使用した際の安定性の観点から、ヒドロキシ基、ブロックイソシアナト基が好ましい。これらの官能基（Ｘ）は、一種を単独で含んでいても、２種以上を含んでいても良い。 The functional group (X) possessed by the binder resin (A-1) does not have an amino group or a quaternary ammonium structure, and the functional group (Y) possessed by the polymer dispersant (C) described later, and is not particularly limited as long as it is a group that can be crosslinked by Examples of the functional group (X) include a hydroxy group, a carboxy group, a blocked isocyanato group, an epoxy group, an oxetanyl group, an alkyl ester group (preferably an alkyl ester group having 1 to 3 carbon atoms), a mercapto group, and the like. Among these, a hydroxy group and a blocked isocyanato group are preferable from the viewpoint of stability when used in a millbase because of their high reactivity. These functional groups (X) may contain one type alone or may contain two or more types.
　バインダー樹脂（Ａ－１）の種類としては、ネガ型レジストに一般的に用いられるバインダー樹脂であれば特に限定されない。例えば、（メタ）アクリル樹脂、ビニルエステル樹脂等が挙げられる。中でも、感光性着色組成物として優れた現像性を有する点から、（メタ）アクリル樹脂が好ましい。 The type of binder resin (A-1) is not particularly limited as long as it is a binder resin commonly used for negative resists. Examples thereof include (meth)acrylic resins and vinyl ester resins. Among them, a (meth)acrylic resin is preferable because it has excellent developability as a photosensitive coloring composition.
　（メタ）アクリル樹脂としては、官能基（Ｘ）を有するエチレン性不飽和基含有化合物と、（メタ）アクリレートモノマーとの共重合体が好ましい。官能基（Ｘ）を有するエチレン性不飽和基含有化合物は、官能基（Ｘ）とエチレン性不飽和基とを有する化合物である。エチレン性不飽和基としては、ビニル基、アリル基、（メタ）アクリロイル基等が挙げられる。 The (meth)acrylic resin is preferably a copolymer of an ethylenically unsaturated group-containing compound having a functional group (X) and a (meth)acrylate monomer. An ethylenically unsaturated group-containing compound having a functional group (X) is a compound having a functional group (X) and an ethylenically unsaturated group. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, and (meth)acryloyl groups.
　官能基（Ｘ）がヒドロキシ基である場合、官能基（Ｘ）を有するエチレン性不飽和基含有化合物としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、１，６－ヘキサンジオール（メタ）アクリレート、３－メチルペンタンジオール（メタ）アクリレート等のヒドロキシ基を有するエチレン性不飽和基含有化合物が挙げられる。 When the functional group (X) is a hydroxy group, examples of ethylenically unsaturated group-containing compounds having the functional group (X) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1 , 6-hexanediol (meth)acrylate, 3-methylpentanediol (meth)acrylate, and other ethylenically unsaturated group-containing compounds having a hydroxyl group.
　官能基（Ｘ）がカルボキシ基である場合、官能基（Ｘ）を有するエチレン性不飽和基含有化合物としては、例えば、（メタ）アクリル酸、イタコン酸、クロトン酸、桂皮酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－（メタ）アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、α－ブロモ（メタ）アクリル酸、β－フリル（メタ）アクリル酸、クロトン酸、プロピオール酸、桂皮酸、α－シアノ桂皮酸、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノイソプロピル、フマル酸モノメチル、イタコン酸モノエチル等の不飽和一塩基酸、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノイソプロピル、フマル酸モノメチル、イタコン酸モノエチル等の不飽和二塩基酸モノエステル、もしくは、カルボキシ基を有するエチレン性不飽和基含有化合物が挙げられる。
　官能基（Ｘ）がブロックイソシアナト基である場合、官能基（Ｘ）を有するエチレン性不飽和基含有化合物としては、例えば、２－イソシアナトエチル（メタ）アクリレート、２－イソシアナトプロピル（メタ）アクリレート、３－イソシアナトプロピル（メタ）アクリレート、２－イソシアナト－１－メチルエチル（メタ）アクリレート、２－イソシアナト－１，１－ジメチルエチル（メタ）アクリレート、４－イソシアナトシクロヘキシル（メタ）アクリレート、メタクリロイルイソシアネート等のイソシアネート化合物におけるイソシアナト基をブロック剤でブロック化した化合物、等のブロックイソシアナト基を有するエチレン性不飽和基含有化合物が挙げられる。 When the functional group (X) is a carboxy group, examples of ethylenically unsaturated group-containing compounds having the functional group (X) include (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, 2-(meth ) Acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, α-bromo (meth) acrylic acid, β-furyl (meth) acrylic acid, croton unsaturated monobasic acids such as acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconate, monomethyl maleate, monoethyl maleate, Unsaturated dibasic acid monoesters such as monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate, or ethylenically unsaturated group-containing compounds having a carboxy group may be mentioned.
When the functional group (X) is a blocked isocyanato group, examples of ethylenically unsaturated group-containing compounds having the functional group (X) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth) ) acrylate, 3-isocyanatopropyl (meth) acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyanatocyclohexyl (meth) acrylate , a compound obtained by blocking the isocyanate group in an isocyanate compound such as methacryloyl isocyanate with a blocking agent, and an ethylenically unsaturated group-containing compound having a blocked isocyanato group.
　官能基（Ｘ）がエポキシ基である場合、官能基（Ｘ）を有するエチレン性不飽和基含有化合物としては、例えば、グリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、脂環式エポキシ基を有する（メタ）アクリレートおよびそのラクトン付加物、３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレート、ジシクロペンテニル（メタ）アクリレートのエポキシ化物、並びにジシクロペンテニルオキシエチル（メタ）アクリレートのエポキシ化物等のエポキシ基含有（メタ）アクリレート等のエポキシ基を有するエチレン性不飽和基含有化合物が挙げられる。
　官能基（Ｘ）がオキセタニル基である場合、官能基（Ｘ）を有するエチレン性不飽和基含有化合物としては、例えば、（３－エチルオキセタン－３－イル）メチル（メタ）アクリレート、４－［３－（３－エチルオキセタン－３－イルメトキシ）プロポキシ］スチレン、４－［６－（３－エチルオキセタン－３－イルメトキシ）ヘキシルオキシ］スチレン、４－［５－（３－エチルオキセタン－３－イルメトキシ）ペンチルオキシ］スチレン、２－ビニル－２－メチルオキセタン等のオキセタニル基を有するエチレン性不飽和基含有化合物が挙げられる。 When the functional group (X) is an epoxy group, examples of the ethylenically unsaturated group-containing compound having the functional group (X) include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, lipid (Meth)acrylates having a cyclic epoxy group and their lactone adducts, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylates, epoxidized dicyclopentenyl (meth)acrylates, and dicyclopentenyl Ethylenically unsaturated group-containing compounds having an epoxy group, such as epoxy group-containing (meth)acrylates such as epoxidized oxyethyl (meth)acrylate, can be mentioned.
When the functional group (X) is an oxetanyl group, examples of ethylenically unsaturated group-containing compounds having the functional group (X) include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-[ 3-(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy) ) Ethylenically unsaturated group-containing compounds having an oxetanyl group such as pentyloxy]styrene and 2-vinyl-2-methyloxetane.
　官能基（Ｘ）がアルキルエステル基である場合、官能基（Ｘ）を有するエチレン性不飽和基含有化合物としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、シトラコン酸ジエチル、マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル、等の炭素数１～３のアルキルエステル基を有するエチレン性不飽和基含有化合物が挙げられる。
　官能基（Ｘ）がメルカプト基である場合、官能基（Ｘ）を有するエチレン性不飽和基含有化合物としては、例えば、２－スルファニルエチル（メタ）アクリレート、３－スルファニルプロピル(メタ)アクリレート、または４－スルファニルブチル(メタ)アクリレート、２－ビニルベンゼンチオール、１１－ブロモ－１－ウンデカンチオール等のメルカプト基を有するエチレン性不飽和基含有化合物等が挙げられる。 When the functional group (X) is an alkyl ester group, the ethylenically unsaturated group-containing compound having the functional group (X) includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, diethyl citraconate, maleic acid Ethylenically unsaturated group-containing compounds having an alkyl ester group of 1 to 3 carbon atoms such as diethyl, diethyl fumarate, diethyl itaconate, and the like can be mentioned.
When the functional group (X) is a mercapto group, examples of ethylenically unsaturated group-containing compounds having the functional group (X) include 2-sulfanylethyl (meth)acrylate, 3-sulfanylpropyl (meth)acrylate, or Ethylenically unsaturated group-containing compounds having a mercapto group such as 4-sulfanylbutyl (meth)acrylate, 2-vinylbenzenethiol, 11-bromo-1-undecanethiol, and the like can be mentioned.
　上記イソシアネート化合物をブロック化する前記ブロック剤としては、例えば、ε－カプロラクタム、δ－バレロラクタム、γ－ブチロラクタム、β－プロピオラクタム等のラクタム系； メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、メチルセロソルブ、ブチルセロソルブ、メチルカルビトール、ベンジルアルコール、フェニルセロソルブ、フルフリルアルコール、シクロヘキサノール等のアルコール系； フェノール、クレゾール、キシレノール、エチルフェノール、ｏ－イソプロピルフェノール、ｐ－ｔｅｒｔ－ブチルフェノール等のブチルフェノール、ｐ－ｔｅｒｔ－オクチルフェノール、ノニルフェノール、ジノニルフェノール、スチレン化フェノール、オキシ安息香酸エステル、チモール、ｐ－ナフトール、ｐ－ニトロフェノール、ｐ－クロロフェノール等のフェノール系； マロン酸ジメチル、マロン酸ジエチル、アセト酢酸メチル、アセト酢酸エチル、アセチルアセトン等の活性メチレン系；ブチルメルカプタン、チオフェノール、ｔｅｒｔ－ドデシルメルカプタン等のメルカプタン系； ジフェニルアミン、フェニルナフチルアミン、アニリン、カルバゾール等のアミン系； アセトアニリド、アセトアニシジド、酢酸アミド、ベンズアミド等の酸アミド系； コハク酸イミド、マレイン酸イミド等の酸イミド系； イミダゾール、２－メチルイミダゾール、２－エチルイミダゾール等のイミダゾール系； 尿素、チオ尿素、エチレン尿素等の尿素系； Ｎ－フェニルカルバミン酸フェニル、２－オキサゾリドン等のカルバミド酸塩系： エチレンイミン、ポリエチレンイミン等のイミン系； ホルムアルドオキシム、アセトアルドオキシム、アセトオキシム、メチルエチルケトオキシム、メチルイソブチルケトオキシム、シクロヘキサノンオキシム等のオキシム系； 重亜硫酸ソーダ、重亜硫酸カリウム等の重亜硫酸塩系などが挙げられる。これらの中でも、感光性着色組成物としての低温硬化性が良好である観点から、前記ブロック剤が、マロン酸ジエチル、 ３，５－ジメチルピラゾール及びメチルエチルケトオキシムが好ましく、３，５－ジメチルピラゾール及びメチルエチルケトオキシムがより好ましい。 Examples of the blocking agent that blocks the isocyanate compound include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; methanol, ethanol, propanol, butanol, ethylene glycol, methyl Alcohols such as cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; Phenolics such as tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid ester, thymol, p-naphthol, p-nitrophenol, p-chlorophenol; dimethyl malonate, diethyl malonate, methyl acetoacetate, active methylene compounds such as ethyl acetoacetate and acetylacetone; mercaptan compounds such as butyl mercaptan, thiophenol and tert-dodecylmercaptan; amine compounds such as diphenylamine, phenylnaphthylamine, aniline and carbazole; acids such as acetanilide, acetanisidide, acetic acid amide and benzamide Amide type; acid imide type such as succinimide and maleic acid imide; imidazole type such as imidazole, 2-methylimidazole and 2-ethylimidazole; urea type such as urea, thiourea and ethylene urea; phenyl N-phenylcarbamate , 2-oxazolidone, etc.; imines, such as ethyleneimine and polyethyleneimine; oximes, such as formaldoxime, acetoaldoxime, acetoxime, methylethylketoxime, methylisobutylketoxime, cyclohexanone oxime; sodium bisulfite , and bisulfites such as potassium bisulfite. Among these, the blocking agent is preferably diethyl malonate, 3,5-dimethylpyrazole and methylethylketoxime, and 3,5-dimethylpyrazole and methylethylketo Oximes are more preferred.
　上記官能基（Ｘ）を有するエチレン性不飽和基含有化合物の中でも、合成容易性の観点から、ヒドロキシ基を有するエチレン性不飽和基含有化合物、カルボキシ基を有するエチレン性不飽和基含有化合物、ブロックイソシアナト基を有するエチレン性不飽和基含有化合物、エポキシ基を有するエチレン性不飽和基含有化合物、が好ましく；ヒドロキシアルキル（メタ）アクリレート、（メタ）アクリル酸、ブロックイソシアナト基含有（メタ）アクリレート、エポキシ基含有（メタ）アクリレート、がより好ましく；ブロックイソシアナト基含有（メタ）アクリレートがさらに好ましい。これらの化合物は一種を単独で使用しても、２種以上を使用しても良い。 Among the ethylenically unsaturated group-containing compounds having the functional group (X), from the viewpoint of ease of synthesis, an ethylenically unsaturated group-containing compound having a hydroxy group, an ethylenically unsaturated group-containing compound having a carboxy group, a block An ethylenically unsaturated group-containing compound having an isocyanato group and an ethylenically unsaturated group-containing compound having an epoxy group are preferable; hydroxyalkyl (meth)acrylate, (meth)acrylic acid, blocked isocyanato group-containing (meth)acrylate , epoxy group-containing (meth)acrylates; more preferred are blocked isocyanato group-containing (meth)acrylates. These compounds may be used individually by 1 type, or may use 2 or more types.
　前述官能基（Ｘ）を有するエチレン性不飽和基含有化合物と共重合して、バインダー樹脂（Ａ－１）を与える（メタ）アクリレートモノマーとしては、前記官能基（Ｘ）を有さず、前述の官能基（Ｘ）を有するエチレン性不飽和基含有化合物と共重合可能な（メタ）アクリレートモノマーであれば特に限定されない。前記（メタ）アクリレートモノマーとしては、例えば、炭素数４以上のアルキル（メタ）アクリレート、脂環式アルキル（メタ）アクリレート、芳香族含有（メタ）アクリレート等が挙げられる。
　前記炭素数４以上のアルキル（メタ）アクリレートとしては、例えば、ｔｅｒｔ－ブチル（メタ）アクリルレート、ペンチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソアミル（メタ）アクリレート、ドデシル（メタ）アクリレート等が挙げられる。
　前記脂環式アルキル（メタ）アクリレートとしては、例えば、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、エチルシクロヘキシル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート等が挙げられる。
　前記芳香族含有（メタ）アクリレートとしては、例えば、ベンジル（メタ）アクリレート、トリフェニルメチル（メタ）アクリレート、クミル（メタ）アクリレート、ナフタレン（メタ）アクリレート、アントラセン（メタ）アクリレート等が挙げられる。
　これらの中でも、ミルベースに使用した際の分散安定性の観点から、炭素数６以上のアルキル（メタ）アクリレート（例えば、２－エチルヘキシル（メタ）アクリレート）、ジシクロペンタニル（メタ）アクリレート、ベンジル（メタ）アクリレートが好ましい。これらの化合物は一種を単独で使用しても、２種以上を使用しても良い。 The (meth)acrylate monomer that is copolymerized with the ethylenically unsaturated group-containing compound having the functional group (X) to give the binder resin (A-1) does not have the functional group (X). is not particularly limited as long as it is a (meth)acrylate monomer copolymerizable with an ethylenically unsaturated group-containing compound having a functional group (X) of Examples of the (meth)acrylate monomers include alkyl (meth)acrylates having 4 or more carbon atoms, alicyclic alkyl (meth)acrylates, and aromatic-containing (meth)acrylates.
Examples of the alkyl (meth)acrylate having 4 or more carbon atoms include tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isoamyl (meth)acrylate. , dodecyl (meth)acrylate and the like.
Examples of the alicyclic alkyl (meth)acrylates include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl ( meth)acrylate, adamantyl (meth)acrylate and the like.
Examples of the aromatic-containing (meth)acrylates include benzyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, naphthalene (meth)acrylate, and anthracene (meth)acrylate.
Among these, from the viewpoint of dispersion stability when used in a mill base, alkyl (meth)acrylates having 6 or more carbon atoms (for example, 2-ethylhexyl (meth)acrylate), dicyclopentanyl (meth)acrylate, benzyl ( Meth)acrylates are preferred. These compounds may be used individually by 1 type, or may use 2 or more types.
　バインダー樹脂（Ａ－１）が（メタ）アクリル樹脂である場合、官能基（Ｘ）を有するエチレン性不飽和基含有化合物および（メタ）アクリレートモノマーに加えて、他のエチレン性不飽和基含有モノマーを共重合させても良い。他のエチレン性不飽和基含有モノマーとしては、スチレン、スチレンのα－、ｏ－、ｍ－、ｐ－アルキル誘導体等のスチレン類、ノルボルネン（ビシクロ［２．２．１］ヘプト－２－エン）、５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－エチルビシクロ［２．２．１］ヘプト－２－エン、テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－メチルテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－エチルテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、ジシクロペンタジエン、トリシクロ［５．２．１．０２，６］デカ－８－エン、トリシクロ［５．２．１．０２，６］デカ－３－エン、トリシクロ［４．４．０．１２，５］ウンデカ－３－エン、トリシクロ［６．２．１．０１，８］ウンデカ－９－エン、トリシクロ［６．２．１．０１，８］ウンデカ－４－エン、テトラシクロ［４．４．０．１２，５．１７，１０．０１，６］ドデカ－３－エン、８－メチルテトラシクロ［４．４．０．１２，５．１７，１０．０１，６］ドデカ－３－エン、８－エチリデンテトラシクロ［４．４．０．１２，５．１７，１２］ドデカ－３－エン、８－エチリデンテトラシクロ［４．４．０．１２，５．１７，１０．０１，６］ドデカ－３－エン、ペンタシクロ［６．５．１．１３，６．０２，７．０９，１３］ペンタデカ－４－エン、ペンタシクロ［７．４．０．１２，５．１９，１２．０８，１３］ペンタデカ－３－エン、酢酸ビニル、ビニルトルエン等のビニル化合物が挙げられる。 When the binder resin (A-1) is a (meth)acrylic resin, in addition to the ethylenically unsaturated group-containing compound and (meth)acrylate monomer having a functional group (X), other ethylenically unsaturated group-containing monomers may be copolymerized. Other ethylenically unsaturated group-containing monomers include styrene, styrenes such as α-, o-, m-, and p-alkyl derivatives of styrene, and norbornene (bicyclo[2.2.1]hept-2-ene). , 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10 ] dodec-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17 , 10] dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]dec-8-ene, tricyclo[5.2.1.02,6]dec-3-ene, tricyclo [4.4.0.12,5]undec-3-ene, tricyclo[6.2.1.01,8]undec-9-ene, tricyclo[6.2.1.01,8]undec-4 -ene, tetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01 , 6]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,12]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5 .17,10.01,6]dodeca-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadeca-4-ene, pentacyclo[7.4.0.12 , 5.19, 12.08, 13] and vinyl compounds such as pentadecan-3-ene, vinyl acetate and vinyltoluene.
　バインダー樹脂（Ａ－１）としてビニルエステル樹脂を用いる場合、エポキシ樹脂と（メタ）アクリル酸を反応させてビニルエステル樹脂を合成する過程で、エポキシ基が開環してヒドロキシ基が生成することにより、官能基（Ｘ）としてのヒドロキシ基が導入される。
　官能基（Ｘ）としてさらにカルボキシ基を導入する場合には、ビニルエステル樹脂が有するヒドロキシ基に、コハク酸無水物、マレイン酸無水物等の多塩基酸無水物を付加させることにより、カルボキシ基を導入すればよい。
　官能基（Ｘ）としてエポキシ基を導入する場合には、ビニルエステル樹脂を合成する過程で、原料となるエポキシ樹脂のエポキシ基の一部を反応させずに残せばよい。
　官能基（Ｘ）として、ブロックイソシアナト基、アルキルエステル基、メルカプト基、オキセタニル基等を導入したい場合には、例えば、これらの官能基とカルボキシ基を有する化合物をビニルエステル樹脂が有するヒドロキシ基に付加させて導入する方法等が挙げられる。 When a vinyl ester resin is used as the binder resin (A-1), in the process of synthesizing the vinyl ester resin by reacting the epoxy resin and (meth)acrylic acid, the epoxy group is ring-opened to form a hydroxy group. , a hydroxy group is introduced as the functional group (X).
When a carboxy group is further introduced as the functional group (X), the carboxy group is added by adding a polybasic acid anhydride such as succinic anhydride or maleic anhydride to the hydroxy group of the vinyl ester resin. should be introduced.
When an epoxy group is introduced as the functional group (X), part of the epoxy group of the raw material epoxy resin may be left unreacted in the process of synthesizing the vinyl ester resin.
When it is desired to introduce a blocked isocyanato group, an alkyl ester group, a mercapto group, an oxetanyl group, or the like as the functional group (X), for example, a compound having these functional groups and a carboxy group is added to the hydroxy group of the vinyl ester resin. Examples include a method of adding and introducing.
　バインダー樹脂（Ａ－１）は、感光性着色組成物を露光、現像する際の優れた現像性や、樹脂硬化膜の基材への密着性向上の観点から、エチレン性不飽和基が導入されていてもよい。例えば、バインダー樹脂（Ａ－１）が有する官能基（Ｘ）の一部に、官能基（Ｘ）と反応性を有する官能基（Ｙ）及びエチレン性不飽和基を有する化合物を付加することにより、バインダー樹脂（Ａ－１）に単独での硬化機能を付与することができる。官能基（Ｙ）及びエチレン性不飽和基を有する化合物としては、例えば、官能基（Ｘ）としてヒドロキシ基及びメルカプト基から選択される一種以上を有するバインダー樹脂（Ａ－１）に対して、ブロックイソシアナト基及びアルキルエステルを有する基から選択される一種以上と、エチレン性不飽和基を有する化合物が挙げられる。
　また、官能基（Ｘ）としてカルボキシ基を有するバインダー樹脂（Ａ－１）に対して、エポキシ基及びオキセタニル基から選択される一種以上と、エチレン性不飽和基を有する化合物が挙げられる。
　また、官能基（Ｘ）としてブロックイソシアナト基及びアルキルエステルを有する基から選択される一種以上を有するバインダー樹脂（Ａ－１）に対して、ヒドロキシ基及びメルカプト基から選択される一種以上と、エチレン性不飽和基を有する化合物が挙げられる。
　また、官能基（Ｘ）としてエポキシ基及びオキセタニル基から選択される一種以上を有するバインダー樹脂（Ａ－１）に対して、カルボキシ基と、エチレン性不飽和基を有する化合物が挙げられる。
　それぞれ具体的には、前述のバインダー樹脂（Ａ－１）が（メタ）アクリル樹脂である場合の、官能基（Ｘ）を有するエチレン性不飽和基含有化合物と具体例として挙げたものと同様の化合物を適宜選択することができる。 The binder resin (A-1) is introduced with an ethylenically unsaturated group from the viewpoint of excellent developability during exposure and development of the photosensitive coloring composition and improved adhesion of the cured resin film to the substrate. may be For example, by adding a compound having a functional group (Y) reactive with the functional group (X) and an ethylenically unsaturated group to part of the functional group (X) of the binder resin (A-1) , the binder resin (A-1) can be imparted with a single curing function. As the compound having a functional group (Y) and an ethylenically unsaturated group, for example, the binder resin (A-1) having one or more selected from a hydroxy group and a mercapto group as the functional group (X), block Compounds having an ethylenically unsaturated group and at least one selected from groups having an isocyanato group and an alkyl ester are exemplified.
Further, for the binder resin (A-1) having a carboxyl group as the functional group (X), compounds having one or more selected from an epoxy group and an oxetanyl group and an ethylenically unsaturated group can be mentioned.
Further, for the binder resin (A-1) having at least one selected from groups having a blocked isocyanato group and an alkyl ester as the functional group (X), at least one selected from a hydroxy group and a mercapto group, A compound having an ethylenically unsaturated group can be mentioned.
In addition, for the binder resin (A-1) having one or more selected from an epoxy group and an oxetanyl group as the functional group (X), a compound having a carboxy group and an ethylenically unsaturated group can be mentioned.
Specifically, when the binder resin (A-1) described above is a (meth)acrylic resin, the ethylenically unsaturated group-containing compound having a functional group (X) and the same as those listed as specific examples A compound can be selected appropriately.
　バインダー樹脂（Ａ－１）の固形分酸価は、感光性着色組成物を露光、現像する際の現像性を向上させる観点から、１０～３００ｍｇＫＯＨ／ｇであることが好ましく、２０～２００ｍｇＫＯＨ／ｇであることがより好ましく、３０～１５０ｍｇＫＯＨ／ｇであることがさらに好ましい。酸価が１０以上であると、感光性着色組成物の現像性向上効果が十分に発揮される。酸価が３００以下であると、顔料分散組成物としての安定性が良好である。 The solid content acid value of the binder resin (A-1) is preferably from 10 to 300 mgKOH/g, preferably from 20 to 200 mgKOH/g, from the viewpoint of improving developability during exposure and development of the photosensitive coloring composition. is more preferably 30 to 150 mgKOH/g. When the acid value is 10 or more, the effect of improving the developability of the photosensitive coloring composition is sufficiently exhibited. When the acid value is 300 or less, the stability as a pigment dispersion composition is good.
　なお、バインダー樹脂（Ａ－１）の酸価は、ＪＩＳ　Ｋ６９０１　５．３に従ってブロモチモールブルーとフェノールレッドとの混合指示薬を用いて測定された値である。バインダー樹脂（Ａ－１）の酸価とは、バインダー樹脂（Ａ－１）１ｇ中に含まれる酸性成分を中和するのに要する水酸化カリウムのｍｇ数を意味する。 The acid value of the binder resin (A-1) is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3. The acid value of the binder resin (A-1) means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the binder resin (A-1).
　バインダー樹脂（Ａ－１）の酸価は、バインダー樹脂（Ａ－１）の共重合の際に、官能基（Ｘ）を有するエチレン性不飽和基含有化合物としてカルボキシ基を有するエチレン性不飽和基含有化合物を使用し、この配合量によって調整できる。また、バインダー樹脂（Ａ－１）がヒドロキシ基を有する場合には、ここへ多塩基酸無水物を付加してカルボキシ基を導入することにより、酸価を調整できる。多塩基酸無水物としては、１，２，３，６－テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、４－メチルヘキサヒドロ無水フタル酸、ビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸無水物、メチルビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸無水物、無水コハク酸、オクテニルコハク酸無水物等が挙げられる。 The acid value of the binder resin (A-1) is determined by the ethylenically unsaturated group having a carboxyl group as the ethylenically unsaturated group-containing compound having the functional group (X) during the copolymerization of the binder resin (A-1). A contained compound is used and can be adjusted by this compounding amount. Further, when the binder resin (A-1) has a hydroxy group, the acid value can be adjusted by adding a polybasic acid anhydride to introduce a carboxy group. Polybasic acid anhydrides include 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, acid anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, octenylsuccinic anhydride and the like.
　バインダー樹脂（Ａ－１）にヒドロキシ基を含有させる方法としては、以下の方法（１）～（３）などが挙げられる。
　方法（１）：官能基（Ｘ）を有するエチレン性不飽和基含有化合物として、ヒドロキシ基を有するエチレン性不飽和基含有化合物を使用し、バインダー樹脂（Ａ－１）を共重合する方法。
　方法（２）：官能基（Ｘ）を有するエチレン性不飽和基含有化合物として、カルボキシ基を有するエチレン性不飽和基含有化合物を使用し、バインダー樹脂（Ａ－１）の前駆体を共重合し；その後、官能基（Ｙ）及びエチレン性不飽和基を有する化合物として、エポキシ基を有するエチレン性不飽和基含有化合物を前記前駆体のカルボキシ基に付加してエチレン性不飽和基を導入すし；それとともに、エポキシ基の開環によりヒドロキシ基を導入する方法。
　方法（３）：官能基（Ｘ）を有するエチレン性不飽和基含有化合物として、エポキシ基を有するエチレン性不飽和基含有化合物を使用し、バインダー樹脂（Ａ－１）の前駆体を共重合し；その後、官能基（Ｙ）及びエチレン性不飽和基を有する化合物として、カルボキシ基を有するエチレン性不飽和基含有化合物を前記前駆体のエポキシ基に付加してエチレン性不飽和基を導入し；それとともに、エポキシ基の開環によりヒドロキシ基を導入する方法。 The following methods (1) to (3) and the like can be mentioned as the method for adding a hydroxy group to the binder resin (A-1).
Method (1): A method of using an ethylenically unsaturated group-containing compound having a hydroxy group as the ethylenically unsaturated group-containing compound having a functional group (X) and copolymerizing the binder resin (A-1).
Method (2): Using an ethylenically unsaturated group-containing compound having a carboxy group as the ethylenically unsaturated group-containing compound having a functional group (X), and copolymerizing a precursor of the binder resin (A-1). then, as a compound having a functional group (Y) and an ethylenically unsaturated group, an ethylenically unsaturated group-containing compound having an epoxy group is added to the carboxy group of the precursor to introduce an ethylenically unsaturated group; In addition, a method of introducing a hydroxy group by ring-opening of an epoxy group.
Method (3): Using an ethylenically unsaturated group-containing compound having an epoxy group as the ethylenically unsaturated group-containing compound having a functional group (X), and copolymerizing a precursor of the binder resin (A-1). then, as a compound having a functional group (Y) and an ethylenically unsaturated group, an ethylenically unsaturated group-containing compound having a carboxy group is added to the epoxy group of the precursor to introduce an ethylenically unsaturated group; In addition, a method of introducing a hydroxy group by ring-opening of an epoxy group.
　バインダー樹脂（Ａ－１）の重量平均分子量としては、１０００～５００００が好ましく、３０００～３００００がより好ましく、５０００～２００００がさらに好ましい。重量平均分子量が５０００以上、２００００以下であると、ミルベースにした際に良好な分散安定性が得られる。 The weight average molecular weight of the binder resin (A-1) is preferably 1,000 to 50,000, more preferably 3,000 to 30,000, even more preferably 5,000 to 20,000. When the weight average molecular weight is 5,000 or more and 20,000 or less, good dispersion stability can be obtained when used as a mill base.
　バインダー樹脂（Ａ－１）固形１ｇ中に含まれる官能基（Ｘ）の量は、１００～３０００μｍｏｌ／ｇであることが好ましく、３００～２５００μｍｏｌ／ｇであることがより好ましく、５００～２０００μｍｏｌ／ｇであることがさらに好ましい。官能基（Ｘ）の量が、１００μｍｏｌ／ｇ以上であると、塗膜にした際に良好な耐溶剤性を持つミルベースを作製することができる。官能基（Ｘ）の量が、３０００μｍｏｌ／ｇ以下であるとミルベースにした際に良好な分散安定性が得られる。 The amount of the functional group (X) contained in 1 g of the binder resin (A-1) solid is preferably 100 to 3000 μmol/g, more preferably 300 to 2500 μmol/g, and more preferably 500 to 2000 μmol/g. is more preferable. When the amount of the functional group (X) is 100 μmol/g or more, it is possible to produce a millbase having good solvent resistance when formed into a coating film. When the amount of the functional group (X) is 3000 μmol/g or less, good dispersion stability can be obtained when mill base is formed.
〔バインダー樹脂（Ａ－１）の構成比〕
　バインダー樹脂（Ａ－１）が（メタ）アクリル樹脂である場合、官能基（Ｘ）を有するエチレン性不飽和基含有化合物の含有量は、共重合モノマーを１００モル％として、１０～７５モル％が好ましく、２０～８０モル％がより好ましく、３０～７０モル％がさらに好ましい。含有量が１０モル％以上であると、後述する高分子分散剤（Ｃ）が有する官能基（Ｙ）との架橋量を十分に確保することができ、低温硬化性が良好な感光性着色組成物が得られる。含有量が７５モル％以下であると、顔料分散組成物の保存安定性が良好である。 [Composition ratio of binder resin (A-1)]
When the binder resin (A-1) is a (meth)acrylic resin, the content of the ethylenically unsaturated group-containing compound having a functional group (X) is 10 to 75 mol% based on 100 mol% of the copolymerizable monomer. is preferred, 20 to 80 mol% is more preferred, and 30 to 70 mol% is even more preferred. When the content is 10 mol% or more, a sufficient amount of crosslinking with the functional group (Y) of the polymer dispersant (C) described later can be ensured, and the low-temperature curability of the photosensitive coloring composition is good. you get something. When the content is 75 mol% or less, the pigment dispersion composition has good storage stability.
　また、官能基（Ｙ）及びエチレン性不飽和基を有する化合物を官能基（Ｘ）に付加し、バインダー樹脂（Ａ－１）にエチレン性不飽和基を導入する場合には、その付加率は、官能基（Ｘ）の総モル数に対し、１０～８０モル％であることが好ましく、２０～７０モル％であることがより好ましい。付加率が１０モル％以上であるとミルベースを塗膜にした際に耐溶剤性が向上し、付加率が８０モル％以下であるとミルベースにした際に良好な分散安定性が得られる。 Further, when a compound having a functional group (Y) and an ethylenically unsaturated group is added to the functional group (X) to introduce an ethylenically unsaturated group into the binder resin (A-1), the addition rate is , preferably 10 to 80 mol %, more preferably 20 to 70 mol %, relative to the total number of moles of the functional group (X). When the addition rate is 10 mol % or more, the solvent resistance is improved when the mill base is made into a coating film, and when the addition rate is 80 mol % or less, good dispersion stability is obtained when the mill base is made.
　（メタ）アクリレートモノマーの含有量は、共重合モノマーを１００モル％として、２５～９０モル％が好ましく、３０～７０モル％が好ましく、３５～６０モル％が好ましい。 The content of the (meth)acrylate monomer is preferably 25 to 90 mol%, preferably 30 to 70 mol%, and preferably 35 to 60 mol%, based on 100 mol% of the copolymerized monomer.
〔バインダー樹脂（Ａ－１）の製造方法〕
　バインダー樹脂（Ａ－１）が（メタ）アクリル樹脂である場合、例えば、以下に示す製造方法を用いて製造できる。すなわち、官能基（Ｘ）を有するエチレン性不飽和基含有化合物と、（メタ）アクリレートモノマーと、必要に応じて用いる他のエチレン性不飽和基含有モノマーとからなる原料モノマーと、重合用溶剤と、重合開始剤とを混合し、窒素雰囲気下、通常７０℃～１３０℃の条件下でラジカル重合して、バインダー樹脂（Ａ－１）である（メタ）アクリル樹脂が得られる。重合用溶剤としては、原料モノマーの共重合反応に不活性な溶剤であればよく、特に限定されない。後述する溶剤（Ｄ－１）に含まれる溶剤と一部または全部が異なるものであってもよい。重合用溶剤が、顔料分散組成物の含有している溶剤（Ｄ－１）に含まれる溶剤と一部または全部が同じである場合、共重合反応終了後の反応液から重合用溶媒を分離、除去することなく、溶剤（Ｄ－１）の一部として用いることができ、好ましい。 [Method for producing binder resin (A-1)]
When the binder resin (A-1) is a (meth)acrylic resin, it can be produced, for example, using the production method shown below. That is, a raw material monomer comprising an ethylenically unsaturated group-containing compound having a functional group (X), a (meth)acrylate monomer, and optionally another ethylenically unsaturated group-containing monomer, and a polymerization solvent , and a polymerization initiator, and radically polymerized under a nitrogen atmosphere, usually at 70° C. to 130° C., to obtain a (meth)acrylic resin as the binder resin (A-1). The solvent for polymerization is not particularly limited as long as it is inert to the copolymerization reaction of the raw material monomers. It may be partially or wholly different from the solvent contained in the solvent (D-1) described below. When the solvent for polymerization is partially or entirely the same as the solvent contained in the solvent (D-1) contained in the pigment dispersion composition, the solvent for polymerization is separated from the reaction solution after completion of the copolymerization reaction, It can be used as part of the solvent (D-1) without removal, which is preferable.
　重合用溶剤としては、後述する溶剤（Ｄ－１）が含有してもよい溶剤として例示するものと同様のものが挙げられる。これらの中でも、取り扱いの観点から、（ポリ）アルキレングリコールモノアルキルエーテルアセテート類を用いることが好ましく、特に、プロピレングリコールモノメチルエーテルアセテートを用いることが好ましい。 Examples of the solvent for polymerization include the same solvents as those exemplified as solvents that may be contained in the solvent (D-1) described later. Among these, from the viewpoint of handling, it is preferable to use (poly)alkylene glycol monoalkyl ether acetates, and it is particularly preferable to use propylene glycol monomethyl ether acetate.
　重合用溶剤の使用量は、特に限定されないが、原料モノマー１００質量部に対して、好ましくは３０質量部～１０００質量部であり、より好ましくは５０質量部～８００質量部である。重合用溶剤の使用量が３０質量部以上であると、原料モノマーの共重合反応を安定して行うことができ、官能基含有樹脂前駆体（ａ）の着色およびゲル化を防止できる。重合用溶剤の使用量が１０００質量部以下であると、連鎖移動作用による官能基含有樹脂前駆体（ａ）の分子量の低下を抑制できるとともに、反応溶液の粘度を適切な範囲に制御できる。 The amount of the polymerization solvent used is not particularly limited, but is preferably 30 to 1,000 parts by mass, more preferably 50 to 800 parts by mass, relative to 100 parts by mass of the raw material monomer. When the amount of the polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the raw material monomers can be stably carried out, and coloration and gelation of the functional group-containing resin precursor (a) can be prevented. When the amount of the polymerization solvent used is 1000 parts by mass or less, the decrease in the molecular weight of the functional group-containing resin precursor (a) due to the chain transfer effect can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.
（重合開始剤）
　原料モノマーの共重合反応に用いることが可能な重合開始剤としては、特に限定されないが、例えば、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（イソ酪酸）ジメチル、過酸化ベンゾイル、ｔ－ブチルパーオキシ－２－エチルヘキサノエート等が挙げられる。これらの重合開始剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　重合開始剤の使用量は、特に限定されないが、原料モノマー１００質量部に対して、好ましくは０．１質量部～２０質量部であり、より好ましくは０．５質量部～１６質量部である。 (Polymerization initiator)
The polymerization initiator that can be used in the copolymerization reaction of the raw material monomers is not particularly limited. valeronitrile), 2,2′-azobis(isobutyrate)dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and the like. These polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 16 parts by mass with respect to 100 parts by mass of the raw material monomer. .
　バインダー樹脂（Ａ－１）にエチレン性不飽和基を導入する場合には、必要に応じて重合禁止剤や触媒を追加し、官能基（Ｙ）及びエチレン性不飽和基を有する化合物を添加し、５０～１５０℃の条件下で、１～１０時間反応させればよい。 When introducing an ethylenically unsaturated group into the binder resin (A-1), a polymerization inhibitor or catalyst is added as necessary, and a compound having a functional group (Y) and an ethylenically unsaturated group is added. , 50 to 150° C. for 1 to 10 hours.
〔顔料（Ｂ）〕
　本実施形態における顔料（Ｂ）は、他の組成物と均一に分散しカラーフィルターの画素を形成することができれば、特に限定されない。赤、緑、青といった光の三原色の顔料をはじめ、補色として利用できる黄、橙、紫等の顔料、及びブラックマトリックスで利用される黒、茶等の顔料等、各色の顔料を使用することができる。また、顔料（Ｂ）の化学構造としては、イソインドリノン、イソインドリン、アゾメチン、アントラキノン、アントロン、キサンテン、ジケトピロロピロール、ペリレン、ペリノン、キナクリドン、インジゴイド、ジオキサジン、インジゴイド、フタロシアニン、アントシアニン、アゾ系等のあらゆる有機顔料や、カーボンブラックやチタンブラック、二酸化チタン等の無機顔料が挙げられる。 [Pigment (B)]
The pigment (B) in the present embodiment is not particularly limited as long as it can be uniformly dispersed with other compositions to form pixels of a color filter. Pigments of each color can be used, including pigments of the three primary colors of light such as red, green, and blue, pigments such as yellow, orange, and purple that can be used as complementary colors, and pigments such as black and brown that are used in the black matrix. can. The chemical structure of the pigment (B) includes isoindolinone, isoindoline, azomethine, anthraquinone, anthrone, xanthene, diketopyrrolopyrrole, perylene, perinone, quinacridone, indigoid, dioxazine, indigoid, phthalocyanine, anthocyanin, azo and inorganic pigments such as carbon black, titanium black and titanium dioxide.
　中でも、本実施形態における顔料（Ｂ）は、下記式（１）で示されるハロゲン化フタロシアニン骨格を有する緑色顔料を含むことが好ましい。 Among them, the pigment (B) in the present embodiment preferably contains a green pigment having a halogenated phthalocyanine skeleton represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（１）中、Ｍは２価または４価の金属原子を表す。色再現性の観点から亜鉛又は銅が好ましく、特に亜鉛が好ましい。Ｘは水素原子、塩素原子、臭素原子のいずれか１種を表し、塩素原子又は臭素原子を少なくとも１以上含む。輝度や色再現性に応じて塩素原子と臭素原子の付加割合が変わり、塩素原子が多く臭素原子が少ないほど高輝度となり、反対に臭素原子が多く塩素原子が少ないほど色再現性が良い傾向がある。塩素原子は１以上１０以下が好ましく、１．５以上８以下がより好ましい。臭素原子は５以上１５以下が好ましく、７以上１４以下がより好ましい。 In formula (1), M represents a divalent or tetravalent metal atom. From the viewpoint of color reproducibility, zinc or copper is preferred, and zinc is particularly preferred. X represents any one of a hydrogen atom, a chlorine atom and a bromine atom, and contains at least one chlorine atom or a bromine atom. The addition ratio of chlorine atoms and bromine atoms changes depending on the brightness and color reproducibility. The more chlorine atoms and fewer bromine atoms, the higher the brightness. Conversely, the more bromine atoms and fewer chlorine atoms, the better the color reproducibility. be. The number of chlorine atoms is preferably 1 or more and 10 or less, more preferably 1.5 or more and 8 or less. The number of bromine atoms is preferably 5 or more and 15 or less, more preferably 7 or more and 14 or less.
　ハロゲン化フタロシアニン骨格を有する緑色顔料と前記高分子分散剤（Ｃ）を用いることで、十分な顔料分散性や顔料分散組成物の保存安定性が得られ、高輝度かつ色再現範囲の広いカラーフィルターを提供することができると共に、着色パターンの耐熱性、耐溶剤性、パターン密着性を付与することができる。 By using a green pigment having a halogenated phthalocyanine skeleton and the polymer dispersant (C), sufficient pigment dispersibility and storage stability of the pigment dispersion composition are obtained, and a color filter with high brightness and a wide color reproduction range can be provided, and the heat resistance, solvent resistance, and pattern adhesion of the colored pattern can be imparted.
　ハロゲン化フタロシアニン顔料としては、市販品を用いても良いし、自ら準備しても良い。市販品の一例としては、Ｃ．Ｉ．ピグメントグリーン７、３６、５８、５９等が挙げられ、中でも高輝度化や色再現性の高さからＣ．Ｉ．ピグメントグリーン５８、５９の使用が好ましい。
　自ら準備する場合は、公知の製造方法を利用する。例えば、芳香環の水素原子の一部又は全てがハロゲン原子に置換されたフタロ酸やフタロニトリル等を出発原料とし、モリブデン酸アンモニウム等の触媒下フタロシアニン骨格を形成する方法や、フタロシアニンを塩素ガスや臭素ガスでハロゲン化する方法が挙げられる。これらの方法で得られた粗顔料をボールミル、振動ミル等の粉砕機内で乾式摩砕し、公知のソルベントソルトミリング法等で処理することで、所望の緑色顔料を得ることができる。 As the halogenated phthalocyanine pigment, a commercially available product may be used, or one may be prepared by oneself. An example of a commercially available product is C.I. I. Pigment Green 7, 36, 58, 59, etc., among which C.I. I. The use of Pigment Greens 58, 59 is preferred.
When preparing by oneself, a well-known manufacturing method is utilized. For example, a method of forming a phthalocyanine skeleton in the presence of a catalyst such as ammonium molybdate using phthaloic acid, phthalonitrile, or the like in which some or all of the hydrogen atoms in the aromatic ring are substituted with halogen atoms as a starting material, or a method of forming a phthalocyanine skeleton in the presence of chlorine gas or the like. A method of halogenation with bromine gas is mentioned. A desired green pigment can be obtained by dry-grinding the crude pigment obtained by these methods in a pulverizer such as a ball mill or a vibrating mill, followed by a known solvent salt milling method or the like.
　本実施形態における顔料（Ｂ）について、ハロゲン化フタロシアニン骨格を有する緑色顔料は単独で用いてもよいし、２種以上を組み合わせて用いても良い。また、ハロゲン化フタロシアニン骨格を有する緑色顔料ではない他の顔料を併用しても良い。
　他の顔料の具体例としては、Ｃ．Ｉ．ピグメントイエロー１、３、１２、１３、１４、１５、１６、１７、２０、２４、３１、５３、８３、８６、９３、９４、１０９、１１０、１１７、１２５、１２８、１３７、１３８、１３９、１４７、１４８、１５０、１５３、１５４、１６６、１７３、１９４、２１４等の黄色顔料；Ｃ．Ｉ．ピグメントオレンジ１３、３１、３６、３８、４０、４２、４３、５１、５５、５９、６１、６４、６５、７１、７３等の橙色顔料；Ｃ．Ｉ．ピグメントレッド９、９７、１０５、１２２、１２３、１４４、１４９、１６６、１６８、１７６、１７７、１８０、１９２、２０９、２１５、２１６、２２４、２４２、２５４、２５５、２６４、２６５等の赤色顔料；Ｃ．Ｉ．ピグメントブルー１５、１５：３、１５：４、１５：６、６０等の青色顔料；Ｃ．Ｉ．ピグメントバイオレット１、１９、２３、２９、３２、３６、３８等の紫色顔料；Ｃ．Ｉ．ピグメントブラウン２３、２５等の茶色顔料；Ｃ．Ｉ．ピグメントブラック１、７、カーボンブラック、チタンブラック、酸化鉄等の黒色顔料等が挙げられる。これらの顔料は、目的とする画素の色に応じて、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Regarding the pigment (B) in the present embodiment, the green pigment having a halogenated phthalocyanine skeleton may be used alone, or two or more of them may be used in combination. Also, other pigments other than green pigments having a halogenated phthalocyanine skeleton may be used in combination.
Specific examples of other 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, 147, 148, 150, 153, 154, 166, 173, 194, 214; I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. I. red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; C. I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60; C.I. I. purple pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. I. Pigment Brown 23, 25 and other brown pigments; C.I. I. Pigment Black 1, 7, carbon black, titanium black, black pigments such as iron oxide, and the like. These pigments may be used alone or in combination of two or more, depending on the desired pixel color.
　さらに、本実施形態における顔料（Ｂ）について、顔料だけではなく染料を併用しても良い。染料を併用する場合、顔料を用いる場合と比べ高輝度化、色再現範囲の拡大、良好な現像性の発現が期待できる。一方、顔料を併用する場合、染料と比べ耐熱性に優れ、着色パターン形成後の色変化が少ない。求められる性能や目的とする画素の色に応じて、染料と顔料を併用してもよい。 Furthermore, for the pigment (B) in this embodiment, not only the pigment but also the dye may be used in combination. When a dye is used in combination, higher brightness, an expanded color reproduction range, and better developability can be expected than when a pigment is used. On the other hand, when a pigment is used together, the heat resistance is superior to that of the dye, and the color change after formation of the colored pattern is small. A dye and a pigment may be used in combination depending on the required performance and the desired pixel color.
　染料としては、溶剤（Ｄ）やアルカリ現像液に対する溶解性、樹脂組成物中の他の成分との相互作用、耐熱性等の観点から、カルボキシ基等の酸性基を有する酸性染料、酸性染料の窒素化合物との塩、酸性染料のスルホンアミド体等を用いることが好ましい。このような染料の具体例としては、ａｃｉｄ　ａｌｉｚａｒｉｎ　ｖｉｏｌｅｔ　Ｎ；ａｃｉｄ　ｂｌａｃｋ１、２、２４、４８；ａｃｉｄ　ｂｌｕｅ１、７、９、２５、２９、４０、４５、６２、７０、７４、８０、８３、９０、９２、１１２、１１３、１２０、１２９、１４７；ａｃｉｄ　ｃｈｒｏｍｅ　ｖｉｏｌｅｔ　Ｋ；ａｃｉｄ　Ｆｕｃｈｓｉｎ；ａｃｉｄ　ｇｒｅｅｎ１、３、５、２５、２７、５０；ａｃｉｄ　ｏｒａｎｇｅ６、７、８、１０、１２、５０、５１、５２、５６、６３、７４、９５；ａｃｉｄ　ｒｅｄ１、４、８、１４、１７、１８、２６、２７、２９、３１、３４、３５、３７、４２、４４、５０、５１、５２、５７、６９、７３、８０、８７、８８、９１、９２、９４、９７、１０３、１１１、１１４、１２９、１３３、１３４、１３８、１４３、１４５、１５０、１５１、１５８、１７６、１８３、１９８、２１１、２１５、２１６、２１７、２４９、２５２、２５７、２６０、２６６、２７４；ａｃｉｄ　ｖｉｏｌｅｔ　６Ｂ、７、９、１７、１９；ａｃｉｄ　ｙｅｌｌｏｗ１、３、９、１１、１７、２３、２５、２９、３４、３６、４２、５４、７２、７３、７６、７９、９８、９９、１１１、１１２、１１４、１１６；　ｆｏｏｄ　ｙｅｌｌｏｗ　３及びこれらの誘導体等が挙げられる。これらの中でも、アゾ系、キサンテン系、アントラキノン系又はフタロシアニン系の酸性染料が好ましい。これらの染料は、単独で用いてもよいし、２種以上を組み合わせて用いても良い。染料を用いる場合、顔料（Ｂ）１００質量部に対して２０～８０質量部が好ましい。 As the dye, from the viewpoint of solubility in the solvent (D) and alkaline developer, interaction with other components in the resin composition, heat resistance, etc., acid dyes having an acidic group such as a carboxy group, acid dyes, etc. Salts with nitrogen compounds, sulfonamides of acid dyes, and the like are preferably used. Specific examples of such dyes include acid alizarin violet N; acid black 1,2,24,48; acid blue 1,7,9,25,29,40,45,62,70,74,80,83,90 , 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; , 56, 63, 74, 95; 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42 , 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and derivatives thereof. Among these, azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes are preferred. These dyes may be used alone or in combination of two or more. When a dye is used, it is preferably 20 to 80 parts by weight per 100 parts by weight of the pigment (B).
〔高分子分散剤（Ｃ）〕
　本実施形態の高分子分散剤（Ｃ）は、アミノ基および４級アンモニウムカチオン基から選択される一種以上を有し、バインダー樹脂（Ａ－１）が有する官能基（Ｘ）と反応性を有する官能基（Ｙ）を有するものであれば、特に限定されない。３級アミノ基及び４級アンモニウムカチオン基からなる群から選択される少なくとも１種の置換基を有する高分子分散剤が更に好ましい。高分子分散剤（Ｃ）は官能基（Ｙ）を有することにより、バインダー樹脂（Ａ－１）が有する官能基（Ｘ）と反応して架橋することができる。従って、感光性着色組成物を低温硬化させた場合でも、耐溶剤性に優れた樹脂硬化膜が得られる。また、高分子分散剤（Ｃ）がアミノ基および４級アンモニウムカチオン基から選択される一種以上を有する場合には、顔料分散組成物中の顔料の分散性が向上するとともに、感光性着色組成物とした際の現像性が良好である。
　本明細書において、４級アンモニウムカチオン基とは、窒素原子に４つの炭素原子が結合している基を指し、アミド結合やウレア結合は含まれない。 [Polymer dispersant (C)]
The polymeric dispersant (C) of the present embodiment has one or more selected from amino groups and quaternary ammonium cationic groups, and is reactive with the functional group (X) of the binder resin (A-1). It is not particularly limited as long as it has a functional group (Y). Polymeric dispersants having at least one substituent selected from the group consisting of tertiary amino groups and quaternary ammonium cationic groups are more preferred. Since the polymer dispersant (C) has the functional group (Y), it can react with the functional group (X) of the binder resin (A-1) to be crosslinked. Therefore, even when the photosensitive coloring composition is cured at a low temperature, a cured resin film having excellent solvent resistance can be obtained. Further, when the polymer dispersant (C) has one or more selected from amino groups and quaternary ammonium cationic groups, the dispersibility of the pigment in the pigment dispersion composition is improved, and the photosensitive coloring composition Developability is good at the time of.
As used herein, a quaternary ammonium cationic group refers to a group having four carbon atoms bonded to a nitrogen atom, excluding amide and urea bonds.
　官能基（Ｘ）と反応性を有する官能基（Ｙ）としては、バインダー樹脂（Ａ）が含有する官能基（Ｘ）と反応性を有する官能基であれば特に限定されない。具体的には、官能基（Ｘ）との反応性や高分子分散剤（Ｃ）の合成容易性の観点から、官能基（Ｙ）として、ブロックイソシアナト基、アルキルエステル基、エポキシ基、オキセタニル基、ヒドロキシ基、メルカプト基、カルボキシ基等が挙げられる。 The functional group (Y) reactive with the functional group (X) is not particularly limited as long as it is a functional group reactive with the functional group (X) contained in the binder resin (A). Specifically, from the viewpoint of reactivity with the functional group (X) and ease of synthesis of the polymer dispersant (C), the functional group (Y) may be a blocked isocyanato group, an alkyl ester group, an epoxy group, or oxetanyl. group, hydroxy group, mercapto group, carboxy group and the like.
　高分子分散剤（Ｃ）が有していても良いアミノ基としては、１級、２級、３級のアミノ基が挙げられる。それぞれ、１級アミノ基は窒素原子に１つの炭素原子が結合している基、２級アミノ基は窒素原子に２つの炭素原子が結合している基、３級アミノ基は窒素原子に３つの炭素原子が結合している基を指す。 The amino groups that the polymeric dispersant (C) may have include primary, secondary and tertiary amino groups. A primary amino group is a group having one carbon atom attached to the nitrogen atom, a secondary amino group is a group having two carbon atoms attached to the nitrogen atom, and a tertiary amino group is a group having three carbon atoms attached to the nitrogen atom, respectively. Refers to a group to which a carbon atom is attached.
　アミノ基および４級アンモニウムカチオン基のうち、顔料分散組成物の分散性と保存安定性の観点から、少なくとも３級アミノ基を含むことが好ましい。 Of the amino group and the quaternary ammonium cationic group, it is preferable to include at least a tertiary amino group from the viewpoint of the dispersibility and storage stability of the pigment dispersion composition.
　高分子分散剤（Ｃ）としては、アミノ基含有高分子化合物（ｃ－１）と、前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）と、の反応物であることが好ましい。ハロゲン化合物とは、塩素、臭素、ヨウ素などのハロゲン原子が結合している有機化学物質を意味する。
　アミノ基含有高分子化合物（ｃ－１）と、前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）とが反応する際、ハロゲン化合物（ｃ－２）のハロゲン原子が外れた残基がアミノ基含有高分子化合物（ｃ－１）のアミノ基に配位する。中でも、３級アミノ基を含むアミノ基含有高分子化合物（ｃ－１）と、前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）とを反応させて、前記３級アミノ基を４級アンモニウムカチオン基とした高分子分散剤（Ｃ）が好ましい。 The polymeric dispersant (C) is preferably a reaction product of the amino group-containing polymeric compound (c-1) and the halogen compound (c-2) having the functional group (Y). A halogen compound means an organic chemical substance to which a halogen atom such as chlorine, bromine or iodine is attached.
When the amino group-containing polymer compound (c-1) reacts with the halogen compound (c-2) having the functional group (Y), a residue from which the halogen atom of the halogen compound (c-2) is removed is It coordinates with the amino group of the amino group-containing polymer compound (c-1). Among them, an amino group-containing polymer compound (c-1) containing a tertiary amino group is reacted with a halogen compound (c-2) having the functional group (Y) to convert the tertiary amino group to a quaternary A polymeric dispersant (C) having an ammonium cationic group is preferred.
「アミノ基含有高分子化合物（ｃ－１）」
　アミノ基含有高分子化合物（ｃ－１）としては、例えば、アミノ基とエチレン性不飽和基を有するモノマーを単独重合又は他のエチレン性不飽和基を有するモノマーと共重合させたポリアミンが挙げられる。このような高分子化合物としては、例えば、ビニルアミンの重合体もしくはアリルアミンの重合体であるポリアミン；またはビニルアミンもしくはアリルアミンと、他のエチレン性不飽和基を有するモノマーと共重合させたポリアミン；１－置換アジリジン類や２－オキサゾリン等を開環重合させたポリマー；エチレンジアミンやヘキサメチレンジアミン等の多官能アミン化合物とハロアルカン等を重縮合させたポリアルキレンイミン等が挙げられる。前記高分子化合物（ｃ－１）は、アミノ基の他にも、効果を損なわない範囲でアミド、イミド、ウレア、ウレタン等が含まれていても良く、これらに前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）が付加することを妨げない。上述したように、顔料分散性に大きく寄与するのはアミン構造であるため、アミド、イミド、ウレア、ウレタン結合は実質的に含まない方が好ましい。中でもアミノ基とエチレン性不飽和基を有するモノマーと他のエチレン性不飽和基を有するモノマーとをブロック重合させたポリアミンが好ましく、３級アミノ基とエチレン性不飽和基を有するモノマーと他のエチレン性不飽和基を有するモノマーとをブロック重合させたポリアミンがより好ましい。高分子分散剤（Ｃ）としてブロック重合させたポリアミンを用いることで、片末端領域にアミノ基が偏在し、顔料（Ｂ）との親和性が向上する。また、もう一方の片末端領域は、他の顔料分散組成物、具体的にはバインダー樹脂（Ａ－１）や後述する溶剤（Ｄ－１）との親和性が高まることで、顔料分散性や顔料分散組成物の保存安定性を飛躍的に向上することができる。 "Amino group-containing polymer compound (c-1)"
Examples of the amino group-containing polymer compound (c-1) include polyamines obtained by homopolymerizing a monomer having an amino group and an ethylenically unsaturated group or copolymerizing it with another monomer having an ethylenically unsaturated group. . Such polymer compounds include, for example, polyamines that are polymers of vinylamine or polymers of allylamine; or polyamines obtained by copolymerizing vinylamine or allylamine with other monomers having ethylenically unsaturated groups; Polymers obtained by ring-opening polymerization of aziridines, 2-oxazoline and the like; polyalkyleneimines obtained by polycondensation of polyfunctional amine compounds such as ethylenediamine and hexamethylenediamine with haloalkanes and the like. In addition to the amino group, the polymer compound (c-1) may contain amide, imide, urea, urethane, etc. within a range that does not impair the effect, and these have the functional group (Y). It does not prevent the addition of the halogen compound (c-2). As described above, it is the amine structure that greatly contributes to the dispersibility of the pigment, so it is preferred that the amide, imide, urea, and urethane bonds are substantially absent. Among them, polyamine obtained by block polymerization of a monomer having an amino group and an ethylenically unsaturated group and a monomer having another ethylenically unsaturated group is preferable, and a monomer having a tertiary amino group and an ethylenically unsaturated group and other ethylene A polyamine obtained by block polymerization with a monomer having a polyunsaturated group is more preferred. By using a block-polymerized polyamine as the polymeric dispersant (C), amino groups are unevenly distributed in one end region, and the affinity with the pigment (B) is improved. In addition, the other one end region has an increased affinity with another pigment dispersion composition, specifically a binder resin (A-1) or a solvent (D-1) described later, thereby improving pigment dispersibility and The storage stability of the pigment dispersion composition can be dramatically improved.
　アミノ基とエチレン性不飽和基を有するモノマーの具体例としては、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート、ジメチルアミノブチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジエチルアミノプロピル（メタ）アクリレート、ジエチルアミノブチル（メタ）アクリレート、ペンタメチルピペリジル（メタ）アクリレート、テトラメチルピペリジル（メタ）アクリレート、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ダイアセトン（メタ）アクリルアミド、又はアクリロイルモルホリン等の（メタ）アクリルアミド類等が挙げられる。これらのモノマーは単独で用いても良いし、２種以上を用いても良い。中でも、顔料分散組成物の分散性向上や保存安定性向上に大きく寄与することから、３級アミノ基とエチレン性不飽和基を有するモノマーが好ましく、ジメチルアミノエチル（メタ）アクリレートがより好ましい。また、３級アミノ基とエチレン性不飽和基を有するモノマーを使用して、３級アミノ基を有するアミノ基含有高分子化合物（ｃ－１）とし、３級アミノ基の一部へ前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）を反応させて４級アンモニウムカチオン基とすれば、親水性が向上し、感光性着色組成物としての現像性が向上する。 Specific examples of monomers having an amino group and an ethylenically unsaturated group include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl. (Meth)acrylate, diethylaminobutyl (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N- (Meth)acrylamides such as isopropyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, and acryloylmorpholine. These monomers may be used alone or in combination of two or more. Among them, a monomer having a tertiary amino group and an ethylenically unsaturated group is preferred, and dimethylaminoethyl (meth)acrylate is more preferred, since it greatly contributes to improving the dispersibility and storage stability of the pigment dispersion composition. Alternatively, a monomer having a tertiary amino group and an ethylenically unsaturated group is used to obtain an amino group-containing polymer compound (c-1) having a tertiary amino group, and the functional group is added to a part of the tertiary amino group. When the halogen compound (c-2) having (Y) is reacted to form a quaternary ammonium cationic group, the hydrophilicity is improved and the developability as a photosensitive coloring composition is improved.
　他のエチレン性不飽和基を有するモノマーとしては、一例として、アルキル基、アリール基、アラルキル基、シクロアルキル基、（ポリ）オキシアルキレン骨格等を有する（メタ）アクリレートが挙げられるが、他の顔料分散組成物と親和性を損なうものでなければ特に制限は無い。具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、又はエトキシポリエチレングリコール（メタ）アクリレート等の（メタ）アクリレート類、スチレン又はα－メチルスチレン等のスチレン類、エチルビニルエーテル、ｎ－プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ－ブチルビニルエーテル、又はイソブチルビニルエーテル等のビニルエーテル類、酢酸ビニル、又はプロピオン酸ビニル等の脂肪酸ビニル類等が挙げられる。これらのモノマーは単独で用いても良いし、２種以上を用いても良い。 Examples of monomers having other ethylenically unsaturated groups include alkyl groups, aryl groups, aralkyl groups, cycloalkyl groups, (meth)acrylates having a (poly)oxyalkylene skeleton, etc. Other pigments There is no particular limitation as long as it does not impair the affinity with the dispersion composition. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (Meth)acrylates such as (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate, styrene or α-methylstyrene, etc. styrenes, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate. These monomers may be used alone or in combination of two or more.
　アミノ基含有高分子化合物（ｃ－１）は、市販品を用いても良いし、自ら準備しても良い。市販品を利用する場合、好適なアミノ基含有高分子化合物（ｃ－１）の一例として、ビックケミー社製のＤＩＳＰＥＲＢＹＫシリーズ、ルーブリゾール社製のソルスパーズシリーズ、ＢＡＳＦ社製のＥＦＫＡ－ＰＸシリーズ等が挙げられる。自ら準備する場合は、公知の重合体製造方法を利用する。これらのアミノ基含有高分子化合物（ｃ－１）は、必要に応じて、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 For the amino group-containing polymer compound (c-1), a commercially available product may be used, or it may be prepared by oneself. When using a commercially available product, examples of suitable amino group-containing polymer compounds (c-1) include the DISPERBYK series manufactured by BYK-Chemie, the Solspers series manufactured by Lubrizol, and the EFKA-PX series manufactured by BASF. mentioned. When preparing by yourself, a known polymer production method is used. These amino group-containing polymer compounds (c-1) may be used alone or in combination of two or more, as required.
「ハロゲン化合物（ｃ－２）」
　ハロゲン化合物（ｃ－２）としては、前記官能基（Ｙ）を有するモノハロゲン化合物であれば特に限定されない。前記官能基（Ｙ）の数は特に限定されない。例えば、ブロックイソシアナト基、アルキルエステル基、エポキシ基、オキセタニル基、ヒドロキシ基、メルカプト基、およびカルボキシ基からなる群から選択される１種以上を有する化合物の臭素化物、塩素化物、ヨウ素化物等が挙げられる。具体的には、２－ブロモエタノール、エピブロモヒドリン等が挙げられる。これらの化合物は単独で用いても良いし、２種以上を用いても良い。中でも、反応性の観点から、臭素化物が好ましい。 "Halogen compound (c-2)"
The halogen compound (c-2) is not particularly limited as long as it is a monohalogen compound having the functional group (Y). The number of functional groups (Y) is not particularly limited. For example, bromides, chlorides, iodides, etc. of compounds having one or more selected from the group consisting of a blocked isocyanato group, an alkyl ester group, an epoxy group, an oxetanyl group, a hydroxy group, a mercapto group, and a carboxy group. mentioned. Specific examples include 2-bromoethanol and epibromohydrin. These compounds may be used alone, or two or more of them may be used. Among them, bromides are preferred from the viewpoint of reactivity.
　アミノ基含有高分子化合物（ｃ－１）が有するアミノ基の総量に対する、ハロゲン化合物（ｃ－２）の付加率は、５～８０％であることが好ましく、１０～６０％であることがより好ましく、１５～４０％であることがさら好ましい。ハロゲン化合物（ｃ－２）の付加率が５％以上であると、高分子分散剤（Ｃ）に十分量の官能基（Ｙ）が導入される。そのため、バインダー樹脂（Ａ－１）が有する官能基（Ｘ）との架橋量を十分に確保できる。その結果、感光性着色組成物としての低温硬化性が良好で、優れた耐溶剤性を有する樹脂硬化膜が得られる。ハロゲン化合物（ｃ－２）の付加率が８０％以下であると、高分子分散剤（Ｃ）の合成時にゲル化することなく容易に製造することができ、ミルベースにした際に良好な分散安定性が保てる。特にアミノ基含有高分子化合物（ｃ－１）が有するアミノ基が３級アミノ基である場合には、ハロゲン化合物（ｃ－２）の付加率が８０％以下であると、残存する３級アミノ基量を十分に確保することができる。そのため、顔料分散組成物としての分散性や保存安定性が十分なものとなる。 The addition rate of the halogen compound (c-2) to the total amount of amino groups possessed by the amino group-containing polymer compound (c-1) is preferably 5 to 80%, more preferably 10 to 60%. It is preferably 15 to 40%, more preferably 15 to 40%. When the addition rate of the halogen compound (c-2) is 5% or more, a sufficient amount of the functional group (Y) is introduced into the polymeric dispersant (C). Therefore, a sufficient amount of cross-linking with the functional group (X) of the binder resin (A-1) can be ensured. As a result, a cured resin film having good low-temperature curability as a photosensitive coloring composition and excellent solvent resistance can be obtained. When the addition rate of the halogen compound (c-2) is 80% or less, the polymer dispersant (C) can be easily produced without gelation during synthesis, and good dispersion stability is obtained when mill bases are used. maintains sexuality. Especially when the amino group possessed by the amino group-containing polymer compound (c-1) is a tertiary amino group, if the addition rate of the halogen compound (c-2) is 80% or less, the residual tertiary amino A sufficient base amount can be secured. Therefore, the dispersibility and storage stability of the pigment dispersion composition are sufficient.
　高分子分散剤（Ｃ）がアミノ基および４級アンモニウムカチオン基から選択される一種以上を有する場合のアミン含有量（１級アミン、２級アミン、３級アミンの合計量である。）は、アミン価（ＪＩＳ　Ｋ７２３７等に示す規格に沿って測定された値）を測定することにより、その量を定量的に判断することができる。本実施形態の高分子化合物（ｃ－１）のアミン含有量は特に限定されないが、好ましくは１０ｍｇＫＯＨ／ｇ～４００ｍｇＫＯＨ／ｇ、より好ましくは２０ｍｇＫＯＨ／ｇ～２００ｍｇＫＯＨ／ｇ、さらに好ましくは３０ｍｇＫＯＨ／ｇ～１００ｍｇＫＯＨ／ｇである。アミン価が１０ｍｇＫＯＨ／ｇ以上であると、顔料分散組成物の十分な分散性や保存安定性が得られる。 When the polymeric dispersant (C) has one or more selected from amino groups and quaternary ammonium cationic groups, the amine content (the total amount of primary amine, secondary amine, and tertiary amine) is The amount can be determined quantitatively by measuring the amine value (the value measured according to the standards shown in JIS K7237, etc.). The amine content of the polymer compound (c-1) of the present embodiment is not particularly limited, but is preferably 10 mgKOH/g to 400 mgKOH/g, more preferably 20 mgKOH/g to 200 mgKOH/g, still more preferably 30 mgKOH/g to 100 mg KOH/g. When the amine value is 10 mgKOH/g or more, sufficient dispersibility and storage stability of the pigment dispersion composition can be obtained.
　高分子分散剤（Ｃ）がアミノ基を有する場合、顔料分散組成物の分散性や保存安定性の向上に対し、中でも３級アミノ基の寄与率が大きい。従って、高分子分散剤（Ｃ）の３級アミン含有量を十分に確保することが好ましい。そのような観点から、高分子分散剤（Ｃ）の３級アミン価は、好ましくは１０ｍｇＫＯＨ／ｇ～４００ｍｇＫＯＨ／ｇ、より好ましくは３０ｍｇＫＯＨ／ｇ～２００ｍｇＫＯＨ／ｇ、さらに好ましくは４０ｍｇＫＯＨ／ｇ～１００ｍｇＫＯＨ／ｇである。
　３級アミン価は、アミン価Ｖ０（ＪＩＳ　Ｋ７２３７等に示す規格に沿って測定された値）をベースにアミノ基含有モノマーとハロゲン化合物（ｃ－２）の使用量に基づいて算出した値である。 When the polymeric dispersant (C) has an amino group, the tertiary amino group has a particularly large contribution to improving the dispersibility and storage stability of the pigment dispersion composition. Therefore, it is preferable to ensure a sufficient tertiary amine content in the polymeric dispersant (C). From such a viewpoint, the tertiary amine value of the polymer dispersant (C) is preferably 10 mgKOH/g to 400 mgKOH/g, more preferably 30 mgKOH/g to 200 mgKOH/g, still more preferably 40 mgKOH/g to 100 mgKOH/g. is g.
The tertiary amine value is a value calculated based on the amount of amino group-containing monomer and halogen compound (c-2) used, based on the amine value V 0 (value measured in accordance with standards such as JIS K7237). be.
　高分子分散剤（Ｃ）固形１ｇ中に含まれる官能基（Ｙ）の量は、５０～５０００μｍｏｌ／ｇであることが好ましく、１００～３０００μｍｏｌ／ｇであることがより好ましく、１５０～１０００μｍｏｌ／ｇであることがさらに好ましい。官能基（Ｘ）の量が、５０μｍｏｌ／ｇ以上であると、感光性着色組成物としての現像性、低温硬化性に優れ、耐溶剤性の良好な樹脂硬化膜が得られる。官能基（Ｘ）の量が、５０００μｍｏｌ／ｇ以下であるとミルベースにした際に良好な分散安定性が得られる。 The amount of the functional group (Y) contained in 1 g of solid polymer dispersant (C) is preferably 50 to 5000 μmol/g, more preferably 100 to 3000 μmol/g, and more preferably 150 to 1000 μmol/g. is more preferable. When the amount of the functional group (X) is 50 μmol/g or more, a cured resin film having excellent developability and low-temperature curability as a photosensitive coloring composition and good solvent resistance can be obtained. When the amount of the functional group (X) is 5000 μmol/g or less, good dispersion stability can be obtained when mill base is formed.
　本実施形態の高分子分散剤（Ｃ）の重量平均分子量は、好ましくは１０００～４００００、より好ましくは１０００～３００００である。さらに、高分子分散剤（Ｃ）の分子量分布（ポリスチレン換算の重量平均分子量を数平均分子量で除した値）は、好ましくは１．０～３．０、より好ましくは１．０～２．０の範囲内である。高分子分散剤（Ｃ）の分子量や分子量分布が上記範囲内にあると、顔料分散組成物の粘度を適切な範囲に制御することができる。その結果、十分な顔料分散性や顔料分散組成物の保存安定性が得られると共に、優れた耐熱性、耐溶剤性、パターン密着性、現像性等を確保することができる。 The weight-average molecular weight of the polymeric dispersant (C) of the present embodiment is preferably 1,000 to 40,000, more preferably 1,000 to 30,000. Furthermore, the molecular weight distribution of the polymeric dispersant (C) (the value obtained by dividing the polystyrene equivalent weight average molecular weight by the number average molecular weight) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. is within the range of When the molecular weight and molecular weight distribution of the polymeric dispersant (C) are within the above ranges, the viscosity of the pigment dispersion composition can be controlled within an appropriate range. As a result, sufficient pigment dispersibility and storage stability of the pigment dispersion composition can be obtained, and excellent heat resistance, solvent resistance, pattern adhesion, developability, etc. can be ensured.
〔官能基（Ｘ）と官能基（Ｙ）の好ましい組み合わせ〕
　バインダー樹脂（Ａ－１）が有する官能基（Ｘ）と、高分子分散剤（Ｃ）が有する官能基（Ｙ）の好ましい組み合わせとしては、感光性着色組成物としての低温硬化性向上の観点から、以下の組み合わせ（１）～（４）が挙げられる。
　組み合わせ（１）：官能基（Ｘ）としてヒドロキシ基及びメルカプト基から選択される一種以上、官能基（Ｙ）としてブロックイソシアナト基及びアルキルエステルを有する基から選択される一種以上の組み合わせ。
　組み合わせ（２）：官能基（Ｘ）としてカルボキシ基、官能基（Ｙ）としてエポキシ基及びオキセタニル基から選択される一種以上の組み合わせ。
　組み合わせ（３）：官能基（Ｘ）としてブロックイソシアナト基及びアルキルエステルを有する基から選択される一種以上、官能基（Ｙ）としてヒドロキシ基及びメルカプト基から選択される一種以上の組み合わせ。
　組み合わせ（４）：官能基（Ｘ）としてエポキシ基及びオキセタニル基から選択される一種以上、官能基（Ｙ）としてカルボキシ基の組み合わせ。 [Preferred combination of functional group (X) and functional group (Y)]
A preferred combination of the functional group (X) possessed by the binder resin (A-1) and the functional group (Y) possessed by the polymer dispersant (C) is from the viewpoint of improving the low-temperature curability of the photosensitive coloring composition. , and the following combinations (1) to (4).
Combination (1): A combination of one or more groups selected from hydroxy groups and mercapto groups as functional groups (X) and one or more groups selected from groups having blocked isocyanato groups and alkyl esters as functional groups (Y).
Combination (2): A combination of one or more selected from a carboxy group as the functional group (X) and an epoxy group and an oxetanyl group as the functional group (Y).
Combination (3): A combination of one or more selected from blocked isocyanato groups and alkyl ester-containing groups as functional groups (X) and one or more selected from hydroxy groups and mercapto groups as functional groups (Y).
Combination (4): A combination of one or more types selected from an epoxy group and an oxetanyl group as the functional group (X) and a carboxy group as the functional group (Y).
　さらに上記組み合わせ以外の官能基が併用されていても良い。例えば、バインダー樹脂（Ａ－１）が有する官能基（Ｘ）としては、感光性着色組成物としての現像性向上の観点から、いずれの組み合わせにおいてもカルボキシ基が併用されていることが好ましい。 Furthermore, functional groups other than the above combinations may be used in combination. For example, as the functional group (X) possessed by the binder resin (A-1), a carboxy group is preferably used in combination in any combination from the viewpoint of improving developability as a photosensitive coloring composition.
＜高分子分散剤（Ｃ）の製造方法＞
　高分子分散剤（Ｃ）は、例えば以下の方法で製造することができる。すなわち、アミノ基含有高分子化合物（ｃ－１）のアミノ基に、前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）を付加することにより製造することができる。前記高分子化合物（ｃ－１）のアミノ基に、前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）を付加する方法としては、ブロモ塩化反応を利用することが好ましい。具体的には、高分子化合物（ｃ－１）、前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）、そして任意の割合で溶液を混合させ、室温～１５０℃、好ましくは３０℃～１３０℃の条件下で反応させることで、高分子化合物（ｃ－１）と前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）との反応物となる高分子分散剤（Ｃ）を得る。 <Method for producing polymer dispersant (C)>
The polymeric dispersant (C) can be produced, for example, by the following method. That is, it can be produced by adding the halogen compound (c-2) having the functional group (Y) to the amino group of the amino group-containing polymer compound (c-1). As a method for adding the halogen compound (c-2) having the functional group (Y) to the amino group of the polymer compound (c-1), it is preferable to use a bromochlorination reaction. Specifically, the polymer compound (c-1), the halogen compound (c-2) having the functional group (Y), and the solution are mixed in an arbitrary ratio, and the temperature is from room temperature to 150° C., preferably from 30° C. A polymer dispersant (C), which is a reaction product of the polymer compound (c-1) and the halogen compound (c-2) having the functional group (Y), is obtained by reacting at 130°C. .
〔溶剤（Ｄ－１）〕
　溶剤（Ｄ－１）は、本実施形態の顔料分散組成物、または感光性着色組成物に含まれる各成分と反応せず、かつこれらを溶解または分散可能な溶剤であれば特に限定されない。溶剤（Ｄ－１）としては、バインダー樹脂（Ａ－１）或いは高分子分散剤（Ｃ）を製造する際に用いた溶剤と同じものを用いることができ、反応後に含まれている溶剤をそのまま用いることもでき、更に加えることもできる。また、その他の成分を加える際に、そこに共存しているものでもよい。溶剤（Ｄ－１）の具体例としては、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、酢酸エチル、酢酸ブチル、酢酸イソプロピル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールエチルエーテルアセテート等が挙げられる。これらは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。また、これらの中でも、カラーフィルターを製造する際に好ましく使用されるプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のグリコールエーテル系溶剤が好ましい。 [Solvent (D-1)]
The solvent (D-1) is not particularly limited as long as it does not react with each component contained in the pigment dispersion composition or the photosensitive coloring composition of the present embodiment and is capable of dissolving or dispersing them. As the solvent (D-1), the same solvent as used in producing the binder resin (A-1) or the polymer dispersant (C) can be used, and the solvent contained after the reaction can be used as it is. can be used, and more can be added. Moreover, when adding another component, it may coexist there. Specific examples of the solvent (D-1) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate and the like. These may be used alone or in combination of two or more. Among these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, which are preferably used when manufacturing color filters, are preferred.
＜顔料分散組成物の製造方法＞
　本実施形態の顔料分散組成物は、バインダー樹脂（Ａ－１）、高分子分散剤（Ｃ）、顔料（Ｂ）、溶剤（Ｃ－１）を所定量秤量し、公知の分散処理工程を用いて顔料（Ｂ）を微細化し分散する。この分散処理工程において、ペイントシェイカー、ビーズミル、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザー、プラネタリミキサー、自転公転ミキサー等の装置が多用される。また、この分散処理工程において、直径０．０１～１０ｍｍのビーズを用いると、顔料（Ｂ）の均一な微細化を効率良く行うことができる。ビーズの材質に制限は無いが、硬さや顔料分散組成物へのコンタミ等を踏まえると、ガラスビーズやジルコニアビーズの使用が好ましい。分散処理の好適な時間、温度、ビーズの直径、使用量に関しては、顔料分散組成物の組成や装置の大きさ等により適正な条件が異なるため、適宜調整すればよい。
　最後に、顔料分散組成物に微細なゴミ、ならびに顔料（Ｂ）の粗粒や凝集物を除去する目的で、顔料分散組成物をガラスフィルター等でろ過処理することが好ましい。 <Method for producing pigment dispersion composition>
The pigment dispersion composition of the present embodiment is obtained by weighing predetermined amounts of the binder resin (A-1), the polymer dispersant (C), the pigment (B), and the solvent (C-1), and using a known dispersion treatment process. to make the pigment (B) finer and dispersed. Apparatuses such as paint shakers, bead mills, ball mills, roll mills, stone mills, jet mills, homogenizers, planetary mixers, and rotation/revolution mixers are often used in this dispersion treatment process. In addition, in this dispersing treatment step, if beads having a diameter of 0.01 to 10 mm are used, the pigment (B) can be uniformly finely divided efficiently. Although the material of the beads is not limited, glass beads and zirconia beads are preferably used in consideration of hardness, contamination of the pigment dispersion composition, and the like. Appropriate time, temperature, diameter of beads and usage amount of the dispersion treatment may be adjusted as appropriate, since appropriate conditions vary depending on the composition of the pigment dispersion composition, the size of the apparatus, and the like.
Finally, for the purpose of removing fine dust, coarse particles and aggregates of the pigment (B) from the pigment dispersion composition, it is preferable to filter the pigment dispersion composition with a glass filter or the like.
〔顔料分散組成物の配合比〕
　バインダー樹脂（Ａ－１）の含有量は、顔料（Ｂ）１００質量部に対して、１０～８０質量部であることが好ましく、１５～５０質量部であることがより好ましく、２０～４０質量部であることがさらに好ましい。バインダー樹脂（Ａ－１）の含有量が１０質量部以上であると、十分な現像性が得られる。バインダー樹脂（Ａ－１）の含有量が８０質量部以下であると、ミルベースにした際に良好な分散安定性を得られる。 [Blending ratio of pigment dispersion composition]
The content of the binder resin (A-1) is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass, and 20 to 40 parts by mass with respect to 100 parts by mass of the pigment (B). Part is more preferred. When the content of the binder resin (A-1) is 10 parts by mass or more, sufficient developability can be obtained. When the content of the binder resin (A-1) is 80 parts by mass or less, good dispersion stability can be obtained when used as a mill base.
　高分子分散剤（Ｃ）の含有量は、顔料（Ｂ）１００質量部に対して、１０～８０質量部であることが好ましく、１５～５０質量部であることがより好ましく、２０～４０質量部であることがさらに好ましい。高分子分散剤（Ｃ）の含有量が１０質量部以上であると、ミルベースにした際に良好な分散安定性が得られる。高分子分散剤（Ｃ）の含有量が８０質量部以下であると、十分な現像性が得られる。 The content of the polymeric dispersant (C) is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass, and 20 to 40 parts by mass, relative to 100 parts by mass of the pigment (B). Part is more preferred. When the content of the polymeric dispersant (C) is 10 parts by mass or more, good dispersion stability can be obtained when mill bases are formed. Sufficient developability is obtained as content of a polymeric dispersing agent (C) is 80 mass parts or less.
　溶剤（Ｄ－１）の配合量は、溶剤（Ｄ－１）を除く顔料分散組成物の成分の総和を１００質量部としたときに、好ましくは１００～９００部、より好ましくは１２０～６００部、さらに好ましくは１５０～４００部である。溶剤（Ｄ－１）の含有量が上記範囲内であれば、適切な粘度を有する顔料分散組成物となる。 The amount of the solvent (D-1) is preferably 100 to 900 parts, more preferably 120 to 600 parts when the total of the components of the pigment dispersion composition excluding the solvent (D-1) is 100 parts by mass. , more preferably 150 to 400 parts. If the content of the solvent (D-1) is within the above range, the pigment dispersion composition will have an appropriate viscosity.
＜感光性着色組成物＞
高分子分散剤（Ｃ）の含有量は、顔料（Ｂ）１００質量部に対して、１０～８０質量部であることが好ましく、１５～５０質量部であることがより好ましく、２０～４０質量部であることがさらに好ましい。高分子分散剤（Ｃ）の含有量が１０質量部以上であると、ミルベースにした際に良好な分散安定性が得られる。高分子分散剤（Ｃ）の含有量が８０質量部以下であると、十分な現像性が得られる。
　本実施形態の感光性着色組成物は、上記顔料分散組成物と、バインダー樹脂（Ａ－２）と、反応性希釈剤（Ｅ）と、光重合開始剤（Ｆ）と、を含有する。本実施形態の感光性着色組成物は溶剤（Ｄ－２）を含んでもよい。
　本実施形態の感光性着色組成物において、顔料（Ｂ）１００質量部に対して、前記バインダー樹脂（Ａ－１）と（Ａ－２）との合計バインダー樹脂（Ａ）を５０～２８０質量部、前記高分子分散剤（Ｃ）を１０～８０質量部、前記反応性希釈剤（Ｅ）を４０～２００質量部、前記光重合開始剤（Ｆ）を０．１～１０質量部含有することが好ましい。
　溶剤（Ｄ－２）は、上記顔料分散組成物に含まれている溶剤（Ｄ－１）と共通のものを使用してもよく、異なるものを追添しても良い。 <Photosensitive coloring composition>
The content of the polymeric dispersant (C) is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass, and 20 to 40 parts by mass, relative to 100 parts by mass of the pigment (B). Part is more preferred. When the content of the polymeric dispersant (C) is 10 parts by mass or more, good dispersion stability can be obtained when mill bases are formed. Sufficient developability is obtained as content of a polymeric dispersing agent (C) is 80 mass parts or less.
The photosensitive coloring composition of the present embodiment contains the pigment dispersion composition, a binder resin (A-2), a reactive diluent (E), and a photopolymerization initiator (F). The photosensitive coloring composition of the present embodiment may contain a solvent (D-2).
In the photosensitive coloring composition of the present embodiment, the total binder resin (A) of the binder resin (A-1) and (A-2) is 50 to 280 parts by mass with respect to 100 parts by mass of the pigment (B). , 10 to 80 parts by mass of the polymer dispersant (C), 40 to 200 parts by mass of the reactive diluent (E), and 0.1 to 10 parts by mass of the photopolymerization initiator (F). is preferred.
As the solvent (D-2), the same solvent as the solvent (D-1) contained in the pigment dispersion composition may be used, or a different solvent may be added.
〔バインダー樹脂（Ａ－２）〕
　バインダー樹脂（Ａ－２）は、感光性着色組成物として用いることができる従来公知の樹脂を特に制限なく使用することができ、上記顔料分散組成物に含まれているバインダー樹脂（Ａ－１）と共通のものを使用してもよく、異なるものでも良い。また、バインダー樹脂（Ａ－２）として新たに追加せず、バインダー樹脂（Ａ－１）を（Ａ－２）として利用しても良い。
　前記バインダー樹脂（Ａ－１）と（Ａ－２）との合計バインダー樹脂（Ａ）の含有量は、顔料（Ｂ）１００質量部に対して、５０～２８０質量部であることが好ましく、７５～２３０質量部であることがより好ましく、１００～２００質量部であることがさらに好ましい。 [Binder resin (A-2)]
As the binder resin (A-2), a conventionally known resin that can be used as a photosensitive coloring composition can be used without particular limitation, and the binder resin (A-1) contained in the pigment dispersion composition , may be used in common, or different ones may be used. Alternatively, the binder resin (A-1) may be used as (A-2) without newly adding it as the binder resin (A-2).
The total binder resin (A) content of the binder resins (A-1) and (A-2) is preferably 50 to 280 parts by mass with respect to 100 parts by mass of the pigment (B). It is more preferably from 100 to 200 parts by mass, more preferably from 100 to 200 parts by mass.
〔反応性希釈剤（Ｅ）〕
　反応性希釈剤（Ｅ）は、ビニル基、（メタ）アクリロイルオキシ基等のエチレン性不飽和二重結合を含む低分子化合物であれば特に限定されない。反応性希釈剤（Ｃ）の具体例としては、スチレン、α－メチルスチレン、α－クロロメチルスチレン、ビニルトルエン、ジビニルベンゼン、ジアリルフタレート、ジアリルベンゼンホスホネート等の芳香族ビニル系モノマー類；酢酸ビニル、アジピン酸ビニル等のポリカルボン酸モノマー類；メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、β－ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリス（ヒドロキシエチル）イソシアヌレートのトリ（メタ）アクリレート等の（メタ）アクリル系モノマー；トリアリルシアヌレート等が挙げられる。これらは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。これらの中でも、（メタ）アクリロイルオキシ基を複数有する化合物が好ましく、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリス（ヒドロキシエチル）イソシアヌレートのトリ（メタ）アクリレート等の（メタ）アクリロイルオキシ基を３個以上有する化合物がより好ましい。 [Reactive diluent (E)]
The reactive diluent (E) is not particularly limited as long as it is a low-molecular-weight compound containing an ethylenically unsaturated double bond such as a vinyl group or (meth)acryloyloxy group. Specific examples of the reactive diluent (C) include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; Polycarboxylic acid monomers such as vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate , ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, (Meth)acrylic monomers such as pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate; triallyl cyanurate and the like. These may be used alone or in combination of two or more. Among these, compounds having a plurality of (meth)acryloyloxy groups are preferable, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl)isocyanurate A compound having 3 or more (meth)acryloyloxy groups such as tri(meth)acrylate of is more preferable.
　反応性希釈剤（Ｅ）の含有量は、顔料（Ｂ）１００質量部に対して、４０～２００質量部であることが好ましく、６０～１８０質量部であることがより好ましく、８０～１６０質量部であることがさらに好ましい。 The content of the reactive diluent (E) is preferably 40 to 200 parts by mass, more preferably 60 to 180 parts by mass, and 80 to 160 parts by mass with respect to 100 parts by mass of the pigment (B). Part is more preferred.
〔光重合開始剤（Ｆ）〕
　光重合開始剤（Ｆ）は光ラジカル発生剤が好ましく、その具体例としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル等のベンゾインとそのアルキルエーテル類；アセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン、４－（１－ｔ－ブチルジオキシ－１－メチルエチル）アセトフェノン等のアセトフェノン類；２－メチルアントラキノン、２－アミルアントラキノン、２－ｔ－ブチルアントラキノン、１－クロロアントラキノン等のアントラキノン類；２，４－ジメチルチオキサントン、２，４－ジイソプロピルチオキサントン、２－クロロチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン、４－（１－ｔ－ブチルジオキシ－１－メチルエチル）ベンゾフェノン、３，３’，４，４’－テトラキス（ｔ－ブチルジオキシカルボニル）ベンゾフェノン等のベンゾフェノン類；２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパン－１－オン；２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）ブタノン－１；アシルホスフィンオキサイド類；及びキサントン類等が挙げられる。これらは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 [Photopolymerization initiator (F)]
The photopolymerization initiator (F) is preferably a photoradical generator, and specific examples include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenones such as acetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone Anthraquinones such as; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and other ketals; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone, 4-(1-t-butyldioxy -1-methylethyl)benzophenone, benzophenones such as 3,3′,4,4′-tetrakis(t-butyldioxycarbonyl)benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2- morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; acylphosphine oxides; and xanthones. These may be used alone or in combination of two or more.
　光重合開始剤（Ｆ）の含有量は、顔料（Ｂ）１００質量部に対して、０．１～１０質量部であることが好ましく、１～９質量部であることがより好ましく、２～８質量部であることがさらに好ましい。 The content of the photopolymerization initiator (F) is preferably 0.1 to 10 parts by mass, more preferably 1 to 9 parts by mass, based on 100 parts by mass of the pigment (B). It is more preferably 8 parts by mass.
〔その他の成分〕
　本実施形態の感光性着色組成物は、上記の成分に加えて、所定の特性を付与するために光酸発生剤、光塩基発生剤、カップリング剤、レベリング剤等の公知の添加剤、フィラー等を配合してもよい。これらの成分の配合量は、本発明の効果を阻害しない範囲であれば特に限定されない。 [Other ingredients]
In addition to the above components, the photosensitive coloring composition of the present embodiment contains known additives such as photoacid generators, photobase generators, coupling agents, leveling agents, etc., and fillers to impart predetermined properties. etc. may be added. The blending amount of these components is not particularly limited as long as it does not impair the effects of the present invention.
＜感光性着色組成物の製造方法＞
　本実施形態の感光性着色組成物は、公知の混合装置を用い、上記の各成分を混合することによって製造することができる。例えば、先に顔料分散組成物を調整した後、バインダー樹脂（Ａ－２）、反応性希釈剤（Ｅ）、光重合開始剤（Ｆ）等を順番に混合することで製造することができる。また、必要に応じて、顔料分散組成物に含まれている溶剤（Ｄ－１）以外に、溶剤（Ｄ－２）を添加してもよい。その場合、感光性着色組成物に含まれている溶剤（Ｄ）が、溶剤（Ｄ－１）と溶剤（Ｄ－２）とを含む。なお、溶剤（Ｄ－２）は、溶剤（Ｄ－１）と共通のものを使用してもよく、異なるものでもよい。 <Method for producing a photosensitive coloring composition>
The photosensitive coloring composition of the present embodiment can be produced by mixing the components described above using a known mixing device. For example, it can be produced by first preparing a pigment dispersion composition and then sequentially mixing a binder resin (A-2), a reactive diluent (E), a photopolymerization initiator (F), and the like. Further, if necessary, a solvent (D-2) may be added in addition to the solvent (D-1) contained in the pigment dispersion composition. In that case, the solvent (D) contained in the photosensitive coloring composition contains the solvent (D-1) and the solvent (D-2). The solvent (D-2) may be the same as the solvent (D-1), or may be different.
　上記のようにして得られる感光性着色組成物は、顔料分散性や顔料分散組成物の保存安定性が十分で、高輝度化の達成が可能で、かつ分散剤や着色剤のブリードアウトを抑制し優れた耐熱性、耐溶剤性、パターン密着性、現像性等の各種レジスト特性を発現することができる。その結果、信頼性に優れた着色パターンを形成することができる。すなわち、前記感光性着色組成物を用いることにより、信頼性に優れたカラーフィルターを提供することができる。 The photosensitive coloring composition obtained as described above has sufficient pigment dispersibility and storage stability of the pigment dispersion composition, can achieve high brightness, and suppresses bleeding out of the dispersant and coloring agent. It is possible to express various resist properties such as excellent heat resistance, solvent resistance, pattern adhesion and developability. As a result, a highly reliable colored pattern can be formed. That is, by using the photosensitive coloring composition, a highly reliable color filter can be provided.
＜樹脂硬化膜＞
　本実施形態の樹脂硬化膜を、例えば、以下の方法で作製することができる。
　本実施形態の感光性着色組成物を、ガラスなどの基板上に、目的に応じて最終の硬化塗膜の平均厚さが所定の値となるように塗膜した後、例えば、５０～１５０℃で１～５０分間加熱し溶剤を揮発させる。次に塗膜の全面を露光（例えば、ランプとして、ウシオ電機株式会社製ＵＳＨ－２５０ＢＹを使用、露光量４０ｍＪ／ｃｍ２）させ、さらに、例えば、５０～２００℃で１０～１８０分間ベーキングすることで硬化塗膜が得られる。また、フォトマスクを介して塗膜を露光し、アルカリ現像液で現像すれば所定の着色パターンを有する硬化塗膜が得られる。 <Resin cured film>
The cured resin film of this embodiment can be produced, for example, by the following method.
After coating the photosensitive coloring composition of the present embodiment on a substrate such as glass so that the average thickness of the final cured coating film becomes a predetermined value according to the purpose, for 1 to 50 minutes to volatilize the solvent. Next, the entire surface of the coating film is exposed (for example, USH-250BY manufactured by Ushio Inc. is used as a lamp, the exposure amount is 40 mJ/cm 2 ), and further, for example, baking is performed at 50 to 200° C. for 10 to 180 minutes. to obtain a cured coating film. Further, by exposing the coating film through a photomask and developing it with an alkaline developer, a cured coating film having a predetermined color pattern can be obtained.
＜カラーフィルター＞
　次に、本発明の感光性着色組成物の硬化物からなる着色パターンを有するカラーフィルターについて説明する。本発明のカラーフィルターは、上記の感光性着色組成物を用いて形成される着色パターンを有する。カラーフィルターは、通常、基板と、その上に形成されるＲＧＢの画素、それぞれの画素の境界に形成されるブラックマトリックス及び画素とブラックマトリックスの上に形成される保護膜とから構成される。この構成において、画素及びブラックマトリックス（着色パターン）が上記の感光性着色組成物を用いて形成されることを除けば、その他の構成は公知のものを採用することができる。 <Color filter>
Next, a color filter having a colored pattern made of a cured product of the photosensitive coloring composition of the present invention will be described. The color filter of the present invention has a colored pattern formed using the above photosensitive coloring composition. A color filter is generally composed of a substrate, RGB pixels formed thereon, a black matrix formed at the boundaries of each pixel, and a protective film formed over the pixels and the black matrix. In this configuration, except that the pixels and the black matrix (coloring pattern) are formed using the above-mentioned photosensitive coloring composition, other known configurations can be adopted.
　次に、カラーフィルターの製造方法の一実施形態について説明する。まず、基板上に着色パターンを形成する。具体的には、基板上に、ブラックマトリックス及びＲＧＢの画素を順次形成する。基板の材質は、特に限定されるものではなく、ガラス基板、シリコン基板、ポリカーボネート基板、ポリエステル基板、ポリアミド基板、ポリアミドイミド基板、ポリイミド基板、アルミニウム基板、プリント配線基板、アレイ基板などを適宜用いることができる。 Next, an embodiment of a method for manufacturing a color filter will be described. First, a colored pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamideimide substrates, polyimide substrates, aluminum substrates, printed wiring substrates, array substrates, etc. can be used as appropriate. can.
　着色パターンは、フォトリソグラフィ法により形成することができる。具体的には、上記の感光性着色組成物を基板上に塗布して塗布膜を形成した後、所定のパターンのフォトマスクを介して塗布膜を露光して露光部分を光硬化させる。そして、未露光部分をアルカリ水溶液で現像した後、ベーキングすることにより、所定の着色パターンを形成することができる。 The colored pattern can be formed by photolithography. Specifically, after coating the photosensitive coloring composition on a substrate to form a coating film, the coating film is exposed through a photomask having a predetermined pattern to photo-cure the exposed portion. By developing the unexposed portion with an alkaline aqueous solution and then baking, a predetermined colored pattern can be formed.
　感光性着色組成物の塗布方法としては、特に限定されないが、スクリーン印刷法、ロールコート法、カーテンコート法、スプレーコート法、スピンコート法などを用いることができる。また、感光性着色組成物の塗布後、必要に応じて、循環式オーブン、赤外線ヒーター、ホットプレートなどの加熱手段を用いて加熱することにより溶剤（Ｄ）を揮発させてもよい。加熱条件は、特に限定されず、使用する感光性着色組成物の種類に応じて適宜設定すればよい。一般には、５０℃～１２０℃の温度で３０秒～３０分加熱すればよい。 The method for applying the photosensitive coloring composition is not particularly limited, but screen printing, roll coating, curtain coating, spray coating, spin coating, and the like can be used. Moreover, after applying the photosensitive coloring composition, if necessary, the solvent (D) may be volatilized by heating using a heating means such as a circulating oven, an infrared heater, or a hot plate. The heating conditions are not particularly limited, and may be appropriately set according to the type of photosensitive coloring composition to be used. In general, heating may be performed at a temperature of 50° C. to 120° C. for 30 seconds to 30 minutes.
　次いで、形成された塗膜にネガ型のマスクを介して紫外線、エキシマレーザー光等の活性エネルギー線を照射して部分的に露光する。照射するエネルギー線量は、感光性着色組成物の組成に応じて適宜選択すればよく、例えば、３０～２０００ｍＪ／ｃｍ２であることが好ましい。露光に用いられる光源としては、特に限定されないが、低圧水銀ランプ、中圧水銀ランプ、高圧水銀ランプ、キセノンランプ、メタルハライドランプなどを用いることができる。 Next, the formed coating film is partially exposed by irradiating it with active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The energy dose to be irradiated may be appropriately selected according to the composition of the photosensitive coloring composition, and is preferably, for example, 30 to 2000 mJ/cm2. The light source used for exposure is not particularly limited, but low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, and the like can be used.
　現像に用いられるアルカリ水溶液としては、特に限定されないが、炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、水酸化ナトリウム、水酸化カリウムなどの水溶液；エチルアミノ基、ジエチルアミノ基、ジメチルエタノールアミノ基などのアミノ基系化合物の水溶液；テトラメチルアンモニウム、３－メチル－４－アミノ－Ｎ，Ｎ－ジエチルアニリン、３－メチル－４－アミノ－Ｎ－エチル－Ｎ－β－ヒドロキシエチルアニリン、３－メチル－４－アミノ－Ｎ－エチル－Ｎ－β－メタンスルホンアミドエチルアニリン、３－メチル－４－アミノ－Ｎ－エチル－Ｎ－β－メトキシエチルアニリン及びこれらの硫酸塩、塩酸塩又はｐ－トルエンスルホン酸塩などのｐ－フェニレンジアミノ基系化合物の水溶液などを用いることができる。なお、これらの水溶液には、必要に応じて消泡剤や界面活性剤を添加してもよい。また、上記のアルカリ水溶液による現像の後、水洗して乾燥させることが好ましい。 The alkaline aqueous solution used for development is not particularly limited, but aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; amino groups such as ethylamino group, diethylamino group, and dimethylethanolamino group Aqueous solutions of compounds; tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino -N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates, etc. can be used. In addition, you may add a defoaming agent and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash with water and dry after the development with the above alkaline aqueous solution.
　また、ベーキングの条件は、特に限定されず、使用する感光性着色組成物の種類に応じて加熱処理を行えばよい。一般には、８０～２５０℃で１０～６０分間加熱すればよい。 Also, the baking conditions are not particularly limited, and heat treatment may be performed according to the type of photosensitive coloring composition to be used. Generally, heating at 80 to 250° C. for 10 to 60 minutes is sufficient.
　上記のような塗布、露光、現像及びベーキングを、ブラックマトリックス用の感光性着色組成物、及び赤色、緑色、青色の画素用感光性着色組成物を用いて順次繰り返すことにより、所望の着色パターンを形成することができる。その後、着色パターン（ＲＧＢの各画素及びブラックマトリックス）上に保護膜を形成するが、保護膜としては、特に限定されず、公知のものを用いて形成すればよい。 A desired coloring pattern is obtained by successively repeating the coating, exposure, development and baking as described above using a photosensitive coloring composition for black matrix and photosensitive coloring compositions for red, green and blue pixels. can be formed. After that, a protective film is formed on the colored pattern (RGB pixels and black matrix).
　このようにして製造されるカラーフィルターは、顔料の均一な微細化を実現することで顔料分散性が優れ、高輝度化を達成し、優れた耐熱性、耐溶剤性、密着性を有し、分散剤や着色剤のブリードアウトの抑制が期待できる。 The color filter produced in this way has excellent pigment dispersibility by achieving uniform fineness of the pigment, achieves high brightness, and has excellent heat resistance, solvent resistance, and adhesion. Suppression of bleeding out of dispersants and coloring agents can be expected.
＜画像表示素子＞
　本実施形態の画像表示素子は、上記のカラーフィルターを備えた画像表示素子であり、その具体例として、液晶表示素子、有機ＥＬ表示素子、ＣＣＤ素子やＣＭＯＳ素子などの固体撮像素子などが挙げられる。本実施形態の画像表示素子の製造は、上記のカラーフィルターを使用すること以外、常法に従って行えばよい。例えば、液晶表示素子を製造する場合には、基板上に、上記カラーフィルターを形成し、次いで、電極、スペーサー等を順次形成する。そして、もう一枚の基板上に電極等を形成し、両者を張り合わせて所定量の液晶を注入、封止すればよい。 <Image display device>
The image display device of the present embodiment is an image display device having the color filter described above, and specific examples thereof include a liquid crystal display device, an organic EL display device, a solid-state imaging device such as a CCD device and a CMOS device, and the like. . The image display device of this embodiment may be manufactured according to a conventional method, except for using the color filter described above. For example, when manufacturing a liquid crystal display device, the above color filter is formed on a substrate, and then electrodes, spacers and the like are sequentially formed. Then, an electrode or the like is formed on another substrate, the two substrates are pasted together, a predetermined amount of liquid crystal is injected, and the substrate is sealed.
　以下、実施例を参照して本発明を詳細に説明するが、本発明はこれらの実施例により限定されない。なお、この実施例において、部及びパーセントとあるのは特に断らない限り、全て質量基準である。 The present invention will be described in detail below with reference to examples, but the present invention is not limited by these examples. In the examples, all parts and percentages are based on mass unless otherwise specified.
＜バインダー樹脂（Ａ－１）が有する官能基（Ｘ）の含有量＞
　バインダー樹脂（Ａ－１）の質量当たりの、官能基（Ｘ）のモル数であり、原料モノマーの使用量に基づいて算出した計算値である。 <Content of functional group (X) possessed by binder resin (A-1)>
It is the number of moles of the functional group (X) per mass of the binder resin (A-1), and is a calculated value calculated based on the amount of raw material monomer used.
＜官能基（Ｘ）含有化合物量＞
　官能基（Ｘ）含有化合物量は、バインダー樹脂（Ａ－１）の原料としての全モノマー１００モル％に対して、官能基（Ｘ）含有化合物の使用量（モル％）である。実際のバインダー樹脂（Ａ－１）の原料に含まれている全モノマーの使用量及び官能基（Ｘ）含有化合物の使用量に基づいて算出した計算値である。 <Amount of compound containing functional group (X)>
The amount of the functional group (X)-containing compound is the amount (mol %) of the functional group (X)-containing compound used with respect to 100 mol % of all monomers as raw materials for the binder resin (A-1). It is a calculated value calculated based on the amount of all the monomers and the amount of the functional group (X)-containing compound that are contained in the raw material of the actual binder resin (A-1).
＜未反応官能基（Ｘ）量＞
　未反応官能基（Ｘ）量は、前記官能基（Ｘ）含有化合物量から付加反応で消費した官能基（Ｘ）量を除く後の量である。前記算出した官能基（Ｘ）含有化合物量、バインダー樹脂（Ａ－１）への付加反応ために添加したモノマーの実際の使用量に基づいて算出した計算値である。 <Amount of unreacted functional group (X)>
The amount of unreacted functional group (X) is the amount after removing the amount of functional group (X) consumed in the addition reaction from the amount of the functional group (X)-containing compound. It is a calculated value calculated based on the calculated amount of the compound containing the functional group (X) and the actual amount of the monomer added for the addition reaction to the binder resin (A-1).
＜バインダー樹脂（Ａ－１）の官能基（Ｘ）の総量に対する、付加率（Ｃ＝Ｃ導入率）＞　官能基（Ｙ）及びエチレン性不飽和基を有する化合物を官能基（Ｘ）に付加し、バインダー樹脂（Ａ－１）にエチレン性不飽和基を導入する場合には、その付加率は、官能基（Ｘ）の総モル数１００モル％に対して、前記化合物のモル比（モル％）である。実際の官能基（Ｘ）含有モノマーの使用量及び付加反応用前記化合物の使用量に基づいて算出した。 <Addition rate (C=C introduction rate) with respect to the total amount of functional groups (X) in the binder resin (A-1)> Adding a compound having a functional group (Y) and an ethylenically unsaturated group to the functional group (X) However, when an ethylenically unsaturated group is introduced into the binder resin (A-1), the addition rate is the molar ratio (mol %). It was calculated based on the amount of the actual functional group (X)-containing monomer used and the amount of the compound for the addition reaction used.
＜固形分濃度＞
　バインダー樹脂（Ａ－１）合成後の溶液のうち、溶剤を除く成分を合計した割合である。 <Solid content concentration>
It is the total proportion of the components excluding the solvent in the solution after synthesis of the binder resin (A-1).
＜固形分酸価＞
　酸価は、ＪＩＳ　Ｋ６９０１　５．３に従ってブロモチモールブルーとフェノールレッドとの混合指示薬を用いて測定した。 <Solid content acid value>
The acid value was measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3.
＜重量平均分子量、数平均分子量の測定法＞
　重量平均分子量、数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて、下記条件にて測定した標準ポリスチレン換算重量平均分子量、数平均分子量を意味する。
　　カラム：ショウデックス（登録商標）　ＬＦ－８０４＋ＬＦ－８０４（昭和電工株式会社製）
　　カラム温度：４０℃
　　試料：測定対象物の０．２％テトラヒドロフラン溶液
　　展開溶媒：テトラヒドロフラン
　　検出器：示差屈折計（ショウデックス　ＲＩ－７１Ｓ）（昭和電工株式会社製）
　　流速：１ｍＬ／ｍｉｎ <Measurement method of weight average molecular weight and number average molecular weight>
The weight average molecular weight and number average molecular weight mean the standard polystyrene conversion weight average molecular weight and number average molecular weight measured under the following conditions using gel permeation chromatography (GPC).
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko K.K.)
Column temperature: 40°C
Sample: 0.2% tetrahydrofuran solution of object to be measured Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Showdex RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1 mL/min
＜アミノ基含有高分子化合物（ｃ－１）が有するアミノ基の総量に対する、ハロゲン化合物（ｃ－２）の付加率＞
　アミノ基含有高分子化合物（ｃ－１）が有するアミノ基の総量に対する、ハロゲン化合物（ｃ－２）の付加率は、実際の高分子化合物（ｃ－１）及び前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）の使用量、高分子分散剤（Ｃ）の官能基（Ｙ）の量、高分子分散剤（Ｃ）のアミン価、高分子分散剤（Ｃ）の３級アミン価に基づいて算出した計算値である。 <Addition rate of halogen compound (c-2) with respect to total amount of amino groups possessed by amino group-containing polymer compound (c-1)>
The addition rate of the halogen compound (c-2) with respect to the total amount of amino groups possessed by the amino group-containing polymer compound (c-1) is the actual polymer compound (c-1) and the functional group (Y). Amount of halogen compound (c-2) used, amount of functional group (Y) of polymeric dispersant (C), amine value of polymeric dispersant (C), tertiary amine value of polymeric dispersant (C) It is a calculated value calculated based on
＜高分子分散剤（Ｃ）のアミン価＞
　高分子分散剤（Ｃ）のアミン価は、前述の方法（ＪＩＳ　Ｋ７２３７）に基づき測定した。また、本明細書に記載の計算方法を用いて３級アミン価を算出した。それぞれの結果を、表１Ａ及び表１Ｂに示す。 <Amine value of polymer dispersant (C)>
The amine value of the polymeric dispersant (C) was measured according to the method described above (JIS K7237). Also, the tertiary amine value was calculated using the calculation method described herein. The respective results are shown in Tables 1A and 1B.
＜高分子分散剤（Ｃ）の官能基（Ｙ）量＞
　高分子分散剤（Ｃ）の質量あたりの、官能基（Ｙ）のモル数であり、実際の高分子化合物（ｃ－１）及び前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）の使用量に基づいて算出した計算値である。 <Functional Group (Y) Amount of Polymer Dispersant (C)>
It is the number of moles of the functional group (Y) per mass of the polymer dispersant (C), and is the actual polymer compound (c-1) and the halogen compound (c-2) having the functional group (Y). It is a calculated value calculated based on the usage amount.
　バインダー樹脂（Ａ－１）の製造例を以下に示す。 A production example of the binder resin (A-1) is shown below.
「バインダー樹脂の合成（合成例ａ１～ａ１２、比較合成例ａ’１～ａ’３）」
＜合成例ａ１＞
　攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、７３．７ｇのプロピレングリコールモノメチルエーテルアセテートを入れた後、窒素ガスで置換しながら撹拌し、１２０℃に昇温した。次に、２７．５ｇのトリシクロデカニルメタクリレート、６６．０ｇのベンジルメタクリレート及び４５．０ｇのアクリル酸、１６．３ｇのエチレングリコールメタクリラート（ＨＥＭＡ）からなるモノマー混合物に、重合開始剤として１５．５ｇのｔ－ブチルパーオキシ－２－エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、１２０℃で２時間攪拌して共重合反応を行った。
　次に、前記フラスコ内をドライエアーに置換した後、２６．６ｇのグリシジルメタクリレート、触媒として０．５ｇのトリフェニルホスフィン及び重合禁止剤として０．４ｇのハイドロキノンモノメチルエーテルを加え、１２０℃で５時間反応を行った後、溶剤としてプロピレングリコールモノメチルエーテルアセテート１３２ｇを加え固形分が４０％となるように調製し、官能基（Ｙ）としてヒドロキシ基、アルカリ可溶性としてカルボン酸を有するバインダー樹脂（Ａ－１）又は（Ａ－２）として試料ＰＲ１を得た。 "Synthesis of Binder Resin (Synthesis Examples a1 to a12, Comparative Synthesis Examples a'1 to a'3)"
<Synthesis example a1>
After putting 73.7 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, the mixture was stirred while being replaced with nitrogen gas, and heated to 120°C. Next, 15.5 g of ethylene glycol methacrylate (HEMA) as a polymerization initiator was added to a monomer mixture consisting of 27.5 g of tricyclodecanyl methacrylate, 66.0 g of benzyl methacrylate and 45.0 g of acrylic acid, 16.3 g of ethylene glycol methacrylate (HEMA). 5 g of t-butyl peroxy-2-ethylhexanoate was added dropwise into the flask from the dropping funnel. After completion of dropping, the mixture was stirred at 120° C. for 2 hours to carry out a copolymerization reaction.
Next, after replacing the inside of the flask with dry air, 26.6 g of glycidyl methacrylate, 0.5 g of triphenylphosphine as a catalyst and 0.4 g of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the mixture was heated at 120°C for 5 hours. After the reaction, 132 g of propylene glycol monomethyl ether acetate was added as a solvent to adjust the solid content to 40%, and the binder resin (A-1 ) or (A-2) to obtain sample PR1.
＜合成例ａ２～ａ１２、比較合成例ａ’１～ａ’３＞
　表２Ａ及び表２Ｂに記載のモノマーを使用し、重合温度、モノマー比率以外は、合成例ａ１と同様の方法に従い、バインダー樹脂（Ａ－１）又は（Ａ－２）として試料ＰＲ２～ＰＲ１２、ｃＰＲ１～ｃＰＲ３を得た。 <Synthesis Examples a2 to a12, Comparative Synthesis Examples a′1 to a′3>
Using the monomers listed in Tables 2A and 2B, according to the same method as in Synthesis Example a1 except for the polymerization temperature and the monomer ratio, samples PR2 to PR12 and cPR1 as the binder resin (A-1) or (A-2) -cPR3 was obtained.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１Ａ及び表１Ｂ中表記の説明は以下である。
　ＴＣＤＭＡ：トリシクロデカニルメタクリレート
　ＢＺＭＡ：ベンジルメタクリレート
　２ＥＨＡ：２－エチルヘキシルアクリレート
　ＨＥＭＡ：ヒドロキシエチルメタクリレート
　４ＨＢＡ：４－ヒドロキシブチルアクリレート
　ＭＡＡ：メタクリル酸
　ＡＡ：アクリル酸
　ＭＯＩ－ＤＥＭ：マロン酸－２－［［［２－メチル－１－オキソ－２－プロペニル］オキシ］エチル］アミノ］カルボニル］－１，３ジエチルエステル
　ＭＯＩ－ＢＰ：２－［（３，５－ジメチルピラゾリル）カルボニルアミノ］エチルメタクリレート
　ＭＯＩ－ＢＭ：２－［０－（１’－メチルプロピリデンアミノ）カルボキシアミノ］エチルメタクリラート
　ＧＭＡ：グリシジルメタクリレート
　３ＥＯＸＭＡ：（３－エチルオキセタン－３－イル）メチルメタクリレート The descriptions of the notations in Tables 1A and 1B are as follows.
TCDMA: tricyclodecanyl methacrylate BZMA: benzyl methacrylate 2EHA: 2-ethylhexyl acrylate HEMA: hydroxyethyl methacrylate 4HBA: 4-hydroxybutyl acrylate MAA: methacrylic acid AA: acrylic acid MOI-DEM: malonic acid-2-[[[2 -methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester MOI-BP: 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate MOI-BM: 2 -[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate GMA: glycidyl methacrylate 3EOXMA: (3-ethyloxetan-3-yl) methyl methacrylate
　高分子分散剤（Ｃ）の製造例を以下に示す。 A production example of the polymer dispersant (C) is shown below.
「アミノ基含有高分子化合物（ｃ－１）の合成（合成例ｂ１～ｂ２）」
＜合成例ｂ１＞
　攪拌装置、滴下ロート、コンデンサー、温度計およびガス導入管を備えたフラスコに、１３３ｇのプロピレングリコールモノメチルエーテルアセテート、８０．５ｇのイソボルニルメタクリレート及び触媒として１３．２ｇのテトラメチルエチレンジアミンを入れ、フラスコ内を窒素に置換しながら５０℃で１時間攪拌した。その後、触媒として９．３ｇのブロモイソ酪酸エチル及び５．６ｇの塩化第一銅を入れ、フラスコを１１０℃に昇温した後４時間重合反応を行った。反応後、溶液をサンプリングし不揮発分を測定し、不揮発分から換算し重合転化率が９８％以上であることを確認した後、６１ｇのプロピレングリコールモノメチルエーテルアセテート及び３級アミノ基を有するモノマーとして１９．５ｇのジメチルアミノエチルメタクリレートを加え、さらに１１０℃で２時間反応を行った。反応後、再度溶液をサンプリングし不揮発分を測定し、不揮発分から換算し重合転化率が９８％以上であることを確認した後、溶液を冷却した。最後に、溶剤としてプロピレングリコールモノメチルエーテルアセテートを固形分が４０．０％となるように添加し、３級アミノ基を含有する高分子化合物（ｃ－１）としてｂＰＤ１（アミン価７０ｍｇＫＯＨ／ｇ、重量平均分子量５５００）を得た。 "Synthesis of Amino Group-Containing Polymer Compound (c-1) (Synthesis Examples b1-b2)"
<Synthesis example b1>
133 g of propylene glycol monomethyl ether acetate, 80.5 g of isobornyl methacrylate and 13.2 g of tetramethylethylenediamine as a catalyst were placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube. The mixture was stirred at 50° C. for 1 hour while purging the inside with nitrogen. Thereafter, 9.3 g of ethyl bromoisobutyrate and 5.6 g of cuprous chloride were added as catalysts, and the flask was heated to 110° C., and polymerization reaction was carried out for 4 hours. After the reaction, the solution was sampled and the non-volatile content was measured, converted into the non-volatile content, and after confirming that the polymerization conversion rate was 98% or more, 61 g of propylene glycol monomethyl ether acetate and a monomer having a tertiary amino group of 19. 5 g of dimethylaminoethyl methacrylate was added and the reaction was further carried out at 110° C. for 2 hours. After the reaction, the solution was sampled again, the non-volatile content was measured, converted into the non-volatile content, and after confirming that the polymerization conversion rate was 98% or more, the solution was cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40.0%, and bPD1 (amine value 70 mgKOH/g, weight An average molecular weight of 5500) was obtained.
＜合成例ｂ２＞
　イソボルニルメタクリレートとジメチルアミノエチルメタクリレートの使用量を変更する以外は上記合成１と同様にして、３級アミノ基を含有する高分子化合物（ｃ－１）として、ｂＰＤ２（アミン価１６０ｍｇＫＯＨ／ｇ、重量平均分子量５５００）を得た。 <Synthesis example b2>
bPD2 (amine value: 160 mgKOH/g, A weight average molecular weight of 5500) was obtained.
「高分子分散剤の合成（合成例ｃ１～ｃ１１、比較合成例ｃ’１～ｃ’２）」
＜合成例ｃ１＞
　高分子化合物（ｃ－１）として合成例ｂ１で得られたｂＰＤ１を３５ｇ（溶剤を除く固形分換算）、前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）として３－ブロモ－２－メチルプロパノール－２－［（３，５－ジメチルピラゾリル）カルボニルアミノ］－エチルエステルを２．８７ｇ（高分子化合物（ｃ－１）のアミノ基の総量に対して２０モル％）、溶剤としてプロピレングリコールモノメチルエーテルアセテートを仕込み量から計算した不揮発分が３０％となるよう加え、フラスコ内を窒素ガスで置換しながら攪拌し、室温から１００℃まで昇温した。ＮＭＲスペクトルにより３－ブロモ－２－メチルプロパノール－２－［（３，５－ジメチルピラゾリル）カルボニルアミノ］－エチルエステルのピークシフトを確認するまで攪拌した後、室温まで降温し、アミノ基含有高分子化合物（ｃ－１）と前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）の反応物として高分子分散剤（ＰＤ１）を得た。 "Synthesis of Polymeric Dispersants (Synthesis Examples c1-c11, Comparative Synthesis Examples c'1-c'2)"
<Synthesis example c1>
35 g of bPD1 obtained in Synthesis Example b1 as the polymer compound (c-1) (in terms of solid content excluding the solvent), and 3-bromo-2- as the halogen compound (c-2) having the functional group (Y) 2.87 g of methylpropanol-2-[(3,5-dimethylpyrazolyl)carbonylamino]-ethyl ester (20 mol% relative to the total amount of amino groups in the polymer compound (c-1)), propylene glycol as a solvent Monomethyl ether acetate was added so that the non-volatile content calculated from the amount charged was 30%, and the mixture was stirred while replacing the atmosphere in the flask with nitrogen gas, and the temperature was raised from room temperature to 100°C. After stirring until the peak shift of 3-bromo-2-methylpropanol-2-[(3,5-dimethylpyrazolyl)carbonylamino]-ethyl ester is confirmed by NMR spectrum, the temperature is lowered to room temperature, and the amino group-containing polymer is A polymeric dispersant (PD1) was obtained as a reaction product of the compound (c-1) and the halogen compound (c-2) having the functional group (Y).
＜合成例ｃ２～ｃ８、ｃ１０＞
　アミノ基含有高分子化合物（ｃ－１）の種類と使用量、前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）の種類と使用量を変更する以外は合成例１と同様にして、高分子分散剤（Ｃ）として、試料ＰＤ２～ＰＤ８、ＰＤ１０を得た。高分子分散剤（Ｃ）の官能基（Ｙ）量を表２Ａ及び表２Ｂに示す。 <Synthesis Examples c2 to c8, c10>
In the same manner as in Synthesis Example 1 except that the type and amount of the amino group-containing polymer compound (c-1) and the type and amount of the halogen compound (c-2) having the functional group (Y) are changed, Samples PD2 to PD8 and PD10 were obtained as polymer dispersants (C). Tables 2A and 2B show the functional group (Y) content of the polymeric dispersant (C).
＜合成例ｃ９＞
　アミノ基含有高分子化合物（ｃ－１）として３級アミン分散剤ＥＦＫＡ－ＰＸ４３００（ＢＡＳＦ社製、固形分３０％、アミン価５７ｍｇＫＯＨ／ｇ、重量平均分子量２５０００）を用いる以外は、合成例ｃ５と同様にして試料ＰＤ９を得た。官能基（Ｙ）含有高分子分散剤の官能基（Ｙ）量を表２Ｂに示す。 <Synthesis example c9>
Except for using a tertiary amine dispersant EFKA-PX4300 (manufactured by BASF, solid content 30%, amine value 57 mgKOH / g, weight average molecular weight 25000) as the amino group-containing polymer compound (c-1), Synthesis Example c5 and Sample PD9 was obtained in the same manner. Table 2B shows the amount of functional group (Y) in the functional group (Y)-containing polymeric dispersant.
＜合成例ｃ１１＞
　アミノ基含有高分子化合物（ｃ－１）としてポリメントＮＫ－３８０（日本触媒社製、固形分３０％、アミン価５６ｍｇＫＯＨ／ｇ、重量平均分子量１０００００）を用いる以外は、合成例ｃ３と同様にして試料ＰＤ１１を得た。官能基（Ｙ）含有高分子分散剤の官能基（Ｙ）量を表２Ｂに示す。 <Synthesis example c11>
In the same manner as in Synthesis Example c3, except that Polyment NK-380 (manufactured by Nippon Shokubai Co., Ltd., solid content 30%, amine value 56 mgKOH/g, weight average molecular weight 100000) is used as the amino group-containing polymer compound (c-1). Sample PD11 was obtained. Table 2B shows the amount of functional group (Y) in the functional group (Y)-containing polymeric dispersant.
＜比較合成例ｃ’１～ｃ’２＞
　前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）の代わりに、表１Ａ及び表１Ｂに記載の官能基（Ｙ）を含まないハロゲン化合物を用いることと、反応温度を４０℃にすること以外は分散剤合成例１と同様にして、官能基（Ｙ）を含まない高分子分散剤として試料ｃＰＤ１～ｃＰＤ２を得た。官能基（Ｙ）非含有高分子分散剤官能基（Ｙ）量を表２Ｂに示す。 <Comparative Synthesis Examples c'1 to c'2>
Instead of the halogen compound (c-2) having the functional group (Y), use a halogen compound not containing the functional group (Y) described in Tables 1A and 1B, and set the reaction temperature to 40 ° C. Samples cPD1 and cPD2 were obtained as polymer dispersants containing no functional group (Y) in the same manner as in Dispersant Synthesis Example 1, except for the above. Functional Group (Y)-Free Polymeric Dispersant Functional Group (Y) content is shown in Table 2B.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表２Ａ及び表２Ｂ中表記の説明は以下である。
　ＥＦＫＡ－ＰＸ４３００：ＢＡＳＦ製、固形分３０％、３級アミン分散剤、アミン価５７ｍｇＫＯＨ／ｇ、重量平均分子量２５０００
　ｂＰＤ１：合成例ｂ１で得られたアミノ基含有高分子化合物（ｃ－１）　アミン価７０ｍｇＫＯＨ／ｇ
　ｂＰＤ２：合成例ｂ２で得られたアミノ基含有高分子化合物（ｃ－１）　アミン価１６０ｍｇＫＯＨ／ｇ
　ポリメントＮＫ－３８０：日本触媒社製、固形分３０％、１，２級アミン分散剤、アミン価５６ｍｇＫＯＨ／ｇ、重量平均分子量１０００００）
　ブロモ化ＭＯＩ－ＢＰ：２－ブロモ－２－メチルプロピオン酸，２－［（３，５－ジメチルピラゾリル）カルボニルアミノ］エチルエステル
　ブロモ化ＭＯＩ－ＤＥＭ：マロン酸－２－［［［２－ブロモ－２－メチル－１－オキソ－２－プロパニル］オキシ］エチル］アミノ］カルボニル］－１，３ジエチルエステル　エピブロモヒドリン：３－ブロモプロピレンオキシド
　ブロモ化ＥＶＭＯ：３－エチル－３－［２－ブロモエトキシメチル］－オキセタン
　ＥＢｒ：エチレンブロモヒドリン：
　３ＢｒＰ：３－ブロモ－１，２－プロパンジオール：
　１１ＢｒＵｎ：１１－ブロモ－１－ウンデカンチオール：
　ＢｒＡｃ：ブロモ酢酸
　ＢｒＥ：ブロモエチレン
　ＡＢｒ：アリルブロマイド The descriptions of the notations in Tables 2A and 2B are as follows.
EFKA-PX4300: manufactured by BASF, solid content 30%, tertiary amine dispersant, amine value 57 mgKOH/g, weight average molecular weight 25000
bPD1: amino group-containing polymer compound (c-1) obtained in Synthesis Example b1, amine value 70 mgKOH/g
bPD2: amino group-containing polymer compound (c-1) obtained in Synthesis Example b2, amine value 160 mgKOH/g
Polyment NK-380: manufactured by Nippon Shokubai Co., Ltd., solid content 30%, primary and secondary amine dispersant, amine value 56 mgKOH/g, weight average molecular weight 100,000)
Brominated MOI-BP: 2-bromo-2-methylpropionic acid, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl ester Brominated MOI-DEM: Malonic acid-2-[[[2-bromo- 2-methyl-1-oxo-2-propanyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester epibromohydrin: 3-bromopropylene oxide brominated EVMO: 3-ethyl-3-[2-bromo ethoxymethyl]-oxetane EBr: ethylene bromohydrin:
3BrP: 3-bromo-1,2-propanediol:
11BrUn: 11-bromo-1-undecanethiol:
BrAc: bromoacetic acid BrE: bromoethylene ABr: allyl bromide
　顔料分散組成物の製造例を以下に示す。 An example of producing a pigment dispersion composition is shown below.
＜実施例ａ１～ａ１９＞
　直径０．１ｍｍのジルコニアビーズ（ニッカトー製ＹＴＺボール）２００ｇを充填したＳＵＳ容器（内径５０ｍｍ×高さ１００ｍｍ）に、顔料（Ｂ）としてＣ．Ｉ．ピグメントグリーン５８（ＤＩＣ製Ｆａｓｔｏｇｅｎ　Ｇｒｅｅｎ　Ａ１１０）を７．５ｇ（１００質量部）、高分子分散剤（Ｃ）として合成例ｃ１～ｃ１１で得られた試料ＰＤ１～ＰＤ１１のいずれか、バインダー樹脂（Ａ）として合成例ａ１～ａ１１で得られた試料ＰＲ１～ＰＲ１１を表３Ａ及び表３Ｂに示す組成で混合し、溶剤（Ｄ－１）としてプロピレングリコールモノメチルエーテルアセテートを加え、ジルコニアビーズを除いた固形分が２４％となるように調製し、ペイントシェイカー（Ｒｅｄ　Ｄｅｖｉｌ　Ｅｑｕｉｐｍｅｎｔ製Ｒｅｄ　Ｄｅｖｉｌ　５４００）で室温下、２時間混合して分散させた後、内容物をガラスフィルターで吸引ろ過することにより、顔料分散組成物ＭＢ１～ＭＢ１９を得た。 <Examples a1 to a19>
A C.I. I. 7.5 g (100 parts by mass) of Pigment Green 58 (Fastogen Green A110 manufactured by DIC), one of samples PD1 to PD11 obtained in Synthesis Examples c1 to c11 as a polymer dispersant (C), and a binder resin (A) Samples PR1 to PR11 obtained in Synthesis Examples a1 to a11 were mixed with the compositions shown in Tables 3A and 3B, propylene glycol monomethyl ether acetate was added as a solvent (D-1), and the solid content excluding zirconia beads was 24%, mixed and dispersed at room temperature for 2 hours with a paint shaker (Red Devil 5400, manufactured by Red Devil Equipment), and then suction-filtered the contents with a glass filter to obtain a pigment dispersion composition. MB1 to MB19 were obtained.
＜比較例ａ’１～ａ’６＞
　直径０．１ｍｍのジルコニアビーズ（ニッカトー製ＹＴＺボール）２００ｇを充填したＳＵＳ容器（内径５０ｍｍ×高さ１００ｍｍ）に、顔料（Ｂ）としてＣ．Ｉ．ピグメントグリーン５８（ＤＩＣ製Ｆａｓｔｏｇｅｎ　Ｇｒｅｅｎ　Ａ１１０）を７．５ｇ（１００質量部）、高分子分散剤として比較合成例ｃ’１、ｃ’２で得られた試料ｃＰＤ１～ｃＰＤ２のいずれか、バインダー樹脂として合成例ａ１～ａ１１、比較合成例ａ’１～ａ’３で得られた試料を表３Ｂに示す組成で混合し、溶剤（Ｄ－１）としてプロピレングリコールモノメチルエーテルアセテートを加え、ジルコニアビーズを除いた固形分が２４％となるように調製し、ペイントシェイカー（Ｒｅｄ　Ｄｅｖｉｌ　Ｅｑｕｉｐｍｅｎｔ製Ｒｅｄ　Ｄｅｖｉｌ　５４００）で室温下、２時間混合して分散させた後、内容物をガラスフィルターで吸引ろ過することにより、顔料分散組成物ｃＭＢ１～ｃＭＢ６を得た。 <Comparative Examples a'1 to a'6>
A C.I. I. 7.5 g (100 parts by mass) of Pigment Green 58 (DIC Fastogen Green A110), one of the samples cPD1 to cPD2 obtained in Comparative Synthesis Examples c'1 and c'2 as a polymer dispersant, and a binder resin The samples obtained in Synthesis Examples a1 to a11 and Comparative Synthesis Examples a′1 to a′3 were mixed with the composition shown in Table 3B, propylene glycol monomethyl ether acetate was added as the solvent (D-1), and zirconia beads were removed. It was prepared so that the solid content was 24%, mixed and dispersed at room temperature for 2 hours with a paint shaker (Red Devil 5400 manufactured by Red Devil Equipment), and then the contents were subjected to suction filtration through a glass filter. Pigment dispersion compositions cMB1 to cMB6 were obtained.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
＜顔料分散性の評価＞
　調製した直後の顔料分散組成物の粘度をＥ型粘度計（東機産業株式会社製ＲＥ－８０Ｌ、コーンサイズ４．８ｃｍ、回転数２０ｒｐｍ、測定温度２５℃）で測定することで評価した。また、粘度の測定結果より、顔料分散性を下記基準により１～５の５段階で評価し、３以上を合格とした。評価結果を前記表３Ａ及び表３Ｂに示した。
　「５」：６．０ｍＰａ・ｓ未満
　「４」：６．０ｍＰａ・ｓ以上８．０ｍＰａ・ｓ未満
　「３」：８．０ｍＰａ・ｓ以上１０．０ｍＰａ・ｓ未満
　「２」：１０．０ｍＰａ・ｓ以上
　「１」：流動性無し <Evaluation of Pigment Dispersibility>
The viscosity of the pigment dispersion composition immediately after preparation was evaluated by measuring it with an E-type viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd., cone size 4.8 cm, number of revolutions 20 rpm, measurement temperature 25° C.). Further, based on the viscosity measurement results, the pigment dispersibility was evaluated on a scale of 1 to 5 according to the following criteria, and 3 or more was considered acceptable. The evaluation results are shown in Tables 3A and 3B.
"5": Less than 6.0 mPa s "4": 6.0 mPa s or more and less than 8.0 mPa s "3": 8.0 mPa s or more and less than 10.0 mPa s "2": 10.0 mPa s s or more "1": No liquidity
＜顔料分散組成物の保存安定性の評価＞
　調製した顔料分散組成物を室温で１カ月保管した後の顔料分散組成物の粘度をＥ型粘度計（東機産業株式会社製ＲＥ－８０Ｌ、測定温度２５℃）で測定することで評価した。室温で１カ月保管した後の顔料分散組成物の粘度の上昇率「（保管後粘度－調整後粘度）×１００／調整後粘度」が、調製した直後と比較し、下記基準により１～５の５段階で評価した。評価結果を前記表３Ａ及び表３Ｂに示した。
　「５」：５％未満
　「４」：５％以上１０％未満
　「３」：１０％以上２０％未満
　「２」：２０％以上４０％未満
　「１」：１４日以内に流動性を失う <Evaluation of storage stability of pigment dispersion composition>
After the prepared pigment dispersion composition was stored at room temperature for one month, the viscosity of the pigment dispersion composition was measured with an E-type viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd., measurement temperature 25° C.) and evaluated. The rate of increase in the viscosity of the pigment dispersion composition after storage for one month at room temperature "(viscosity after storage - viscosity after adjustment) x 100/viscosity after adjustment" is 1 to 5 according to the following criteria compared to immediately after preparation. It was evaluated in 5 stages. The evaluation results are shown in Tables 3A and 3B.
“5”: Less than 5% “4”: 5% to 10% “3”: 10% to less than 20% “2”: 20% to less than 40% “1”: Lose liquidity within 14 days
感光性着色組成物（ＣＲ）の製造例を以下に示す。 A production example of the photosensitive coloring composition (CR) is shown below.
＜実施例ｂ１～ｂ１９、比較例ｂ’１～ｂ’６＞
　前記実施例ａ１～ａ１９で得られた顔料分散組成物ＭＢ１～ＭＢ１９、及び比較例ａ’１～ａ’６で得られた顔料分散組成物ｃＭＢ１～ｃＭＢ４の固形分（溶剤以外の成分の総量）を１００質量部としたときに、バインダー樹脂（Ａ－２）として樹脂合成例ａ１０で得られた試料ＰＲ１０を固形分として８０質量部、反応性希釈剤（Ｅ）としてジペンタエリスリトールヘキサアクリレートを８０質量部、光重合開始剤（Ｆ）として１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル－］－，－１－（Ｏ－アセチルオキシム）を４質量部混合し、溶剤（Ｄ－２）としてプロピレングリコールモノメチルエーテルアセテートを加え全体の固形分が３０％となるように混合することで、感光性着色組成物ＣＲ１～１９及びｃＣＲ１～ｃＣＲ６を調製した。なお、顔料（Ｂ）１００質量部に対する各成分配合量としては、バインダー樹脂（Ａ－２）が１２８質量部、反応性希釈剤（Ｅ）が１２８質量部、光重合開始剤（Ｆ）が６．４質量部である。表４Ａ及び表４Ｂに各種材料の使用部数を示す。 <Examples b1 to b19, Comparative Examples b'1 to b'6>
Solid content of pigment dispersion compositions MB1 to MB19 obtained in Examples a1 to a19, and pigment dispersion compositions cMB1 to cMB4 obtained in Comparative Examples a′1 to a′6 (total amount of components other than solvent) is 100 parts by mass, 80 parts by mass of sample PR10 obtained in Resin Synthesis Example a10 as a binder resin (A-2) as a solid content, and 80 parts by mass of dipentaerythritol hexaacrylate as a reactive diluent (E) 4 parts by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-,-1-(O-acetyloxime) as a photopolymerization initiator (F) Partial mixing, adding propylene glycol monomethyl ether acetate as a solvent (D-2) and mixing so that the total solid content is 30%, photosensitive coloring compositions CR1 to 19 and cCR1 to cCR6 were prepared. The blending amount of each component for 100 parts by mass of the pigment (B) is 128 parts by mass of the binder resin (A-2), 128 parts by mass of the reactive diluent (E), and 6 parts by mass of the photopolymerization initiator (F). .4 parts by mass. Tables 4A and 4B show the parts used for various materials.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
＜耐溶剤試験用緑色レジスト（１）の作製＞
　得られた感光性着色組成物ＣＲ１～ＣＲ１９、ｃＣＲ１～ｃＣＲ６を、５ｃｍ角ガラス基板（無アルカリガラス基板）上に、最終の硬化塗膜の平均厚さが１．５μｍとなるようにスピンコートした後、１００℃で３分間加熱し溶剤を揮発させた。次に塗膜の全面を露光（ランプとして、ウシオ電機株式会社製ＵＳＨ－２５０ＢＹを使用、露光量４０ｍＪ／ｃｍ２）させた後、さらに１００℃で３０分間ベーキングすることで硬化塗膜である緑色レジスト（１）を得た。 <Preparation of green resist (1) for solvent resistance test>
The resulting photosensitive coloring compositions CR1 to CR19 and cCR1 to cCR6 were spin-coated onto a 5 cm square glass substrate (non-alkali glass substrate) so that the final cured coating film had an average thickness of 1.5 μm. After that, it was heated at 100° C. for 3 minutes to volatilize the solvent. Next, the entire surface of the coating film is exposed (USH-250BY manufactured by Ushio Inc. is used as a lamp, the exposure amount is 40 mJ/cm 2 ), and then baked at 100° C. for 30 minutes to give a green color that is a cured coating film. A resist (1) was obtained.
＜現像性試験用緑色レジスト（２）の作製＞
　得られた感光性着色組成物ＣＲ１～１９、ｃＣＲ１～ｃＣＲ６を、５ｃｍ角ガラス基板（無アルカリガラス基板）上に、最終の硬化塗膜の平均厚さが１．５μｍとなるようにスピンコートした後、１００℃で３分間加熱し溶剤を揮発させた。次に、基板上にラインアンドスペースやドットパターンのフォトマスクを設置して塗膜を露光（ランプとして、ウシオ電機株式会社製ＵＳＨ－２５０ＢＹを使用、露光量４０ｍＪ／ｃｍ２）し、光硬化させた後、０．２質量％の水酸化カリウム水溶液で現像し、さらに１００℃で３０分間ベーキングすることで硬化塗膜である緑色カラーレジスト（２）を得た。 <Preparation of green resist (2) for developability test>
The obtained photosensitive coloring compositions CR1 to 19 and cCR1 to cCR6 were spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) so that the final cured coating film had an average thickness of 1.5 μm. After that, it was heated at 100° C. for 3 minutes to volatilize the solvent. Next, a line-and-space or dot pattern photomask is placed on the substrate, and the coating film is exposed (Ushio Inc. USH-250BY is used as the lamp, the exposure amount is 40 mJ/cm 2 ) and photocured. After that, the resist was developed with a 0.2% by mass aqueous solution of potassium hydroxide and further baked at 100° C. for 30 minutes to obtain a green color resist (2) as a cured coating film.
＜耐溶剤性試験＞
　上記緑色レジスト全面を２５℃のプロピレングリコールモノメチルエーテルアセテートに１５分間浸漬させた。その後、緑色レジストを取り出し、空気乾燥させた。緑色レジストの残膜率を確認することで、感光性着色組成物の耐溶剤性を評価した。測定結果より、感光性着色組成物の耐溶剤性を下記基準により１～５の５段階で評価し、３以上を合格とした。評価結果を前記表４Ａ及び表４Ｂに示した。
　「５」：残膜率９５％以上
　「４」：残膜率９０％以上９５％未満
　「３」：残膜率８５％以上９０％未満
　「２」：残膜率８０％以上８５％未満
　「１」：残膜率８０％未満 <Solvent resistance test>
The entire surface of the green resist was immersed in propylene glycol monomethyl ether acetate at 25° C. for 15 minutes. The green resist was then removed and air dried. The solvent resistance of the photosensitive coloring composition was evaluated by checking the residual film ratio of the green resist. From the measurement results, the solvent resistance of the photosensitive coloring composition was evaluated on a scale of 1 to 5 according to the following criteria, and 3 or more was considered acceptable. The evaluation results are shown in Tables 4A and 4B.
"5": Remaining film rate of 95% or more "4": Remaining film rate of 90% or more and less than 95% "3": Remaining film rate of 85% or more and less than 90% "2": Remaining film rate of 80% or more and less than 85% "1": Less than 80% residual film rate
＜現像性試験＞
　現像性試験は、現像速度を評価した。現像速度については、上記緑色カラーレジスト（２）の現像工程において、０．２質量％の水酸化カリウム水溶液での現像中、パターンが見え終わるまでに掛かる時間を測定し、下記基準により１～５の５段階で評価し、３以上を合格とした。評価結果を前記表４Ａ及び表４Ｂに示した。
　「５」：４０秒未満
　「４」：４０秒以上５０秒未満
　「３」：５０秒以上６０秒未満
　「２」：６０秒以上７０秒未満
　「１」：７０秒以上 <Developability test>
The developability test evaluated development speed. Regarding the development speed, in the development step of the green color resist (2), the time required for the pattern to finish being visible during development with a 0.2% by mass potassium hydroxide aqueous solution was measured, and the rate was 1 to 5 according to the following criteria. , and 3 or more was regarded as a pass. The evaluation results are shown in Tables 4A and 4B.
"5": less than 40 seconds "4": 40 seconds to less than 50 seconds "3": 50 seconds to less than 60 seconds "2": 60 seconds to less than 70 seconds "1": 70 seconds or more
　表３Ａ及び表３Ｂ、表４Ａ及び表４Ｂの結果からわかるように、実施例ａ１～ａ１９、及び実施例ｂ１～ｂ１９のでは、顔料分散組成物の優れた顔料分散性および保存安定性が得られた。また実施例ａ１～ａ１９で得られた顔料分散組成物を用いて作製した感光性着色組成物は、官能基Ｘと官能基Ｙの反応により、１００℃という低温で硬化し、優れた耐溶剤性、優れた現像性が得られた。
　対して、比較例ａ’４及び比較例ｂ’４では、顔料分散組成物の顔料分散性が著しく悪く、顔料分散組成物として使用することは困難であり、感光性着色組成物にした際の硬化性が不十分であり、耐溶剤性が悪い結果となり感光性着色組成物として使用することも困難であった。また、比較例ａ’１、ａ’５、ａ’６、及び比較例ｂ’１、ｂ’５、ｂ’６では、顔料分散組成物の顔料分散性及び保存安定性、感光性着色組成物の現像性は良かった一方、感光性着色組成物の耐溶剤性は悪かった。 As can be seen from the results in Tables 3A and 3B and Tables 4A and 4B, in Examples a1 to a19 and Examples b1 to b19, excellent pigment dispersibility and storage stability of the pigment dispersion composition were obtained. rice field. Further, the photosensitive coloring composition prepared using the pigment dispersion composition obtained in Examples a1 to a19 cured at a low temperature of 100 ° C. due to the reaction of the functional group X and the functional group Y, and had excellent solvent resistance. , excellent developability was obtained.
On the other hand, in Comparative Examples a'4 and Comparative Examples b'4, the pigment dispersibility of the pigment dispersion composition was significantly poor, and it was difficult to use it as a pigment dispersion composition, and when it was made into a photosensitive coloring composition, Curability was insufficient and solvent resistance was poor, making it difficult to use as a photosensitive coloring composition. Further, in Comparative Examples a'1, a'5, a'6, and Comparative Examples b'1, b'5, b'6, the pigment dispersibility and storage stability of the pigment dispersion composition, the photosensitive coloring composition While the developability of the photosensitive coloring composition was good, the solvent resistance of the photosensitive coloring composition was poor.
　以上より、本発明により、顔料分散性や保存安定性が優れた顔料分散組成物、及びその顔料分散組成物を含む感光性着色組成物、及びその感光性着色組成物を含み、耐溶剤性、現像性に優れ、分散剤や顔料の溶出やブリードアウトの抑制が期待されるカラーフィルターを提供することができる。 As described above, the present invention includes a pigment dispersion composition having excellent pigment dispersibility and storage stability, and a photosensitive coloring composition containing the pigment dispersion composition, and the photosensitive coloring composition, solvent resistance, It is possible to provide a color filter that is excellent in developability and is expected to suppress elution and bleeding out of dispersants and pigments.
　本発明によれば、顔料分散性や保存安定性が良好な顔料分散組成物を提供することができる。また、当該顔料分散組成物を用いることにより、優れた耐溶剤性、現像性を有する硬化物が得られる感光性着色組成物を提供することができる。さらに、当該感光性着色組成物の硬化物を有するカラーフィルター、これを具備する画像表示素子を提供することができる。 According to the present invention, it is possible to provide a pigment dispersion composition with good pigment dispersibility and storage stability. In addition, by using the pigment dispersion composition, it is possible to provide a photosensitive coloring composition from which a cured product having excellent solvent resistance and developability can be obtained. Further, it is possible to provide a color filter having a cured product of the photosensitive coloring composition, and an image display device having the same.

Claims (14)

  1. 　バインダー樹脂（Ａ－１）と、
    　顔料（Ｂ）と、
    　高分子分散剤（Ｃ）と、
    　溶剤（Ｄ－１）と、
    を含有する顔料分散組成物であって、
    　前記バインダー樹脂（Ａ－１）が、官能基（Ｘ）を有し、
    　前記高分子分散剤（Ｃ）が、アミノ基および４級アンモニウムカチオン基から選択される一種以上を有し、前記官能基（Ｘ）と反応性を有する官能基（Ｙ）を有することを特徴とする顔料分散組成物。     a binder resin (A-1);
    a pigment (B);
    a polymeric dispersant (C);
    a solvent (D-1);
    A pigment dispersion composition containing
    The binder resin (A-1) has a functional group (X),
    The polymer dispersant (C) has one or more selected from amino groups and quaternary ammonium cationic groups, and has a functional group (Y) reactive with the functional group (X). Pigment dispersion composition to.
  2. 　前記高分子分散剤（Ｃ）が、アミノ基含有高分子化合物（ｃ－１）と、前記官能基（Ｙ）を有するハロゲン化合物（ｃ－２）と、の反応物である請求項１に記載の顔料分散組成物。 2. The polymer dispersing agent (C) according to claim 1, which is a reaction product of an amino group-containing polymer compound (c-1) and a halogen compound (c-2) having the functional group (Y). pigment dispersion composition.
  3. 　前記アミノ基含有高分子化合物（ｃ－１）のアミノ基が３級アミノ基である請求項２に記載の顔料分散組成物。 The pigment dispersion composition according to claim 2, wherein the amino group of the amino group-containing polymer compound (c-1) is a tertiary amino group.
  4. 　前記バインダー樹脂（Ａ－１）の有する官能基（Ｘ）が、ヒドロキシ基及びメルカプト基から選択される一種以上であり、
    　前記高分子分散剤（Ｃ）の有する官能基（Ｙ）が、ブロックイソシアナト基及びアルキルエステルを有する基から選択される一種以上である請求項１～３のいずれか一項に記載の顔料分散組成物。     The functional group (X) possessed by the binder resin (A-1) is one or more selected from a hydroxy group and a mercapto group,
    The pigment dispersion according to any one of claims 1 to 3, wherein the functional group (Y) possessed by the polymeric dispersant (C) is one or more selected from groups having a blocked isocyanato group and an alkyl ester. Composition.
  5. 　前記バインダー樹脂（Ａ－１）の有する官能基（Ｘ）が、カルボキシ基であり、
    　前記高分子分散剤（Ｃ）の有する、官能基（Ｙ）が、エポキシ基及びオキセタニル基から選択される一種以上である請求項１～３のいずれか一項に記載の顔料分散組成物。     the functional group (X) of the binder resin (A-1) is a carboxy group,
    The pigment dispersion composition according to any one of claims 1 to 3, wherein the functional group (Y) possessed by the polymer dispersant (C) is one or more selected from an epoxy group and an oxetanyl group.
  6. 　前記バインダー樹脂（Ａ－１）の有する官能基（Ｘ）が、ブロックイソシアナト基及びアルキルエステルを有する基から選択される一種以上であり、
    　前記高分子分散剤（Ｃ）の有する官能基（Ｙ）が、ヒドロキシ基及びメルカプト基から選択される一種以上である請求項１～３のいずれか一項に記載の顔料分散組成物。     The functional group (X) of the binder resin (A-1) is one or more selected from a group having a blocked isocyanato group and an alkyl ester,
    The pigment dispersion composition according to any one of claims 1 to 3, wherein the functional group (Y) possessed by the polymeric dispersant (C) is one or more selected from a hydroxy group and a mercapto group.
  7. 　前記バインダー樹脂（Ａ－１）の有する官能基（Ｘ）が、エポキシ基及びオキセタニル基から選択される一種以上であり、
    　前記高分子分散剤（Ｃ）の有する官能基（Ｙ）が、カルボキシ基である請求項１～３のいずれか一項に記載の顔料分散組成物。     The functional group (X) possessed by the binder resin (A-1) is one or more selected from an epoxy group and an oxetanyl group,
    The pigment dispersion composition according to any one of claims 1 to 3, wherein the functional group (Y) possessed by the polymer dispersant (C) is a carboxy group.
  8. 　前記顔料（Ｂ）が、ハロゲン化フタロシアニン骨格を有する顔料を含む請求項１～３のいずれか一項に記載の顔料分散組成物。 The pigment dispersion composition according to any one of claims 1 to 3, wherein the pigment (B) contains a pigment having a halogenated phthalocyanine skeleton.
  9. 　前記顔料（Ｂ）１００質量部に対して、
    　前記バインダー樹脂（Ａ－１）を１０～８０質量部を含有し、
    　前記高分子分散剤（Ｃ）を１０～８０質量部を含有する請求項１～３のいずれか一項に記載の顔料分散組成物。     For 100 parts by mass of the pigment (B),
    Containing 10 to 80 parts by mass of the binder resin (A-1),
    The pigment dispersion composition according to any one of claims 1 to 3, containing 10 to 80 parts by mass of the polymer dispersant (C).
  10. 　請求項１～３のいずれか一項に記載の顔料分散組成物と、
    　バインダー樹脂（Ａ－２）と、
    　反応性希釈剤（Ｅ）と、
    　光重合開始剤（Ｆ）と
    を含有することを特徴とする感光性着色組成物。     The pigment dispersion composition according to any one of claims 1 to 3,
    a binder resin (A-2);
    a reactive diluent (E);
    A photosensitive coloring composition comprising a photopolymerization initiator (F).
  11. 　前記顔料（Ｂ）１００質量部に対して、
    　前記バインダー樹脂（Ａ－１）を１０～８０質量部を含有し、
    　前記高分子分散剤（Ｃ）を１０～８０質量部を含有し、
    　前記バインダー樹脂（Ａ－２）を５０～２８０質量部含有し、
    　前記反応性希釈剤（Ｅ）を４０～２００質量部含有し、
    　前記光重合開始剤（Ｆ）を０．１～１０質量部含有する
    請求項１０に記載の感光性着色組成物。     For 100 parts by mass of the pigment (B),
    Containing 10 to 80 parts by mass of the binder resin (A-1),
    Containing 10 to 80 parts by mass of the polymer dispersant (C),
    Containing 50 to 280 parts by mass of the binder resin (A-2),
    Containing 40 to 200 parts by mass of the reactive diluent (E),
    The photosensitive coloring composition according to claim 10, containing 0.1 to 10 parts by mass of the photopolymerization initiator (F).
  12. 　請求項１０に記載の感光性着色組成物を硬化させてなる樹脂硬化膜。 A cured resin film obtained by curing the photosensitive coloring composition according to claim 10.
  13. 　請求項１０に記載の感光性着色組成物の硬化物を有するカラーフィルター。 A color filter having a cured product of the photosensitive coloring composition according to claim 10.
  14. 　請求項１３に記載のカラーフィルターを具備する画像表示素子。 An image display device comprising the color filter according to claim 13.
PCT/JP2022/040986 2021-12-23 2022-11-02 Pigment dispersion composition, photosensitive colored composition, and color filter WO2023119898A1 (en)

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