WO2022038948A1 - Colored resin composition, color filter, and image display device - Google Patents

Colored resin composition, color filter, and image display device Download PDF

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WO2022038948A1
WO2022038948A1 PCT/JP2021/027091 JP2021027091W WO2022038948A1 WO 2022038948 A1 WO2022038948 A1 WO 2022038948A1 JP 2021027091 W JP2021027091 W JP 2021027091W WO 2022038948 A1 WO2022038948 A1 WO 2022038948A1
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直人 東
宏明 石井
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三菱ケミカル株式会社
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Priority to KR1020237005285A priority Critical patent/KR20230052275A/en
Priority to CN202180050424.7A priority patent/CN115956223A/en
Priority to JP2022543331A priority patent/JPWO2022038948A1/ja
Publication of WO2022038948A1 publication Critical patent/WO2022038948A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/22—Esters containing nitrogen
    • C08F222/225—Esters containing nitrogen the ester chains containing seven or more carbon atoms
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • the present invention relates to a colored resin composition, a color filter, and an image display device.
  • This application claims priority based on Japanese Patent Application No. 2020-139037 filed in Japan on August 20, 2020 and Japanese Patent Application No. 2020-139038 filed in Japan on August 20, 2020. The contents are used here.
  • a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known as methods for manufacturing a color filter used in a liquid crystal display device or the like.
  • the pigment dispersion method having excellent characteristics on average is most widely adopted from the viewpoints of spectral characteristics, durability, pattern shape, accuracy and the like.
  • color filters are required to have higher brightness, higher contrast, and higher color gamut.
  • Pigments are generally used as color materials that determine the color of color filters from the viewpoint of heat resistance, light resistance, etc.
  • pigments are no longer able to meet market demands for high brightness, and colors are used.
  • dyes instead of pigments as materials.
  • Patent Document 2 describes that by using a colored resin composition containing a specific photopolymerizable compound, the residue after development in the production of a color filter can be reduced even if the pigment is contained at a high concentration. Has been done.
  • the colored resin composition described in Patent Document 1 has solubility in a developing solution depending on the temperature at the time of prebaking (drying step of the coating film carried out before the exposure step). It was found that the pattern size changed significantly, especially in the high temperature range. As a result, it has become clear that a high-definition color filter typified by 4K8K, which requires precise line width adjustment, cannot be stably manufactured.
  • Patent Document 2 only a colored resin composition containing a pigment as a colorant was evaluated, and it was unclear what kind of characteristics would be exhibited when a phthalocyanine dye was contained as a colorant.
  • an object of the present invention is to provide a colored resin composition having a small influence of a prebake temperature change on the developer solubility and patterning characteristics.
  • the present invention has the following configurations [1] to [6].
  • a colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer.
  • the colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1).
  • a 1 to A 16 each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), but one or more of A 1 to A 16 .
  • X represents a divalent linking group.
  • the benzene ring in the formula (2) may have an arbitrary substituent. * Represents a bond.
  • R 1 represents an alkylene group having 2 or more carbon atoms.
  • R 2 represents a hydrogen atom or a methyl group.
  • n represents an integer of 1 or more. * Represents a bond.
  • R 1 , R 2 and n are synonymous with the above formula (I).
  • Z is a direct bond, an oxygen atom, a sulfur atom, a 2- to 4-valent aliphatic hydrocarbon group, a 4-valent carbon atom, a 2- to 4-valent non-aromatic heterocyclic group, and a 2- to 4-valent aromatic ring group.
  • p represents an integer of 2 to 6.
  • FIG. 1 is a schematic cross-sectional view showing an example of an organic EL display element having the color filter of the present invention.
  • the "weight average molecular weight” refers to the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
  • the “total solid content” means all components other than the solvent in the colored resin composition. Even if the components other than the solvent are liquid at room temperature, the components are not included in the solvent and are included in the total solid content.
  • the "amine value” represents an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH.
  • "CI” means a color index.
  • the colored resin composition according to the present invention comprises (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E). Contains photopolymerizable monomers. Further, if necessary, additives and the like other than the above-mentioned components may be blended.
  • the (A) colorant contained in the coloring resin composition of the present invention is a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter, "phthalocyanine compound (hereinafter,” phthalocyanine compound (hereinafter, “phthalocyanine compound”). It may be referred to as "1)".)
  • a 1 to A 16 independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A 1 to A 16 represents a fluorine atom, and one or more of A 1 to A 16 represents a group represented by the following general formula (2).
  • X represents a divalent linking group.
  • the benzene ring in the formula (2) may have an arbitrary substituent. * Represents a bond.
  • the (A) colorant in the colored resin composition of the present invention contains a phthalocyanine compound (1). Since one or more of the hydrogen atoms constituting the phthalocyanine skeleton of the phthalocyanine compound (1) are replaced with fluorine atoms having a small atomic radius and the structure does not easily inhibit the association between the phthalocyanine compounds (1), heating or the like is performed. It is considered that the decrease in brightness due to heating can be suppressed by forming an aggregate when the intermolecular distance is shortened. Further, it is considered that the particle size is smaller than that of the pigment even after the association, and the brightness is considered to be high in the pattern after the thermosetting treatment.
  • the phthalocyanine compound (1) is densely present as an aggregate having a small particle size in the coating film after prebaking the colored resin composition of the present invention, and the developer is applied in the subsequent developing step. It is considered that the penetration and dissolution into the membrane are likely to be suppressed. Therefore, it is considered that the pattern shape obtained is likely to change depending on the amount of the residual solvent, and for example, the prebake temperature dependence of the hole diameter is likely to be deteriorated.
  • a 1 to A 16 independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A 1 to A 16 represents a fluorine atom, and one or more of A 1 to A 16 represents a group represented by the following general formula (2).
  • X represents a divalent linking group.
  • the benzene ring in the formula (2) may have an arbitrary substituent. * Represents a bond.
  • Examples of the halogen atom in A 1 to A 16 include a fluorine atom, a chlorine atom, and a bromine atom. Fluorine atoms are preferable from the viewpoint of increasing brightness. Further, 6 or more of A 1 to A 16 are preferably fluorine atoms, 7 or more are more preferable, 8 or more are further preferable, 15 or less, 12 or less are preferable, and 10 or less is preferable. More preferred. When it is at least the above lower limit value, the stability of the phthalocyanine compound (1) tends to be improved, and when it is at least the above upper limit value, the affinity with the dispersant and the solvent in the colored resin composition is improved. Tend. The above upper and lower limits can be combined arbitrarily. For example, the number of substituents representing a fluorine atom in A 1 to A 16 is 1 to 15, preferably 6 to 12, more preferably 7 to 12, and even more preferably 8 to 10.
  • X in the formula (2) represents a divalent linking group.
  • the divalent linking group is not particularly limited, but is an oxygen atom, a sulfur atom, or a -N (R a1 ) -group (R a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms). Can be mentioned. From the viewpoint of stability during calcination, an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.
  • the benzene ring in the formula (2) may have an arbitrary substituent.
  • the substituent is not particularly limited, but is, for example, a halogen atom, an alkyl group ( -RA group), an alkoxy group (-OR A group (where RA represents an alkyl group)), an alkoxycarbonyl group (-COOR).
  • a group (where RA represents an alkyl group)), aryl group (-RB group), aryloxy group (-OR B group (where RB represents an aryl group )), aryloxycarbonyl A group (-COOR B group (where RB represents an aryl group)) is mentioned.
  • An alkoxycarbonyl group is preferable from the viewpoint of development solubility and brightness.
  • the alkyl group contained in these groups may be linear, branched or cyclic, but is preferably linear from the viewpoint of affinity with an organic solvent.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is usually preferably 1 or more, 2 or more, preferably 6 or less, more preferably 5 or less, still more preferably 4 or less.
  • the solvent affinity tends to be improved and the stability with time tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 5, and even more preferably 2 to 4.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like. From the viewpoint of suppressing aggregation, a methyl group or an ethyl group is preferable, and an ethyl group is more preferable.
  • the aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • the number of carbon atoms of the aryl group is not particularly limited, but is usually preferably 4 or more and 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less.
  • the aryl group preferably has 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.
  • Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring having one free valence.
  • the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring.
  • aromatic heterocyclic group examples include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, and an isooxazole having one free valence.
  • the number of substitutions is not particularly limited, but the heat resistance is improved by ⁇ - ⁇ stacking between the dye molecules, and the decrease in brightness due to the decomposition of the dye is suppressed. From the viewpoint of this, it is preferable that the number of substitutions is 1 for one benzene ring.
  • the substitution position may be the o-position, the m-position, or the p-position, but stacking having a close-packed structure is possible. From the viewpoint, the p-position is preferable.
  • a 1 to A 16 represent a fluorine atom, but one or more of A 1 to A 4 is a fluorine atom from the viewpoint of improving brightness by forming an aggregate between two molecules of the phthalocyanine compound (1).
  • At least one of A 5 to A 8 is a fluorine atom
  • one or more of A 9 to A 12 is a fluorine atom
  • one or more of A 13 to A 16 is a fluorine atom.
  • 2 or more of A 1 to A 4 are fluorine atoms
  • two or more of A 5 to A 8 are fluorine atoms
  • two or more of A 9 to A 12 are fluorine atoms. It is more preferable that the atom is an atom and two or more of A 13 to A 16 are fluorine atoms.
  • a 1 to A 16 represents a group represented by the formula (2), but one or more of A 1 to A 4 represents a group represented by the formula (2) from the viewpoint of solubility in an organic solvent and brightness.
  • One or more of A 5 to A 8 is a group represented by the formula (2), and one or more of A 9 to A 12 is represented by the formula (2).
  • Two or more of A 5 to A 8 are groups represented by the formula (2), and two or more of A 9 to A 12 are groups represented by the formula (2). It is more preferable that two or more of A 13 to A 16 are groups represented by the formula (2).
  • a 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 and A 15 are represented by the formula (2).
  • a 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 are halogen atoms;
  • a 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 and A 15 are the groups represented by the formula (2), and A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 and A.
  • 16 is a fluorine atom.
  • phthalocyanine dye (1) examples include the following compounds.
  • Et represents ethyl
  • a known method can be adopted, and for example, the method described in Japanese Patent Application Laid-Open No. 05-345861 can be adopted.
  • the colorant may contain other colorants in addition to the phthalocyanine compound (1).
  • other colorants include pigments and dyes.
  • green pigments, green dyes, yellow pigments, and yellow dyes examples include C.I. I. Pigment Greens 7, 36, 58, 59, 62, 63, and C.I. I. Pigment Green 58 is preferred.
  • the green dyes classified as dyes by the color index C.I. I.
  • a solvent dye for example, C.I. I. Solvent greens 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 can be mentioned.
  • As an acid dye for example, C.I. I.
  • Acid Green 1 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53. From the viewpoint of suppressing dye decomposition during heat firing, C.I. I. Solvent greens 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 are preferred.
  • yellow pigment examples include C.I. I. Pigment Yellow 1, 1, 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,86,87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127: 1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184
  • Examples of the other compound inserted in the nickel azo complex represented by the formula (i) include a compound represented by the following formula (ii).
  • C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and the nickel azo complex represented by the formula (i) are preferable.
  • I. Pigment Yellow 83, 138, 139, 180, 185 and the nickel azo complex represented by the formula (i) are more preferable.
  • yellow dye examples include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples thereof include the specific compounds described in Japanese Patent Application Laid-Open No. 2010-168531.
  • the yellow dyes classified as dyes by the color index C.I. I.
  • a solvent dye for example, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 and the like can be mentioned.
  • acid dye for example, C.I. I.
  • Acid Green 1 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I.
  • Acid Yellow 1 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184.
  • C.I. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129. Examples include the dyes 136, 138 and 141.
  • Examples include dyes of Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65.
  • the average primary particle size of the pigment is usually 0.2 ⁇ m or less, preferably 0.1 ⁇ m or less, and more preferably 0.04 ⁇ m or less.
  • a method such as solvent salt milling is preferably used.
  • the content ratio of the (A) colorant in the colored resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, and 20% by mass in the total solid content of the colored resin composition.
  • the above is further preferable, 25% by mass or more is further preferable, 30% by mass or more is particularly preferable, 80% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, and 40% by mass is 40% by mass.
  • the following are particularly preferred. When it is set to the lower limit value or more, a wide hue tends to be reproduced, and when it is set to the upper limit value or less, the stability with time tends to be ensured.
  • the above upper and lower limits can be combined arbitrarily.
  • the content ratio of the (A) colorant in the colored resin composition is preferably 10 to 80% by mass, more preferably 15 to 80% by mass, and further 20 to 60% by mass in the total solid content of the colored resin composition.
  • the content ratio of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass in the total solid content of the colored resin composition.
  • the above is further preferable, 10% by mass or more is further preferable, 15% by mass or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is further preferable, and 20% by mass is 20% by mass.
  • the following are particularly preferred.
  • the content ratio of the phthalocyanine compound (1) in the colored resin composition is more preferably 3 to 50% by mass, still more preferably 5 to 50% by mass, and 10 to 40% by mass in the total solid content of the colored resin composition. Is even more preferable, and 15 to 30% by mass is particularly preferable.
  • the content thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more in the total solid content of the colored resin composition. 5% by mass or more is further preferable, 7% by mass or more is further preferable, 10% by mass or more is particularly preferable, 30% by mass or less is more preferable, 25% by mass or less is more preferable, and 20% by mass or less is further preferable.
  • 5% by mass or more is further preferable
  • 7% by mass or more is further preferable
  • 10% by mass or more is particularly preferable
  • 30% by mass or less is more preferable
  • 25% by mass or less is more preferable
  • 20% by mass or less is further preferable.
  • the content ratio thereof is preferably 1 to 30% by mass, more preferably 3 to 30% by mass, and 5 to 5 to 30% by mass in the total solid content of the colored resin composition. 25% by mass is further preferable, 7 to 25% by mass is further preferable, and 10 to 29% by mass is particularly preferable.
  • (B) Solvent dissolves a colorant, an alkali-soluble resin, a photopolymerization initiator, a photopolymerizable monomer, and other components in the colored resin composition and pigment dispersion of the present invention. Alternatively, it has a function of dispersing and adjusting the viscosity.
  • the solvent may be any solvent that can dissolve or disperse each component.
  • Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether.
  • Propropylene glycol-t-butyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl Glycol monoalkyl ethers such as -3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
  • Glycoldialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n
  • Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamil ether, ethylisobutyl ether, dihexyl ether; Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl
  • Ketones Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
  • Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methylisobutyrate, ethylene glycol acetate, ethylpropionate, propylpropionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropi
  • solvents examples include mineral spirit, balsol # 2, apco # 18 solvent, apco thinner, and socal solvent No. 1 and No. 2.
  • Solvento # 150 Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all are trade names). These solvents may be used alone or in combination of two or more.
  • a solvent having a boiling point in the range of 100 to 200 ° C. pressure 1013.25 [hPa] conditions; hereinafter, the boiling points are all the same
  • the solvent is selected as the solvent.
  • it is a solvent having a boiling point of 120 to 170 ° C.
  • Glycol alkyl ether acetates are preferable because they have a good balance of coatability, surface tension, etc. in the solvent and the solubility of the constituents in the composition is relatively high.
  • Glycol alkyl ether acetates may be used alone or in combination with other solvents.
  • Glycol monoalkyl ethers are particularly preferable as the solvent to be used in combination.
  • propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of the constituents in the composition.
  • Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the colored resin composition obtained later tends to increase, and the storage stability tends to decrease.
  • the proportion of the glycol monoalkyl ethers in the solvent (B) is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.
  • a solvent having a boiling point of 150 ° C. or higher can be used in combination.
  • the colored resin composition becomes difficult to dry, but it has an effect of making it difficult to destroy the mutual relationship of the constituents in the pigment dispersion liquid due to rapid drying. ..
  • the content ratio of the solvent having a boiling point of 150 ° C. or higher in (B) is preferably 3% by mass to 50% by mass, preferably 5% by mass to 40% by mass. Is more preferable, and 5% by mass to 30% by mass is particularly preferable.
  • the solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers, and in this case, it is not necessary to separately contain a solvent having a boiling point of 150 ° C. or higher.
  • diethylene glycol mono-n-butyl ether acetate diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate.
  • Triacetin Triacetin.
  • a solvent having a boiling point of usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower is suitable.
  • the uniformity of the obtained coating film tends to be good, and when it is at least the above upper limit value, there is a tendency that the residual solvent at the time of firing is easily reduced.
  • the vapor pressure of the solvent is usually 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less.
  • the ink emitted from the nozzle is extremely fine, ranging from several to several tens of pL, so the solvent evaporates and the ink concentrates and dries before landing around the nozzle opening or in the pixel bank. Tends to harden.
  • the solvent (B) contains a solvent having a high boiling point, and specifically, it is preferable to contain a solvent having a boiling point of 180 ° C. or higher. It is more preferable to contain a solvent having a boiling point of 200 ° C. or higher, and it is particularly preferable to contain a solvent having a boiling point of 220 ° C. or higher.
  • the content ratio of the solvent having a boiling point of 180 ° C. or higher in the solvent (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more. By setting the value to the lower limit or more, the effect of preventing evaporation of the solvent from the droplets tends to be sufficiently exhibited.
  • a solvent having a boiling point of 180 ° C. or higher for example, among the various solvents mentioned above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6- Hexanol diacetate, triacetin and the like can be mentioned.
  • a solvent having a boiling point lower than 180 ° C. may be contained for adjusting the viscosity of the colored resin composition and adjusting the solubility of the solid content.
  • a solvent having low viscosity, high solubility, and low surface tension is preferable, and for example, ethers, esters, and ketones are preferable.
  • ethers, esters, and ketones are preferable.
  • cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferable.
  • the ejection stability in the inkjet method may deteriorate.
  • the content ratio of alcohols in the solvent (B) is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
  • the content ratio of the solvent in the colored resin composition of the present invention is not particularly limited, but the upper limit thereof is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. When the value is not more than the upper limit, the coating film tends to be easily formed.
  • the lower limit of the solvent content ratio is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more in consideration of viscosity suitable for coating.
  • the above upper and lower limits can be combined arbitrarily.
  • the content ratio of the solvent in the colored resin composition is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, still more preferably 80 to 85% by mass.
  • the colored resin composition of the present invention contains (C) an alkali-soluble resin.
  • C By containing the alkali-soluble resin, it is possible to achieve both film curability by photopolymerization and solubility by a developing solution.
  • the alkali-soluble resin include Japanese Patent Laid-Open No. 7-2072111, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, and Japanese Patent Application Laid-Open No. 11-140144.
  • (C-1) With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. It may be referred to as an alkali-soluble resin (hereinafter referred to as "resin (C-1)") obtained by adding a polybasic acid anhydride to at least a part of the added resin or the hydroxyl group generated by the addition reaction.
  • resin (C-1) alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the added resin or the hydroxyl group generated by the addition reaction.
  • (C-2) A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter, may be referred to as “resin (C-2)”).
  • C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter, may be referred to as “resin (C-3)”).
  • C-4) (Meta) acrylic resin (hereinafter, may be referred to as “resin (C-4)") (C-5) Epoxy (meth) acrylate resin having a carboxyl group (hereinafter, may be referred to as "resin (C-5)”).
  • resin (C-1) is particularly preferable.
  • the resins (C-2) to (C-5) may be dissolved in an alkaline developer and have solubility to the extent that the desired developing treatment can be carried out, and each of them may be Japanese Patent Application Laid-Open No. 2009-025813.
  • the resin described as the same item in Japanese Patent Publication No. can be preferably adopted.
  • (C-1) An unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer of the epoxy group-containing (meth) acrylate and another radically polymerizable monomer.
  • the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction the resin is "containing an epoxy group”.
  • the (meth) acrylate is unsaturated with 10 to 100 mol% of the epoxy group of the copolymer with respect to the polymer of 5 to 90 mol% of the acrylate and 10 to 95 mol% of the other radically polymerizable monomer. Examples thereof include a resin obtained by adding a basic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.
  • Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth).
  • Acrylate glycidyl ether can be exemplified. Of these, glycidyl (meth) acrylate is preferable.
  • One of these epoxy group-containing (meth) acrylates may be used alone, or two or more thereof may be used in combination.
  • a mono (meth) acrylate having a structure represented by the following general formula (V) is preferable.
  • R 91 to R 98 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 96 and R 98 , or R 95 and R 97 may be connected to each other to form a ring.
  • the ring formed by connecting R 96 and R 98 or R 95 and R 97 is preferably an aliphatic ring, which may be saturated or unsaturated, and may be carbon. The number is preferably 5-6.
  • the structure represented by the formula (V) the structure represented by the following general formula (Va), (Vb), or (Vc) is preferable.
  • the mono (meth) acrylate having the structure represented by the formula (V) one type may be used alone, or two or more types may be used in combination.
  • the mono (meth) acrylate having the structure represented by the formula (V) various known mono (meth) acrylates can be used as long as they have the structure represented by the formula (V), and in particular, the following general formula ( The mono (meth) acrylate represented by VI) is preferable.
  • R 89 represents a hydrogen atom or a methyl group
  • R 90 represents a structure represented by the formula (V).
  • the formula (VI) When a repeating unit derived from a mono (meth) acrylate represented by the formula (VI) is contained in a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, the formula (VI) is used.
  • the content ratio of the repeating unit derived from the represented mono (meth) acrylate is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, among the repeating units derived from other radically polymerizable monomers. 15-50 mol% is particularly preferred.
  • the radically polymerizable monomer other than the mono (meth) acrylate represented by the formula (VI) is not particularly limited, but specifically, for example, styrene and ⁇ - and o- of styrene. , M-, p-alkyl, nitro, cyano, amide, ester derivatives and other vinyl aromatics; butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene and other dienes; (meth) methyl acrylate, (meth) Ethyl acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid- tert-butyl, (meth) pentyl acrylate, (meth) neo-pentyl acrylate, (meth) isoamyl acryl
  • styrene, benzyl (meth) acrylate, and monomaleimide are preferable from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition.
  • the copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer contains any repeating unit derived from styrene, benzyl (meth) acrylate, or monomaleimide, the other radical polymerization.
  • the total content of the repeating unit derived from styrene, the repeating unit derived from benzyl (meth) acrylate, and the repeating unit derived from monomaleimide among the repeating units derived from the sex monomer is 1 to 70 mol%. It is preferable, 3 to 50 mol% is more preferable.
  • a known solution polymerization method can be applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and another radically polymerizable monomer.
  • the solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
  • Examples of the solvent used in the solution polymerization method include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; and diethylene glycol mono such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate.
  • Alkyl ether acetates Propropylene glycol monoalkyl ether acetates; Acetate esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methylcarbitol, ethylcarbitol, butylcarbitol, etc.
  • Triethylene glycol dialkyl ethers Triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; benzene and toluene , Xylene, octane, decane and other hydrocarbons; petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, butyl lactate; dimethylformamide, N- Methylpyrrolidone may be mentioned. These solvents may be used alone or in combination of two or more.
  • the amount of the solvent used in the solution polymerization method is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass with respect to 100 parts by mass of the obtained copolymer. By keeping the amount of the solvent used within the above range, it tends to be easy to control the molecular weight of the copolymer.
  • the radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst can be used. ..
  • the organic peroxide catalyst include catalysts classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.
  • radical polymerization initiator used in the copolymerization reaction examples include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, and t-hexyl peroxybenzoate.
  • Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarboxylicamide. From these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature.
  • the amount of the radical polymerization initiator used is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomers used in the copolymerization reaction.
  • the copolymerization reaction may be carried out by dissolving the monomer used in the polymerization reaction and the radical polymerization initiator in a solvent and raising the temperature with stirring, or using a monomer to which the radical polymerization initiator is added. , The temperature may be dropped in the stirred solvent, or the monomer may be dropped in the temperature obtained by adding the radical polymerization initiator to the solvent.
  • the reaction conditions can be set according to the target molecular weight.
  • the copolymer of the epoxy group-containing (meth) acrylate and another radically polymerizable monomer includes 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate and other radical polymerization. It is preferably composed of 10 to 95 mol% of repeating units derived from sex monomers; 20 to 80 mol% of repeating units derived from epoxy group-containing (meth) acrylates and other radically polymerizable monomers. More preferably, it consists of 80-20 mol% repeating units; 30-70 mol% repeating units derived from epoxy group-containing (meth) acrylates and 70-30 mol repeating units derived from other radically polymerizable monomers. The one consisting of% is particularly preferable.
  • the unsaturated monobasic acid added to the epoxy group a known unsaturated monobasic acid can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
  • the unsaturated monobasic acid to be added to the epoxy group include (meth) acrylic acid; crotonic acid; o-, m-, and p-vinylbenzoic acid; the ⁇ -position is a haloalkyl group, an alkoxyl group, a halogen atom, and a nitro.
  • monocarboxylic acids such as (meth) acrylic acid substituted with a group or a cyano group. Of these, (meth) acrylic acid is preferable.
  • One of these unsaturated monobasic acids may be used alone, or two or more thereof may be used in combination.
  • the resin (C-1) By adding an unsaturated monobasic acid to the epoxy group, the resin (C-1) can be imparted with polymerizable properties.
  • the unsaturated monobasic acid is added to usually 10 to 100 mol%, preferably 30 to 100 mol%, more preferably 50 to 100 mol% of the epoxy group contained in the copolymer. By setting the value to the lower limit or more, the stability of the colored resin composition with time tends to be good.
  • a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer a known method can be adopted.
  • polybasic acid anhydride added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer
  • a known polybasic acid anhydride can be used.
  • the polybasic acid anhydride include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, and chlorendic anhydride; Trimerit anhydride.
  • Examples thereof include anhydrates of three or more bases such as an acid, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and succinic anhydride are preferable.
  • One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.
  • Alkali solubility can be imparted to the resin (C-1) by adding the polybasic acid anhydride to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer.
  • the polybasic acid anhydride is usually 10 to 100 mol%, preferably 20 to 90 mol%, more preferably 30 to 80 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer. Add to%. When it is set to the upper limit value or less, the residual film ratio at the time of development tends to be good, and when it is set to the lower limit value or more, the solubility tends to be sufficient.
  • a method for adding a polybasic acid anhydride to a hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer a known method can be adopted.
  • a glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl groups. good.
  • a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl groups.
  • Examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group and an alkyl group.
  • the structure of the resin (C-1) is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.
  • the polystyrene-equivalent weight average molecular weight measured by GPC of the resin (C-1) is not particularly limited, but is preferably 3000 to 100,000, and particularly preferably 5000 to 50,000. When it is at least the above lower limit value, the heat resistance and film strength tend to be good, and when it is at least the above upper limit value, the solubility in a developing solution tends to be good.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) of the resin (C-1) to the number average molecular weight is preferably 2.0 to 5.0.
  • the (c1) acrylic copolymer resin having an ethylenically unsaturated group in the side chain is preferable.
  • the partial structure of the acrylic copolymer resin having an ethylenically unsaturated group in the side chain including the side chain having an ethylenically unsaturated group is not particularly limited, but the coating film curability and alkali development during ultraviolet exposure are not particularly limited. From the viewpoint of achieving both alkali solubility at the time, for example, it is preferable to have a partial structure represented by the following general formula (CI).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group. * Represents a bond.
  • the partial structure represented by the following general formula (CI') is preferable from the viewpoint of sensitivity and alkali developability.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • RX represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a monovalent group obtained by subtracting one OH group from the polybasic acid or its anhydride.
  • the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid and endomethylene.
  • examples thereof include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferable. Is more preferable.
  • These polybasic acids may be used alone or in combination of two or more.
  • the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure represented by the formula (CI)
  • the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) can be used.
  • the content ratio of the partial structure represented by the formula (CI) contained is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, still more preferably 40 mol% or more.
  • mol% or more is particularly preferable, 65 mol% or more is most preferable, 95 mol% or less is preferable, 90 mol% or less is more preferable, 85 mol% or less is further preferable, and 80 mol% or less is more preferable. More preferably, 75 mol% or less is particularly preferable, and 70 mol% or less is most preferable.
  • the coating film curability at the time of exposure to ultraviolet rays tends to be improved
  • it is at least the above upper limit value the alkali solubility at the time of alkaline development tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the content of the partial structure represented by the formula (CI) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is preferably 10 to 95 mol%, preferably 20 to 90 mol%. More preferably, 30 to 85 mol% is further preferable, 40 to 80 mol% is further preferable, 50 to 75 mol% is particularly preferable, and 65 to 70 mol% is most preferable.
  • the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the formula (CI')
  • the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and even more preferably 40 mol%.
  • the above is even more preferable, 50 mol% or more is particularly preferable, 65 mol% or more is most preferable, 95 mol% or less is preferable, 90 mol% or less is more preferable, 85 mol% or less is further preferable, and 80 mol% is more preferable.
  • the following is even more preferable, 75 mol% or less is particularly preferable, and 70 mol% or less is most preferable.
  • the content of the partial structure represented by the formula (CI) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is preferably 10 to 95 mol%, preferably 20 to 90 mol%. More preferably, 30 to 85 mol% is further preferable, 40 to 80 mol% is further preferable, 50 to 75 mol% is particularly preferable, and 65 to 70 mol% is most preferable.
  • the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains a partial structure represented by the formula (CI), the other partial structure is not particularly limited, but alkali dissolution during alkaline development. From the viewpoint of sex, it is also preferable to have a partial structure represented by the following general formula (CII), for example.
  • CII general formula
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 is an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent.
  • R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.
  • alkyl group in R 4 include linear, branched or cyclic alkyl groups.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, still preferably 20 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less. Even more preferably, 12 or less is particularly preferable.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, still more preferably 5 to 14, and particularly preferably 8 to 12.
  • Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group and a dodecanyl group. From the viewpoint of developability, a dicyclopentanyl group and a dodecanyl group are preferable, and a dicyclopentanyl group is more preferable.
  • Examples of the substituent that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, and methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • Examples of the aromatic ring group in R 4 include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less.
  • lipophilicity tends to be improved and solubility in a solvent tends to be improved
  • hydrophilicity is improved and alkali solubility tends to be improved. be.
  • the above upper and lower limits can be combined arbitrarily.
  • the aromatic ring group preferably has 6 to 24 carbon atoms, more preferably 6 to 22 carbon atoms, still more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 18 carbon atoms.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, or pyrene.
  • the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, or an imidazole ring.
  • Oxadiazole ring indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrazole ring, thienothiophene ring, flopyrol ring, floran ring, thienoflan ring, benzoisoxazole ring, benzoisothiazole ring, Examples thereof include a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a synolin ring, a quinoxalin ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring
  • a benzene ring group and a naphthalene ring group are preferable, and a benzene ring group is more preferable.
  • the substituent that the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group and an epoxy group.
  • Examples of the alkenyl group in R 4 include a linear, branched or cyclic alkenyl group.
  • the number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less.
  • lipophilicity tends to be improved and solubility in a solvent tends to be improved
  • hydrophilicity is improved and alkali solubility tends to be improved. be.
  • the above upper and lower limits can be combined arbitrarily.
  • the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably 2 to 18 carbon atoms, still more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.
  • alkenyl group examples include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-butene-1-yl group, a 3-butene-1-yl group, a 2-pentene-1-yl group, and 3 -Pentene-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl can be mentioned. From the viewpoint of developability, a vinyl group and an allyl group are preferable, and a vinyl group is more preferable.
  • Examples of the substituent that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. Can be mentioned. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent, and has a developability and a film strength. From the viewpoint, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.
  • the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure represented by the formula (CII)
  • the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure.
  • the content ratio of the partial structure represented by the formula (CII) is not particularly limited, but 1 mol% or more is preferable, 5 mol% or more is more preferable, 10 mol% or more is further preferable, and 20 mol% or more is particularly preferable. Further, 70 mol% or less is preferable, 60 mol% or less is more preferable, 50 mol% or less is further preferable, and 40 mol% or less is particularly preferable.
  • the alkali solubility tends to be improved
  • the storage stability of the colored resin composition tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the content ratio of the partial structure represented by the formula (CII) in the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is preferably 1 to 70 mol%, more preferably 5 to 60 mol%. 10 to 50 mol% is more preferable, and 20 to 40 mol% is particularly preferable.
  • the acrylic copolymer resin contains a partial structure represented by the formula (CI), it is represented by the following general formula (CIII) from the viewpoint of suppressing the decrease in brightness due to the improvement of heat resistance as the other partial structure contained. It is preferable that a partial structure is included.
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. It represents an alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
  • t represents an integer from 0 to 5.
  • R 6 has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, and the like. Represents a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent. Examples of the alkyl group in R 6 include linear, branched or cyclic alkyl groups.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, still more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and even more preferably 12 or less. Especially preferable.
  • lipophilicity tends to be improved and solubility in a solvent tends to be improved
  • hydrophilicity is improved and alkali solubility tends to be improved. be.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, still more preferably 3 to 14, and particularly preferably 5 to 12.
  • Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group and a dodecanyl group. From the viewpoint of heat resistance, a dicyclopentanyl group and a dodecanyl group are preferable, and a dicyclopentanyl group is more preferable.
  • Examples of the substituent that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, and methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • Examples of the alkenyl group in R 6 include a linear, branched or cyclic alkenyl group.
  • the number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less.
  • lipophilicity tends to be improved and solubility in a solvent tends to be improved
  • hydrophilicity is improved and alkali solubility tends to be improved. be.
  • the above upper and lower limits can be combined arbitrarily.
  • the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably 2 to 18 carbon atoms, still more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.
  • alkenyl group examples include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-butene-1-yl group, a 3-butene-1-yl group, a 2-pentene-1-yl group, and 3 -Pentene-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl can be mentioned. From the viewpoint of exposure sensitivity during ultraviolet exposure, a vinyl group and an allyl group are preferable, and a vinyl group is more preferable.
  • Examples of the substituent that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. Can be mentioned. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • Examples of the alkynyl group in R 6 include a linear, branched or cyclic alkynyl group.
  • the number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less.
  • lipophilicity tends to be improved and solubility in a solvent tends to be improved
  • hydrophilicity is improved and alkali solubility tends to be improved. be.
  • the above upper and lower limits can be combined arbitrarily.
  • the alkynyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably 2 to 18 carbon atoms, still more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.
  • alkynyl group examples include 1-propyne-3-yl group, 1-butyne-4-yl group, 1-pentyne-5-yl group, 2-methyl-3-butin-2-yl group, 1,4. Examples thereof include -pentadiyne-3-yl group, 1,3-pentadiyne-5-yl group and 1-hexin-6-yl group.
  • Examples of the substituent that the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. Can be mentioned. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • halogen atom in R 6 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Fluorine atoms are preferable from the viewpoint of storage stability of the acrylic copolymer resin.
  • Examples of the alkoxy group in R 6 include a linear, branched or cyclic alkoxy group.
  • the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less.
  • lipophilicity tends to be improved and solubility in a solvent tends to be improved
  • hydrophilicity is improved and alkali solubility tends to be improved. be.
  • the above upper and lower limits can be combined arbitrarily.
  • the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, further preferably 1 to 16 carbon atoms, still more preferably 1 to 14 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group.
  • Examples of the substituent that the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, and methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • Examples of the alkyl sulfide group in R 6 include linear, branched or cyclic alkyl sulfide groups.
  • the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less.
  • lipophilicity tends to be improved and solubility in a solvent tends to be improved
  • hydrophilicity is improved and alkali solubility tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms of the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, further preferably 1 to 16, further preferably 1 to 14, and particularly preferably 1 to 12.
  • alkyl sulfide group examples include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group. From the viewpoint of developability, a methyl sulfide group and an ethyl sulfide group are preferable.
  • Examples of the substituent that the alkyl group in the alkyl sulfide group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group and a phenyl group.
  • Examples thereof include a group, a carboxyl group, an acryloyl group and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • R 6 has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom and an alkoxy group.
  • a hydroxyalkyl group, a thiol group, or an alkyl sulfide group which may have a substituent and from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.
  • t represents an integer from 0 to 5. From the viewpoint of ease of manufacture, t is preferably 0.
  • the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure represented by the formula (CIII)
  • the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure.
  • the content ratio of the partial structure represented by the formula (CIII) is not particularly limited, but 1 mol% or more is preferable, 2 mol% or more is more preferable, 5 mol% or more is further preferable, and 8 mol% or more is particularly preferable. Further, 50 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is further preferable, and 20 mol% or less is particularly preferable.
  • the content ratio of the partial structure represented by the formula (CIII) in the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is preferably 1 to 50 mol%, more preferably 2 to 40 mol%. 5 to 30 mol% is more preferable, and 8 to 20 mol% is particularly preferable.
  • R 7 represents a hydrogen atom or a methyl group.
  • the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is contained, the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is contained.
  • the content ratio of the partial structure represented by the formula (CIV) in the above is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and 80 mol% or less. It is preferably 70 mol% or less, more preferably 60% mol or less.
  • the alkali solubility tends to be improved
  • the storage stability of the colored resin composition tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the content ratio of the partial structure represented by the formula (CIV) in the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is preferably 5 to 80 mol%, more preferably 10 to 70 mol%. 20-60% mol is more preferred.
  • the acid value of the alkali-soluble resin (C) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 40 mgKOH / g or more, still more preferably 50 mgKOH / g or more, and 60 mgKOH / g.
  • the above is particularly preferable, and 300 mgKOH / g or less is preferable, 250 mgKOH / g or less is more preferable, 200 mgKOH / g or less is further preferable, and 150 mgKOH / g or less is further preferable.
  • the acid value of the alkali-soluble resin (C) is preferably 10 to 300 mgKOH / g, more preferably 30 to 300 mgKOH / g, even more preferably 40 to 250 mgKOH / g, still more preferably 50 to 200 mgKOH / g, and even more preferably 60 to 200 mgKOH / g.
  • 150 mgKOH / g is particularly preferable.
  • the weight average molecular weight of the alkali-soluble resin (C) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, still more preferably 6000 or more, still more preferably 7000 or more, and particularly preferably 8000 or more. Also, it is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less. When it is at least the above lower limit value, heat resistance and coating film curability tend to be improved, and when it is at least the above upper limit value, alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily.
  • the weight average molecular weight of the alkali-soluble resin (C) is preferably 1000 to 30000, more preferably 2000 to 30000, still more preferably 4000 to 20000, further preferably 6000 to 20000, particularly preferably 7000 to 15000, and 8000 to 8000. 10000 is particularly preferable.
  • the content ratio of the (C) alkali-soluble resin in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass in the total solid content of the colored resin composition. % Or more is further preferable, 30% by mass or more is further preferable, 40% by mass or more is particularly preferable, 80% by mass or less is more preferable, 70% by mass or less is more preferable, 60% by mass or less is further preferable, and 50% by mass is more preferable. % Or less is particularly preferable.
  • the content ratio of the (C) alkali-soluble resin in the colored resin composition is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, and 20 to 70% by mass in the total solid content of the colored resin composition. % Is even more preferable, 30 to 60% by mass is even more preferable, and 40 to 50% by mass is particularly preferable.
  • the colored resin composition of the present invention contains (D) a photopolymerization initiator.
  • a photopolymerization initiator By containing a photopolymerization initiator, film curability by photopolymerization can be imparted.
  • the photopolymerization initiator can also be used as a mixture (photopolymerization initiator) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye added as needed.
  • the photopolymerization initiation system is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.
  • Examples of the photopolymerization initiator include metallocene compounds containing titanosen compounds described in Japanese Patent Laid-Open Nos. 59-152396 and Japanese Patent Laid-Open No. 61-151197, and Japanese Patent Application Laid-Open No. 10-39503.
  • N-aryl- ⁇ -amino acids such as hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-phenylglycine, N-aryl- ⁇ -amino acid salts, N-aryl- ⁇ -amino acid esters, etc.
  • Examples thereof include a radical activator of the above, an ⁇ -aminoalkylphenone-based compound, and an oxime ester-based initiator described in Japanese Patent Application Laid-Open No. 2000-80068.
  • photopolymerization initiator that can be used in the present invention are listed below.
  • 2- (4-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4) Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
  • Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, ⁇ -hydroxy-2-methylphenylpropanol, 1-hydroxy-1-methylethyl- (p) -Isopropylphenyl) Ketone, 1-Hydroxy-1- (p-dodecylphenyl) Ketone, 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 1,1,1 -Acetophenone derivatives such as trichloromethyl- (p-butylphenyl) ketone; Thioxanthone
  • Ethyl benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazine derivatives such as 9,10-dimethylbenzphenazine; Anthrone derivatives such as Benz anthrone; Dicyclopentadienyl-Ti-dichloride, dicyclopentagenyl-Ti-bis-phenyl, dicyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentagenyl-Ti-bis-2,4,6-trifluoropheni-1-yl, Dicyclopentagenyl-Ti-2,6-diprul
  • an oxime ester-based compound (oxime ester-based photopolymerization initiator) is preferable.
  • Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in their structure, so that they are highly sensitive in a small amount and stable against thermal reactions. Therefore, it is possible to design a highly sensitive colored resin composition with a small amount.
  • an oxime ester-based compound having a carbazole ring, which may have a substituent is preferable from the viewpoint of light absorption of the exposure light source for i-ray (365 nm).
  • Examples of the oxime ester compound include compounds represented by the following general formula (I-1).
  • R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
  • R 21b represents any substituent, including aromatic or heteroaromatic rings.
  • R 22a represents an alkanoyl group which may have a substituent or an allyloyl group which may have a substituent.
  • the number of carbon atoms of the alkyl group in R 21a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent and sensitivity to exposure. It is 10 or less, more preferably 5 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group and a propyl group.
  • alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-.
  • substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-.
  • substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-.
  • substituents include a methylphenyl group or an N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • Examples of the aromatic ring group in R 21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored resin composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, further preferably 12 or less, and particularly preferably 8 or less. The above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms of the aromatic ring group is preferably 5 to 30, more preferably 5 to 20, further preferably 5 to 12, and particularly preferably 5 to 8.
  • Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a frill group and a fluorenyl group. From the viewpoint of developability, a phenyl group, a naphthyl group and a fluorenyl group are preferable, and a phenyl group and a fluorenyl group are more preferable.
  • Examples of the substituent that the aromatic ring group may have include a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a carboxy group, and a halogen atom. Examples thereof include an amino group, an amide group and an alkyl group.
  • a hydroxyl group and a carboxy group are preferable, and a carboxy group is more preferable.
  • the substituent in the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group, a halogen atom and a nitro group.
  • R 21a an alkyl group which may have a substituent is preferable, an unsubstituted alkyl group is more preferable, and a methyl group is further preferable.
  • R 21b is any substituent, including aromatic or heteroaromatic rings.
  • a carbazolyl group which may have a substituent
  • a thioxanthonyl group which may have a substituent
  • a diphenylsulfide group which may have a substituent or
  • a fluorenyl group which may have a substituent and a group in which these groups and a carbonyl group are linked are preferable.
  • a carbazolyl group which may have a substituent or a group in which a carbazolyl group and a carbonyl group which may have a substituent are linked is preferable.
  • Examples of the substituent that the carbazolyl group may have include an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; F, Halogen atoms such as Cl, Br, I; acyl group with 1 to 10 carbon atoms; alkyl ester group with 1 to 10 carbon atoms; alkoxycarbonyl group with 1 to 10 carbon atoms; alkyl halide group with 1 to 10 carbon atoms; An aromatic ring group having 4 to 10 carbon atoms; an amino group; an aminoalkyl group having 1 to 10 carbon atoms; a hydroxyl group; a nitro group; a CN group; an allylloyl group which may have a substituent; Heteroaryloyl groups may be; examples include tenoyl groups which may have substituents.
  • the carbon number of the alkanoyl group in R 22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. , More preferably 5 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the alkanoyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 10 carbon atoms, still more preferably 2 to 5 carbon atoms, and particularly preferably 3 to 5 carbon atoms.
  • alkanoyl group examples include an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group.
  • substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group and an amide group, which are unsubstituted from the viewpoint of ease of synthesis. Is preferable.
  • the carbon number of the allylloyl group in R 22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Is. The above upper and lower limits can be combined arbitrarily.
  • the allylloyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 15, still more preferably 7 to 10, and particularly preferably 8 to 10.
  • the allylloyl group include a benzoyl group and a naphthoyl group.
  • Examples of the substituent that the allylloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group, which may be unsubstituted from the viewpoint of easiness of synthesis. preferable.
  • Examples of the compound represented by the formula (I-1) include compounds represented by the following general formula (I-2) or (I-3) from the viewpoint of light absorption of the exposure light source for i-line (365 nm). Be done.
  • R 21a and R 22a are synonymous with formula (I-1).
  • R 23a represents an alkyl group which may have a substituent.
  • R 24a represents an alkyl group which may have a substituent, an allylloyl group which may have a substituent, a heteroallyloyl group which may have a substituent, or a nitro group.
  • the benzene ring constituting the carbazole ring may be further condensed by an aromatic ring to form a polycyclic aromatic ring.
  • the number of carbon atoms of the alkyl group in R 23a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further. It is preferably 5 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and a cyclohexyl group.
  • Examples of the substituent that the alkyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group and a nitro group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • R 23a is more preferably an ethyl group from the viewpoint of solubility in a solvent and easiness of synthesis.
  • the number of carbon atoms of the alkyl group in R 24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further. It is preferably 5 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and a cyclohexyl group.
  • alkyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group and a nitro group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • the carbon number of the allylloyl group in R 24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. It is preferably 10 or less, more preferably 9 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the allylloyl group preferably has 7 to 20 carbon atoms, more preferably 8 to 15, still more preferably 9 to 10, and particularly preferably 9.
  • the allylloyl group include a benzoyl group and a naphthoyl group.
  • Examples of the substituent that the allylloyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group and a nitro group. From the viewpoint of ease of synthesis, an ethyl group is preferable.
  • the number of carbon atoms of the heteroallyloyl group in R 24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. , More preferably 10 or less, still more preferably 9 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the heteroallyloyl group preferably has 7 to 20 carbon atoms, more preferably 8 to 15, still more preferably 9 to 10, and particularly preferably 9.
  • heteroaryl group examples include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group, and a bromonaphthoyl group.
  • substituent that the heteroarylloyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group and a nitro group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • R 24a an allylloyl group which may have a substituent is preferable, and a benzoyl group is more preferable, from the viewpoint of sensitivity.
  • the benzene ring constituting the carbazole ring may be further condensed by an aromatic ring to form a polycyclic aromatic ring.
  • oxime ester compounds include, for example, OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Joshu Strong Electronics New Materials Co., Ltd., and N-1919 manufactured by ADEKA Corporation. , NCI-930, NCI-831.
  • oxime ester compound examples include the following compounds.
  • photopolymerization initiators may be used alone or in combination of two or more.
  • a chain transfer agent is a compound having a function of receiving a generated radical and transferring the received radical to another compound.
  • various chain transfer agents can be used as long as they are compounds having the above functions, and examples thereof include mercapto group-containing compounds and carbon tetrachloride, which tend to have a high chain transfer effect. Therefore, it is more preferable to use a mercapto group-containing compound. It is considered that this is because the bond cleavage is likely to occur due to the small SH binding energy, and a hydrogen drawing reaction or a chain transfer reaction is likely to occur. It is effective for improving sensitivity and surface hardening.
  • Examples of the mercapto group-containing compound include 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline.
  • Mercapto group-containing compounds having an aromatic ring such as ⁇ -mercaptonaphthalene, 1,4-dimethylmercaptobenzene; hexanedithiol, decandithiol, butanediolbis (3-mercaptopropionate), butanediolbisthioglycolate, Ethethyleneglycolbis (3-mercaptopropionate), ethyleneglycolbisthioglycolate, trimethylolpropanetris (3-mercaptopropionate), trimethylolpropanetristhioglycolate, trishydroxyethyltristhiopropionate, penta Erislitholtetrakis (3-mercaptopropionate), pentaerythritoltris (3-mercaptopropionate), butanediolbis (3-mercaptobutyrate), ethyleneglycolbis (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptobut
  • 2-mercaptobenzothiazole and 2-mercaptobenzoimidazole are preferable, and as the aliphatic mercapto group-containing compound, trimethylolpropanthris (3-mercaptopropionate), Pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylol propanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-Mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione are preferred.
  • aliphatic mercapto group-containing compounds are preferable, such as trimethylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritoltris (3-mercaptopro).
  • the content ratio of the (D) photopolymerization initiator is not particularly limited, but is preferably 0.5% by mass or more, preferably 0.8% by mass or more in the total solid content of the colored resin composition. Is more preferable, 1.0% by mass or more is further preferable, 1.2% by mass or more is particularly preferable, 10% by mass or less is more preferable, 8% by mass or less is more preferable, and 6% by mass or less is further preferable. Mass% or less is particularly preferable. When it is at least the lower limit value, the curability of the coating film tends to be improved, and when it is at least the upper limit value, visible light absorption is reduced and the brightness tends to be improved. The above upper and lower limits can be combined arbitrarily.
  • the content ratio of the (D) photopolymerization initiator is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass in the total solid content of the colored resin composition. , 1.0 to 6% by mass is more preferable, and 1.2 to 4% by mass is particularly preferable.
  • the content ratio thereof is not particularly limited, but is preferably 0.1% by mass or more, preferably 0.2% by mass or more in the total solid content of the colored resin composition. Is more preferable, 0.3% by mass or more is further preferable, 0.4% by mass or more is particularly preferable, 3% by mass or less is more preferable, 2.5% by mass or less is more preferable, and 2% by mass or less is further preferable. , 1.5% by mass or less is particularly preferable.
  • the solvent resistance tends to be improved
  • the storage stability tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the content ratio is preferably 0.1 to 3% by mass, and 0.2 to 2.5% by mass in the total solid content of the colored resin composition. More preferably, 0.3 to 2% by mass is further preferable, and 0.4 to 1.5% by mass is particularly preferable.
  • the colored resin composition of the present invention contains (E) a photopolymerizable monomer.
  • the photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular weight compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”) is preferable. ..
  • the ethylenic compound is a compound having an ethylenic double bond such that when the colored resin composition of the present invention is irradiated with active light, it is addition-polymerized by the action of a photopolymerization initiator and cured.
  • the monomer in the present invention means a concept opposite to a so-called polymer substance, and means a concept containing a dimer, a trimer, and an oligomer in addition to the monomer in a narrow sense.
  • the (E) photopolymerizable monomer in the colored resin composition of the present invention is a photopolymerizable monomer (e1) having a partial structure represented by the following general formula (I) (hereinafter, “photopolymerizable monomer (e1)””. May be referred to as).
  • R 1 represents an alkylene group having 2 or more carbon atoms.
  • R 2 represents a hydrogen atom or a methyl group.
  • n represents an integer of 1 or more. * Represents a bond.
  • the photopolymerizable monomer (e1) has an alkylene oxide chain
  • the phthalocyanine compound can maintain good developer permeability even in a coating film state having a small residual solvent such as 100 ° C. It is considered that even the colored resin composition containing (1) can suppress the decrease in the prebake temperature dependence of the hole diameter.
  • R 1 represents an alkylene group having 2 or more carbon atoms.
  • the alkylene group has no substituent.
  • the alkylene group may be linear, branched, cyclic, or a combination thereof.
  • a linear alkylene group is preferable from the viewpoint of solvent solubility and solvent resistance.
  • the number of carbon atoms of the alkylene group is not particularly limited as long as it is 2 or more, but it is preferably 4 or less, more preferably 3 or less, still more preferably 2. By setting the value to the upper limit or less, the coating film sensitivity and solvent resistance tend to be improved.
  • the alkylene group preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms, and even more preferably 2.
  • alkylene group examples include an ethylene group, an n-propylene group, an n-butylene group, and an isopropylene group. From the viewpoint of coating film curability, an n-propylene group and an ethylene group are preferable, and an ethylene group is more preferable.
  • n represents an integer of 1 or more, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less. When the value is not more than the upper limit, the curability of the coating film tends to be improved.
  • n is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2.
  • photopolymerizable monomer (e1) a compound represented by the following general formula (II) is preferable from the viewpoint of coating film curability.
  • R 1 , R 2 and n are synonymous with formula (I).
  • Z is a direct bond, an oxygen atom, a sulfur atom, a 2- to 4-valent aliphatic hydrocarbon group, a 4-valent carbon atom, a 2- to 4-valent non-aromatic heterocyclic group, and a 2- to 4-valent aromatic ring group.
  • p represents an integer of 2 to 6.
  • the structures represented by the following general formula (II') contained in one molecule may be the same or different.
  • X is a direct bond, an oxygen atom, a sulfur atom, a 2- to 4-valent aliphatic hydrocarbon group, a 4-valent carbon atom, a 2- to 4-valent non-aromatic heterocyclic group, 2 to 4 It represents an aromatic ring group of valence or a partial structure represented by the formula (III).
  • the 2- to tetravalent aliphatic hydrocarbon group may be linear, branched-chain, cyclic, or a combination thereof.
  • the number of carbon atoms of the 2- to tetravalent aliphatic hydrocarbon group is not particularly limited, but is preferably 10 or less, more preferably 9 or less, further preferably 8 or less, and usually 1 or more. When the value is not more than the upper limit, the curability of the coating film is improved and the solvent resistance tends to be improved.
  • the number of carbon atoms of the 2- to tetravalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 9, and even more preferably 1 to 8.
  • Examples of the 2- to 4-valent aliphatic hydrocarbon group include methane, ethane, propane and butane having 2 to 4 free valences.
  • the non-aromatic heterocycle in the 2- to tetravalent non-aromatic heterocyclic group may be a monocyclic ring or a condensed ring.
  • the non-aromatic heterocycle is a non-aromatic ring containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom.
  • the number of carbon atoms of the 2- to tetravalent non-aromatic heterocyclic group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, preferably 8 or less, and more preferably 6 or less.
  • the heat resistance tends to be improved
  • the solvent solubility tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms of the 2- to tetravalent non-aromatic heterocyclic group is preferably 3 to 8, more preferably 3 to 6, and even more preferably 4 to 6.
  • the 2- to 4-valent non-aromatic heterocyclic group include a piperidine ring and a pyrrolidine ring having 2 to 4 free valences.
  • Examples of the 2- to 4-valent aromatic ring group include a 2- to 4-valent aromatic hydrocarbon ring group and a 2- to 4-valent aromatic heterocyclic group.
  • the aromatic hydrocarbon ring in the 2- to tetravalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.
  • the number of carbon atoms of the aromatic hydrocarbon ring group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, preferably 15 or less, more preferably 12 or less, still more preferably 9 or less. .. When it is at least the lower limit value, the heat resistance tends to be improved, and when it is at least the upper limit value, the brightness tends to be improved.
  • the number of carbon atoms of the 2- to 4-valent aromatic hydrocarbon ring group is preferably 3 to 15, more preferably 4 to 12, and even more preferably 5 to 9.
  • the 2- to 4-valent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, and a benzpyrene ring, which have 2 to 4 free atomic valences. , Chrysene ring, triphenylene ring, acenaphthene ring, fluorene ring, fluorene ring and the like.
  • the aromatic heterocycle in the 2- to tetravalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring.
  • the number of carbon atoms of the aromatic heterocyclic group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, preferably 15 or less, more preferably 12 or less, still more preferably 9 or less.
  • the heat resistance tends to be improved
  • the brightness tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms of the 2- to tetravalent aromatic heterocyclic group is preferably 3 to 15, more preferably 4 to 12, and even more preferably 5 to 9.
  • the 2- to 4-valent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxadi ring having 2 to 4 free atomic valences.
  • Z is preferably an oxygen atom, a sulfur atom, or a tetravalent carbon atom, and more preferably a tetravalent carbon atom.
  • p represents an integer of 2-6. 3 or more is preferable, 5 or less is preferable, and 4 or less is more preferable.
  • the electrical reliability tends to be improved
  • the curability of the coating film tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • p is preferably 3 to 5, and more preferably 3 to 4.
  • Examples of the photopolymerizable monomer (e1) include the following.
  • the (E) photopolymerizable monomer in the colored resin composition of the present invention may be referred to as a photopolymerizable monomer other than the photopolymerizable monomer (e1) (hereinafter, "other photopolymerizable monomer (e2)”. ) May be included.
  • the other photopolymerizable monomer (e2) it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule.
  • the number of ethylenic double bonds contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 5 or more.
  • the number is 8 or less, more preferably 7 or less.
  • the sensitivity tends to be high
  • the solubility in a solvent tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of ethylenic double bonds contained in the polyfunctional ethylenic monomer is preferably 2 to 8, more preferably 4 to 8, and even more preferably 5 to 7.
  • Examples of the other photopolymerizable monomer (e2) include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and aromatic polyhydroxy compounds.
  • Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting a compound with a (meth) acryloyl-containing hydroxy compound.
  • ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid examples include ethylene glycol diacrylate, trimethylol propanetriacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.
  • acrylic acid esters such as dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate.
  • acrylic acid moiety of these acrylates is replaced with a methacrylic acid ester instead of a methacrylic acid moiety, an itaconic acid ester substituted with an itaconic acid moiety, a crotonic acid ester substituted with a crotonic acid moiety, or a maleic acid substituted with a maleic acid moiety.
  • Ester can be mentioned.
  • ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid examples include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
  • the ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single substance but may be a mixture.
  • a condensate of acrylic acid, phthalic acid and ethylene glycol a condensate of acrylic acid, maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin.
  • a condensate of acrylic acid, phthalic acid and ethylene glycol a condensate of acrylic acid, maleic acid and diethylene glycol
  • a condensate of methacrylic acid, terephthalic acid and pentaerythritol a condensate of acrylic acid, adipic acid, butanediol and glycerin.
  • Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate.
  • Alicyclic diisocyanate aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloxymethyl) propane, 3- Examples thereof include a reaction product with a (meth) acryloyl group-containing hydroxy compound such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane.
  • the other photopolymerizable monomer (e2) may be a monomer having an acid value.
  • the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is formed by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
  • the provided polyfunctional monomer is preferable, and in this ester, the polyfunctional monomer in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is particularly preferable.
  • One of these monomers may be used alone, but since it is difficult to use a single compound in production, two or more of these monomers may be mixed and used. Further, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as the monomer.
  • the acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When it is set to the lower limit value or more, the development and dissolution characteristics tend to be good, and when it is set to the upper limit value or less, the manufacturing and handling are improved, and the photopolymerization performance, the surface smoothness of the pixel, etc. are improved. It tends to improve the curability.
  • the acid group as the whole polyfunctional monomer should be adjusted so as to fall within the above range. Is preferable.
  • the polyfunctional monomer having a more preferable acid group contains a succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate commercially available as TO1382 manufactured by Toagosei Co., Ltd. as a main component. It is a mixture to be used.
  • This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Further, the polyfunctional monomer described in paragraphs [0056] and [0057] of Japanese Patent Application Laid-Open No. 2013-140346 can also be used.
  • the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195971 from the viewpoint of improving the chemical resistance of the pixel and the linearity of the edge of the pixel, it is preferable to use the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195971. From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the developing time, it is preferable to use the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195974.
  • the content ratio of the (E) photopolymerizable monomer in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 7% by mass or more in the total solid content of the colored resin composition. More preferably, it is more preferably mass% or more, 12% by mass or more, particularly preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less.
  • the coating film curability tends to be improved
  • the storage stability tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the content ratio of the (E) photopolymerizable monomer in the colored resin composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and 10 to 30% by mass in the total solid content of the colored resin composition. % Is more preferable, and 12 to 20% by mass is particularly preferable.
  • the content ratio of the photopolymerizable monomer (e1) in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 7% by mass or more in the total solid content of the colored resin composition. More preferably, it is more preferably mass% or more, 12% by mass or more, particularly preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less.
  • it is at least the above lower limit the solubility of the developer tends to be improved and the patterning shape when the hot plate temperature rises tends to be improved, and when it is at least the above upper limit, the storage stability and the pattern adhesion are improved. Tend to do.
  • the content ratio of the photopolymerizable monomer (e1) in the colored resin composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and 10 to 30% by mass in the total solid content of the colored resin composition. % Is more preferable, and 12 to 20% by mass is particularly preferable.
  • the content ratio of the photopolymerizable monomer (e1) to the (E) photopolymerizable monomer is not particularly limited, but is preferably 40% by mass or more, more preferably 45% by mass or more, and 50% by mass. % Or more is further preferable, 55% by mass or more is particularly preferable, 98% by mass or less is preferable, 96% by mass or less is more preferable, 94% by mass or less is further preferable, and 92% by mass or less is particularly preferable.
  • the solubility of the developer tends to be improved
  • the patterning property tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • the content ratio of the photopolymerizable monomer (e1) to the (E) photopolymerizable monomer is preferably 40 to 98% by mass, more preferably 45 to 96% by mass, further preferably 50 to 94% by mass, and 55 to 55 to 92% by mass is particularly preferable.
  • the colored resin composition of the present invention may further contain solids other than the above components, if necessary.
  • a component include a dispersant, a dispersion aid, a surfactant, and an adhesion improver.
  • Dispersant Dispersion Aid
  • a dispersant for the purpose of stably dispersing the pigment.
  • the dispersants it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time.
  • the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters.
  • a system dispersant can be mentioned.
  • Examples of the polymer dispersant include EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), and SOLSERSE (registered trademark, manufactured by Rubri).
  • Dispersants described in Japanese Patent Laid-Open No. 2013-119568 manufactured by Zol
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • a block copolymer having a functional group containing a nitrogen atom is preferable, and an acrylic block copolymer having a functional group containing a nitrogen atom is more preferable from the viewpoint of dispersibility and storage stability.
  • the block copolymer having a functional group containing a nitrogen atom includes an A block having a quaternary ammonium base and / or an amino group in the side chain, and a B block having no quaternary ammonium base and an amino group.
  • AB block copolymers and BAB block copolymers are preferable.
  • Examples of the functional group containing a nitrogen atom include a 1- to tertiary amino group and a quaternary ammonium base. From the viewpoint of dispersibility and storage stability, a primary to tertiary amino group is preferable, and a tertiary amino group is more preferable.
  • the structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but from the viewpoint of dispersibility and storage stability, the repeating unit represented by the following general formula (d1) is preferable.
  • R 1 and R 2 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It may be an aralkyl group, and R 1 and R 2 may be bonded to each other to form a cyclic structure.
  • R 3 is a hydrogen atom or a methyl group.
  • X is a divalent linking group.
  • the number of carbon atoms of the alkyl group which may have a substituent in the formula (d1) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. It is more preferably 4 or less. For example, 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is further preferable.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group.
  • Methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group are preferable, and methyl group, ethyl group, propyl group and butyl group are more preferable.
  • the alkyl group may be linear or branched.
  • the alkyl group may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.
  • the number of carbon atoms of the aryl group which may have a substituent in the formula (d1) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. , 8 or less is more preferable. For example, 6 to 16 is preferable, 6 to 12 is more preferable, and 6 to 8 is even more preferable.
  • the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthrasenyl group.
  • a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group and a diethylphenyl group are preferable, and a phenyl group, a methylphenyl group and an ethylphenyl group are more preferable.
  • the carbon number of the aralkyl group which may have a substituent in the formula (d1) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. , 9 or less is more preferable. For example, 7 to 16 is preferable, 7 to 12 is more preferable, and 7 to 9 is even more preferable.
  • the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group.
  • a phenylmethylene group, a phenylethylene group, a phenylpropylene group and a phenylbutylene group are preferable, and a phenylmethylene group and a phenylethylene group are more preferable.
  • R 1 and R 2 are preferably an alkyl group which may have an independent substituent, and more preferably a methyl group or an ethyl group. ..
  • Examples of the substituent that the alkyl group, aralkyl group, and aryl group in the formula (d1) may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • examples of the cyclic structure formed by bonding R 1 and R 2 to each other include a nitrogen-containing heterocyclic monocycle having a 5- to 7-membered ring or a fused ring formed by condensing two of them. ..
  • the nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring.
  • the following cyclic structure (IV) can be mentioned.
  • These cyclic structures may further have a substituent.
  • the divalent linking group X includes, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 13 ⁇ group, and a ⁇ COOR 14 ⁇ group (provided that the divalent linking group X is).
  • R 13 and R 14 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), preferably -COO-R 14- group. Is.
  • the content ratio of the repeating unit represented by the formula (d1) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and further preferably 15 mol. % Or more is more preferable, 20 mol% or more is particularly preferable, 25 mol% or more is particularly preferable, 90 mol% or less is preferable, 70 mol% or less is more preferable, 50 mol% or less is further preferable, and 40 mol is more preferable. % Or less is particularly preferable. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily.
  • the content ratio of the repeating unit represented by the formula (d1) in all the repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, and 10 to 70 mol%. Further preferred, 15-70 mol% is even more preferred, 20-50% is particularly preferred, and 25-40 mol% is particularly preferred.
  • the block copolymer preferably has a repeating unit represented by the following general formula (d2) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability.
  • R 10 is an ethylene group or a propylene group
  • R 11 is an alkyl group which may have a substituent
  • R 12 is a hydrogen atom or a methyl group.
  • n is an integer from 1 to 20.
  • the number of carbon atoms of the alkyl group which may have a substituent in R 11 of the formula (d2) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. Is preferable, 6 or less is more preferable, and 4 or less is further preferable. The above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 2 to 4.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group.
  • Methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group are preferable, and methyl group, ethyl group, propyl group and butyl group are more preferable.
  • the alkyl group may be linear or branched.
  • the alkyl group may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.
  • alkyl group may have examples include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • n in the formula (d2) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, and 5 or less. Is more preferable. The above upper and lower limits can be combined arbitrarily.
  • n is preferably 1 to 10, more preferably 2 to 5.
  • the content ratio of the repeating unit represented by the formula (d2) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 4 mol% or more, and further. It is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. Within the above range, it tends to be possible to achieve both compatibility with a binder component such as a solvent and dispersion stability. The above upper and lower limits can be combined arbitrarily.
  • the content ratio of the repeating unit represented by the formula (d2) in all the repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 4 to 10 mol%. More preferred.
  • the block copolymer preferably has a repeating unit represented by the following general formula (d3) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability.
  • R 8 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
  • R 9 is a hydrogen atom or a methyl group.
  • the number of carbon atoms of the alkyl group which may have a substituent in R 8 of the formula (d3) is not particularly limited, but is usually 1 or more, preferably 10 or less, and preferably 6 or less. Is more preferable. For example, 1 to 10 is preferable, and 1 to 6 is more preferable.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group.
  • Methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group are preferable, and methyl group, ethyl group, propyl group and butyl group are more preferable.
  • the alkyl group may be linear or branched.
  • the alkyl group may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.
  • the number of carbon atoms of the aryl group which may have a substituent in R 8 of the formula (d3) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. Is more preferable. For example, 6 to 16 are preferable, and 6 to 12 are more preferable.
  • the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group and an anthrasenyl group.
  • a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group and a diethylphenyl group are preferable, and a phenyl group, a methylphenyl group and an ethylphenyl group are more preferable.
  • the carbon number of the aralkyl group which may have a substituent in R 8 of the formula (d3) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. Is more preferable. For example, 7 to 16 is preferable, and 7 to 12 is more preferable.
  • the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group and a phenylisopropylene group.
  • a phenylmethylene group, a phenylethylene group, a phenylpropylene group and a phenylbutylene group are preferable, and a phenylmethylene group and a phenylethylene group are more preferable.
  • R 8 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethylene group.
  • substituents that the alkyl group may have in R 8 include a halogen atom and an alkoxy group.
  • the substituent that the aryl group or the aralkyl group may have include a chain-like alkyl group, a halogen atom, and an alkoxy group.
  • the chain-like alkyl group represented by R 8 includes both linear and branched chain-like groups.
  • the content ratio of the repeating unit represented by the formula (d3) in all the repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and further. 80 mol% or less is preferable, and 70 mol% or less is more preferable. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily.
  • the content ratio of the repeating unit represented by the formula (d3) in all the repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and 50 to 70 mol%. More preferred.
  • the block copolymer may have a repeating unit other than the repeating unit represented by the formula (d1), the repeating unit represented by the formula (d2), and the repeating unit represented by the formula (d3).
  • Such repeating units include, for example, styrene-based monomers such as styrene and ⁇ -methylstyrene; (meth) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- Examples thereof include (meth) acrylamide-based monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate ether; and repeating units derived from N-methacryloylmorpholine.
  • the block copolymer having an A block having a repeating unit represented by the formula (d1) and a B block having no repeating unit represented by the formula (d1).
  • the block copolymer is preferably an AB block copolymer or a BAB block copolymer. It is more preferable that the B block has a repeating unit represented by the formula (d2) and / or a repeating unit represented by the formula (d3).
  • a repeating unit other than the repeating unit represented by the formula (d1) may be contained in the A block.
  • Examples of such repeating units include the above-mentioned repeating units derived from (meth) acrylic acid esters.
  • the content of the repeating unit other than the repeating unit represented by the formula (d1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, still more preferably 0 mol%.
  • a repeating unit other than the repeating unit represented by the formula (d2) and the repeating unit represented by the formula (d3) may be contained in the B block.
  • Such repeating units include, for example, styrene-based monomers such as styrene and ⁇ -methylstyrene; (meth) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- Examples thereof include (meth) acrylamide-based monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate ether; and repeating units derived from N-methacryloylmorpholine.
  • the content of the repeating unit represented by the formula (d2) and the repeating unit other than the repeating unit represented by the formula (d3) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. , More preferably 0 mol%.
  • the acid value of the block copolymer is preferably low, and particularly preferably 0 mgKOH / g, from the viewpoint of dispersibility.
  • the acid value represents the number of mg of KOH required to neutralize 1 g of the dispersant solid content.
  • the amine value of the block copolymer is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, further preferably 70 mgKOH / g or more, still more preferably 90 mgKOH / g or more.
  • 100 mgKOH / g or more is particularly preferable, 105 mgKOH / g or more is particularly preferable, 150 mgKOH / g or less is preferable, and 130 mgKOH / g or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • the amine value represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH.
  • the weight average molecular weight of the block copolymer is preferably 1000 to 30,000. When it is within the above range, the dispersion stability is good, and dry foreign matter tends to be less likely to be generated during coating by the slit nozzle method.
  • the block copolymer can be produced by a known method. For example, it can be produced by performing living polymerization of a monomer into which each of the above repeating units is introduced.
  • Examples of the living polymerization method include Japanese Patent Application Laid-Open No. 9-62002, Japanese Patent Application Laid-Open No. 2002-31713, and P.M. Lutz, P. et al. Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K. et al. Ute, et al, Polym. J.
  • the content ratio of the dispersant is not particularly limited, but it is preferably 0.001% by mass or more, preferably 0.01% by mass, in the total solid content of the colored resin composition.
  • the above is more preferable, 0.1% by mass or more is further preferable, 1% by mass or more is further preferable, 2% by mass or more is particularly preferable, 25% by mass or less is preferable, 20% by mass or less is more preferable, and 15 by mass. More preferably, it is more preferably 10% by mass or less, and particularly preferably 10% by mass or less.
  • the content ratio of the dispersant is preferably 0.001 to 25% by mass, more preferably 0.01 to 25% by mass in the total solid content of the colored resin composition. , 0.1 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass.
  • the content ratio of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the pigment. Is 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass or less. It is more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. Within the above range, there is a tendency that a colorable resin composition having excellent dispersion stability and high brightness can be obtained.
  • the content ratio of the dispersant is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the pigment. Up to 50 parts by mass is even more preferable, 15 to 40 parts by mass is even more preferable, and 20 to 30 parts by mass is particularly preferable.
  • a pigment derivative may be contained as a dispersion aid in order to improve the dispersibility of the pigment and the dispersion stability.
  • the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, isoindoline-based, dioxazine-based, anthraquinone-based, indanthrone-based, perylene-based, and perinone-based.
  • examples thereof include derivatives of diketopyrrolopyrrole-based and dioxazine-based pigments.
  • Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, and an amide group directly on the pigment skeleton or an alkyl group or an aryl group. , A group bonded via a heterocyclic group or the like, preferably a sulfonic amide group and a quaternary salt thereof, a sulfonic acid group, and more preferably a sulfonic acid group.
  • these substituents may be substituted in a plurality of one pigment skeleton, or may be a mixture of compounds having different numbers of substitutions.
  • the pigment derivative include a sulfonic acid derivative of an azo pigment, a sulfonic acid derivative of a phthalocyanine pigment, a sulfonic acid derivative of a quinophthalone pigment, a sulfonic acid derivative of an isoindrin pigment, a sulfonic acid derivative of an anthraquinone pigment, and a sulfonic acid derivative of a quinacridone pigment.
  • examples thereof include a sulfonic acid derivative of a diketopyrrolopyrrole pigment and a sulfonic acid derivative of a dioxazine pigment.
  • the surfactant various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but they adversely affect various properties. Nonionic surfactants are preferred because they are less likely.
  • the content ratio of the surfactant is not particularly limited, but is usually 0.001% by mass or more, preferably 0.01 in the total solid content of the colored resin composition. By mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 1% by mass or less, still more preferably 0.5% by mass or less, particularly. It is preferably used in the range of 0.3% by mass or less.
  • the content ratio of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, and 0.05 to 0.5% by mass in the total solid content of the colored resin composition. Is more preferable, and 0.1 to 0.3% by mass is particularly preferable.
  • the colored resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate.
  • the adhesion improving agent include a silane coupling agent and a titanium coupling agent.
  • Silane coupling agents are preferred.
  • the silane coupling agent include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shinetsu Silicone Co., Ltd.), Z-6040. , Z-6043, Z-6062 (manufactured by Toray Dow Corning).
  • the silane coupling agent one type may be used alone, or two or more types may be used in combination in any combination and ratio.
  • An adhesion improver other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention.
  • a phosphoric acid-based adhesion improver and other adhesion improvers can be mentioned.
  • phosphoric acid-based adhesion improver (meth) acryloyloxy group-containing phosphates are preferable.
  • Phosphoric acid-based adhesion improvers represented by the following general formulas (g1), (g2), and (g3) are preferable.
  • R 51 independently represents a hydrogen atom or a methyl group.
  • l and l'independently represent an integer of 1 to 10
  • m independently represents 1, 2 or 3, respectively.
  • adhesion improvers include TEGO (registered trademark) Add Bond LTH (manufactured by Evonik).
  • TEGO registered trademark
  • Add Bond LTH manufactured by Evonik
  • the content ratio thereof is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0 by mass in the total solid content. .3% by mass or more is further preferable, 0.4% by mass or more is particularly preferable, 3% by mass or less is preferable, 2% by mass or less is more preferable, 1.5% by mass or less is further preferable, and 1% by mass or less. Is particularly preferable.
  • the value is not less than the lower limit, the patterning characteristics are improved and the pattern adhesion under high humidity conditions tends to be improved, and when the value is not more than the upper limit, the generation of residues tends to be suppressed.
  • the content ratio thereof is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and 0.3 to 3% by mass in the total solid content. 1.5% by mass is more preferable, and 0.4 to 1% by mass is particularly preferable.
  • the pigment, the solvent and the dispersant are weighed in predetermined amounts, and in the dispersion treatment step, the colorant containing the pigment is dispersed to prepare a pigment dispersion liquid.
  • a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer and the like can be used.
  • the colorant is made into fine particles, so that the coating characteristics of the colored resin composition are improved and the transmittance of pixels in the color filter substrate of the product is improved.
  • the pigment When the pigment is dispersed, it is preferable to appropriately use a dispersion aid, a dispersion resin, or the like as described above.
  • a dispersion aid When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several mm or zirconia beads.
  • the temperature at the time of the dispersion treatment is usually set in the range of 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower.
  • the dispersion time varies depending on the composition of the pigment dispersion liquid, the size of the sand grinder device, and the like, and may be appropriately adjusted.
  • the pigment dispersion obtained by the above dispersion treatment is mixed with a solvent, an alkali-soluble resin, a photopolymerization initiator, and if necessary, components other than the above to obtain a uniform dispersion solution. Since fine dust may be mixed in each of the dispersion treatment step and the mixing step, it is preferable to filter the obtained pigment dispersion liquid with a filter or the like.
  • the pigment is not contained as the colorant, a colorant, a solvent, an alkali-soluble resin, a photopolymerization initiator, and if necessary, components other than the above can be mixed to obtain a uniform solution. It is preferable to filter the obtained solution with a filter or the like.
  • the color filter according to the present invention has pixels prepared by using the colored resin composition of the present invention.
  • the material of the transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate strength.
  • the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethylmethacrylate, and polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylics.
  • polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene
  • polycarbonate polymethylmethacrylate
  • polysulfone thermoplastic resin sheets epoxy resins, unsaturated polyester resins, and poly (meth) acrylics.
  • thermoplastic resin sheet such as a based resin
  • glass or a heat-resistant resin is preferable from the viewpoint of heat resistance.
  • the thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less.
  • the film thickness is usually 0.01 ⁇ m or more, preferably 0.05 ⁇ m or more, and usually 10 ⁇ m or less, preferably 5 ⁇ m or less. For example, it is 0.01 to 10 ⁇ m and 0.05 to 5 ⁇ m.
  • the color filter of the present invention can be manufactured by providing a black matrix on a transparent substrate and further forming red, green, and blue pixel images.
  • the colored resin composition of the present invention is preferably used as a coating liquid for forming green or blue pixels (resist pattern) among red, green, and blue pixels.
  • a pixel image is formed by performing each of coating, heat-drying, image exposure, development, and heat curing.
  • the black matrix is formed on a transparent substrate by using a light-shielding metal thin film or a colored resin composition for a black matrix.
  • a light-shielding metal material a chromium compound such as metallic chromium, chromium oxide, or chromium nitride, a nickel-tungsten alloy, or the like is used, and these may be laminated in a plurality of layers.
  • These metal light-shielding films are generally formed by an etching method, and after forming a desired pattern in a film shape by a positive photoresist, dicerium ammonium nitrate and perchloric acid and / or nitric acid are added to chromium.
  • a black matrix is formed by using an etching solution mixed with the above, and for other materials, it is carved using an etching solution suitable for the material, and finally the positive photoresist is peeled off with a special release agent. be able to.
  • a thin film of these metals or metal / metal oxides is formed on a transparent substrate by a vapor deposition method or a sputtering method.
  • the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, and triangles to form a resist image. After that, the coating film can be etched to form a black matrix.
  • a colored resin composition containing a black colorant is used to form a black matrix.
  • black color materials such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc., or red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes.
  • a black matrix can be formed by using a colored resin composition containing a black color material by mixing in the same manner as the method for forming red, green, and blue pixel images described below.
  • a colored resin composition of one of red, green, and blue is applied onto a transparent substrate provided with a black matrix, dried, and then a photomask is placed on the coating film.
  • a pixel image is formed by image exposure, development, and optionally heat curing or photocuring via a photomask. By performing this operation for each of the three colored resin compositions of red, green, and blue, a color filter image can be formed.
  • the colored resin composition for a color filter can be applied by a spinner method, a wire bar method, a flow coat method, a die coat method, a roll coat method, a spray coat method, or the like.
  • a spinner method a wire bar method
  • a flow coat method a die coat method
  • a roll coat method a spray coat method
  • the amount of coating liquid used is significantly reduced, there is no influence of mist adhering when the spin coating method is used, and the generation of foreign substances is suppressed. It is preferable from the above viewpoint.
  • the thickness of the coating film after drying is usually 0.2 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, and usually 20 ⁇ m or less, preferably 10 ⁇ m or less, more preferably 5 ⁇ m.
  • the range is as follows. For example, it is 0.2 to 20 ⁇ m, 0.5 to 10 ⁇ m, and 0.8 to 5 ⁇ m.
  • the coating film is preferably dried (prebaked) after the colored resin composition is applied to the substrate by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after pre-drying, it is heated again to dry.
  • the conditions for pre-drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like.
  • the drying temperature and drying time are selected according to the type of solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 ° C. or higher.
  • the temperature is in the range of ° C. or lower, preferably 70 ° C. or lower, and the drying time is usually in the range of 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.
  • the temperature condition for reheating and drying is preferably higher than the pre-drying temperature, specifically, usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130 ° C. or higher. It is in the range of °C or less.
  • the drying time is usually 10 seconds or longer, particularly preferably 15 seconds or longer, and usually 10 minutes or shorter, preferably 5 minutes or longer, although it depends on the heating temperature. The higher the drying temperature, the better the adhesiveness to the transparent substrate, but if it is too high, the binder resin may be decomposed, inducing thermal polymerization and causing development defects.
  • a vacuum drying method may be used in which the coating film is dried in the vacuum chamber without raising the temperature.
  • Exposure Step Image exposure is performed by superimposing a negative matrix pattern on a coating film of a colored resin composition and irradiating a light source of ultraviolet rays or visible light through this mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer.
  • the light source used for the above image exposure is not particularly limited.
  • the light source examples include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc.
  • lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc.
  • laser light sources such as an excima laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser.
  • An optical filter can also be used when irradiating light of a specific wavelength for use.
  • a coating film using the colored resin composition according to the present invention is subjected to image exposure with the above-mentioned light source, and then a surfactant and an alkaline compound are applied.
  • a surfactant and an alkaline compound are applied.
  • the aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.
  • alkaline compound examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphorus.
  • Inorganic alkaline compounds such as potassium acid, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di or triethanolamine, mono-di- Or trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc.
  • Examples include organic alkaline compounds. These alkaline compounds may be used alone or in combination of two or more.
  • the surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids.
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids.
  • anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts
  • amphoteric surfactants such as alkyl betaines and amino acids.
  • the organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol and diacetone alcohol.
  • the organic solvent can be used in combination with an aqueous solution.
  • the conditions of the development process are not particularly limited, but the development temperature is usually in the range of 10 ° C. or higher, particularly 15 ° C. or higher, further 20 ° C. or higher, and usually 50 ° C. or lower, particularly 45 ° C. or lower, further 40 ° C. or lower. Is preferable.
  • the developing method can be any one of a dipping developing method, a spray developing method, a brush developing method, an ultrasonic developing method and the like.
  • thermosetting treatment The color filter after development is subjected to a thermosetting treatment.
  • the thermosetting treatment conditions at this time are selected in a temperature range of usually 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 250 ° C. or lower, and the time is 5 minutes or longer and 60 minutes or lower. Selected by range.
  • the formation of a one-color patterning image is completed. This process is repeated in sequence to pattern black, red, green, and blue to form a color filter.
  • the order of patterning of the four colors is not limited to the above-mentioned order.
  • the color filter according to the present invention forms a transparent electrode such as ITO on an image in this state and is used as a part of parts such as a color display and a liquid crystal display device.
  • a top coat layer such as polyamide or polyimide can be provided on the image if necessary.
  • IPS mode plane alignment type drive system
  • a transparent electrode may not be formed.
  • Image display device panel
  • the image display device of the present invention has the color filter of the present invention.
  • the liquid crystal display device and the organic EL display device will be described in detail as the image display device.
  • [4-1] Liquid Crystal Display Device A method for manufacturing a liquid crystal display device according to the present invention will be described.
  • an alignment film is usually formed on the color filter of the present invention, a spacer is sprayed on the alignment film, and then the liquid crystal display device is bonded to a facing substrate to form a liquid crystal cell.
  • the liquid crystal is injected into the cell and connected to the counter electrode to complete the process.
  • a resin film such as polyimide is suitable.
  • a gravure printing method and / or a flexographic printing method is usually adopted for forming the alignment film, and the thickness of the alignment film is several tens of nm.
  • After the alignment film is hardened by heat firing, it is surface-treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface state in which the inclination of the liquid crystal can be adjusted.
  • the spacer used has a size corresponding to the gap (gap) with the facing substrate, and is usually preferably 2 to 8 ⁇ m.
  • a photospacer (PS) of a transparent resin film can be formed on a color filter substrate by a photolithography method, and this can be used instead of the spacer.
  • As the facing substrate an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.
  • the gap for bonding to the facing substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 ⁇ m or more and 8 ⁇ m or less.
  • the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin.
  • the sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
  • the liquid crystal cell whose periphery is sealed is cut into panel units, then depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the inside of the chamber leaks to inject the liquid crystal into the liquid crystal cell. ..
  • the degree of decompression in the liquid crystal cell is usually in the range of 1 ⁇ 10 ⁇ 2 Pa or more, preferably 1 ⁇ 10 -3 or more, and usually 1 ⁇ 10 -7 Pa or less, preferably 1 ⁇ 10 -6 Pa or less. .. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually in the range of 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.
  • the heat retention at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal display.
  • a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected by curing the UV curable resin.
  • the type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic type, an aliphatic type, or a polycyclic compound, and may be any of a lyotropic liquid crystal, a thermotropic liquid crystal, and the like.
  • thermotropic liquid crystal a nematic liquid crystal, a smestic liquid crystal, a cholesteric liquid crystal and the like are known, but any of them may be used.
  • [4-2] Organic EL Display Device When creating an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, the pixels 20 are formed on the transparent support substrate 10 by the colored resin composition of the present invention.
  • a multicolored organic EL element is manufactured by laminating an organic illuminant 500 on a blue color filter on which an organic protective layer 30 is formed and an inorganic oxide film 40.
  • a method of laminating the organic illuminant 500 a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of a color filter, or Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40.
  • the organic EL element 100 thus produced can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.
  • ⁇ Parthalocyanine compound A> A phthalocyanine compound A having the following chemical structure synthesized based on Example 30 of Japanese Patent Application Laid-Open No. 05-345861 was used.
  • Et in the formula represents ethyl.
  • the amine value is 120 mgKOH / g and the acid value is less than 1 mgKOH / g.
  • the content ratios of the repeating units represented by the following formulas (1a), (2a), (3a), (4a), and (5a) in all the repeating units are less than 1 mol%, 34.5 mol%, 6 respectively. It is 9.9 mol%, 13.8 mol%, and 6.9 mol%.
  • reaction vessel was replaced with air, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 50 parts by mass of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Then, 13 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 120 ° C. for 3.5 hours.
  • THPA tetrahydrophthalic anhydride
  • the polystyrene-equivalent weight average molecular weight Mw measured by GPC of the alkali-soluble resin A thus obtained was about 9000, the acid value was 25 mgKOH / g, and the double bond equivalent was 260 g / mol.
  • ⁇ Alkali-soluble resin B> A separable flask equipped with a cooling tube was prepared as a reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate was charged, and after nitrogen substitution, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. did.
  • an alkali-soluble resin B having a polystyrene-equivalent weight average molecular weight Mw measured by GPC of 9000, an acid value of 101 mgKOH / g, and a double bond equivalent of 550 g / mol was obtained.
  • C.I. I. Pigment Green 58 is 13.9 parts by mass
  • dispersant A is 1.9 parts by mass in terms of solid content
  • alkali-soluble resin B is 4.2 parts by mass in terms of solid content
  • propylene glycol monomethyl ether acetate is 80.0 parts by mass as a solvent.
  • a stainless steel container was filled with a mass portion (including a solvent derived from the dispersant A and a solvent derived from the alkali-soluble resin B) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm, and the dispersion treatment was performed with a paint shaker for 6 hours. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a green pigment dispersion A.
  • ⁇ Photopolymerizable Monomer B> A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). It does not correspond to the photopolymerizable monomer (e1).
  • Me in the formula represents methyl.
  • ⁇ Adhesion improver A> A compound having the following chemical structure.
  • C 2 H 4 represents dimethylene and C 3 H 6 represents trimethylene.
  • the obtained colored resin composition was applied onto a 50 mm square, 0.7 mm thick glass substrate (AN100 manufactured by AGC) by a spin coating method, dried under reduced pressure, and then placed on a hot plate at 90 ° C. Prebaked for 90 seconds. Next, the entire surface was exposed with a 2 kW high-pressure mercury lamp at an exposure amount of 40 mJ / cm 2 and an illuminance of 30 mW / cm 2 . Then, using a 0.04 mass% potassium hydroxide aqueous solution, development treatment was carried out at a developer temperature of 23 ° C. for 60 seconds. Then, a spray water washing treatment was performed for 10 seconds at a water pressure of 1 kg / cm 2 . Then, it was heat-cured at 230 ° C. for 20 minutes in a clean oven to prepare a colored substrate.
  • the thermosetting treatment was performed at 230 ° C. for 20 minutes to prepare a pattern substrate.
  • the diameter ( ⁇ m) of the hole portion of the pattern was measured using an optical microscope (hole diameter A).
  • the pattern substrate B was prepared under the same conditions except that the prebake temperature was changed from 80 ° C. to 100 ° C. With respect to the obtained pattern substrate B, the diameter ( ⁇ m) of the hole portion of the pattern was measured using an optical microscope (hole diameter B).
  • the phthalocyanine compound (1) has a structure in which one or more of the hydrogen atoms constituting the phthalocyanine skeleton are replaced with fluorine atoms having a small atomic radius, and the association between the phthalocyanine compounds (1) is not easily inhibited.
  • the decrease in brightness due to heating is suppressed by forming an aggregate when the intermolecular distance is shortened by heating or the like. Also after the meeting, C.I. I. It is considered that the particle size is smaller than that of Pigment Green 58, and the brightness is generally higher in the pattern after the thermosetting treatment.
  • Comparative Example 1 On the other hand, from the comparison between Comparative Example 1 and Comparative Example 2, the use of the phthalocyanine compound (1) worsens the prebake temperature dependence of the hole diameter.
  • Comparative Example 1 it is considered that the phthalocyanine compound (1) forms an aggregate having a small particle size and is densely present in the coating film, so that the permeation and dissolution of the developer into the coating film are easily suppressed. It is thought that it is.
  • the prebake temperature is 80 ° C., it is considered that the presence of a certain amount of residual solvent in the coating film can promote the penetration of the developer into the coating film.
  • the prebake temperature dependence of the hole diameter is deteriorated due to the shortage of the holes, the poor patterning formation, and the small hole diameter.
  • Examples 1, 2 and 3 containing the phthalocyanine compound (1) the prebake temperature dependence of the hole diameter is good while maintaining high brightness.
  • a part or all of the photopolymerizable monomer B of Comparative Example 1 is replaced with the photopolymerizable monomer (e1), but the photopolymerizable monomer (e1) is an alkylene oxide chain.
  • Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

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Abstract

Provided is a colored resin composition in which the effect of temperature changes during prebaking on developer solubility and patterning characteristics is low. The present invention is a colored resin composition containing (A) a coloring agent, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, wherein the coloring agent (A) includes a phthalocyanine compound having a specific chemical structure, and the photopolymerizable monomer (E) includes a photopolymerizable monomer (e1) having a specific partial structure.

Description

着色樹脂組成物、カラーフィルタ、及び画像表示装置Colored resin composition, color filter, and image display device
　本発明は、着色樹脂組成物、カラーフィルタ、及び画像表示装置に関する。
　本願は、２０２０年８月２０日に日本に出願された特願２０２０－１３９０３７号、及び２０２０年８月２０日に日本に出願された特願２０２０－１３９０３８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 colored resin composition, a color filter, and an image display device.
This application claims priority based on Japanese Patent Application No. 2020-139037 filed in Japan on August 20, 2020 and Japanese Patent Application No. 2020-139038 filed in Japan on August 20, 2020. The contents are used here.
　従来、液晶表示装置等に用いられるカラーフィルタを製造する方法としては、顔料分散法、染色法、電着法、印刷法が知られている。中でも、分光特性、耐久性、パターン形状及び精度等の観点から、平均的に優れた特性を有する顔料分散法が最も広範に採用されている。 Conventionally, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known as methods for manufacturing a color filter used in a liquid crystal display device or the like. Among them, the pigment dispersion method having excellent characteristics on average is most widely adopted from the viewpoints of spectral characteristics, durability, pattern shape, accuracy and the like.
　近年、カラーフィルタに対して、より高輝度、高コントラスト且つ高色域化が要求されている。カラーフィルタの色を決める色材としては、耐熱性、耐光性等の観点から一般には顔料が用いられているが、顔料では特に高輝度については市場要求を満たすことが出来なくなってきており、色材として顔料に替えて染料を用いる検討が盛んにおこなわれている。 In recent years, color filters are required to have higher brightness, higher contrast, and higher color gamut. Pigments are generally used as color materials that determine the color of color filters from the viewpoint of heat resistance, light resistance, etc. However, pigments are no longer able to meet market demands for high brightness, and colors are used. There are many studies on the use of dyes instead of pigments as materials.
　例えば、緑色画素用途においてはフタロシアニン系染料を用いる検討がなされている（例えば特許文献１参照）。 For example, studies have been made on the use of phthalocyanine dyes for green pixel applications (see, for example, Patent Document 1).
　その一方で特許文献２には、特定の光重合性化合物を含む着色樹脂組成物を用いることにより、高い濃度で顔料を含んでいても、カラーフィルタの製造における現像後の残渣を少なくできることが記載されている。 On the other hand, Patent Document 2 describes that by using a colored resin composition containing a specific photopolymerizable compound, the residue after development in the production of a color filter can be reduced even if the pigment is contained at a high concentration. Has been done.
日本国特開２０１９－１１３７３２号公報Japanese Patent Application Laid-Open No. 2019-11732 日本国特開２００８－１６４８８６号公報Japanese Patent Application Laid-Open No. 2008-164886
　本発明者らが検討を行ったところ、特許文献１に記載されている着色樹脂組成物では、プリベーク（露光工程の前に実施する塗布膜の乾燥工程）時の温度によって現像液への溶解性が大きく変化し、特に高温域ではパターンサイズが大きく変化してしまうことが見出された。これにより、精密な線幅調整が要求される、４Ｋ８Ｋを代表とする高精細なカラーフィルタが安定的に製造できない問題が明らかとなった。
　特許文献２では着色剤として顔料を含む着色樹脂組成物についてしか評価されておらず、着色剤としてフタロシアニン系染料を含む場合にどのような特性を示すか不明であった。 As a result of studies by the present inventors, the colored resin composition described in Patent Document 1 has solubility in a developing solution depending on the temperature at the time of prebaking (drying step of the coating film carried out before the exposure step). It was found that the pattern size changed significantly, especially in the high temperature range. As a result, it has become clear that a high-definition color filter typified by 4K8K, which requires precise line width adjustment, cannot be stably manufactured.
In Patent Document 2, only a colored resin composition containing a pigment as a colorant was evaluated, and it was unclear what kind of characteristics would be exhibited when a phthalocyanine dye was contained as a colorant.
　そこで本発明は、現像液溶解性及びパターニング特性に対する、プリベークの温度変化の影響が小さい着色樹脂組成物を提供することを目的とする。 Therefore, an object of the present invention is to provide a colored resin composition having a small influence of a prebake temperature change on the developer solubility and patterning characteristics.
　本発明者らが鋭意検討を行った結果、特定の着色剤に、特定の光重合性モノマーを併用することで、上記課題を解決することができることを見出し、本発明に至った。
　すなわち、本発明は以下の［１］～［６］の構成を有する。 As a result of diligent studies by the present inventors, they have found that the above problems can be solved by using a specific photopolymerizable monomer in combination with a specific colorant, and have reached the present invention.
That is, the present invention has the following configurations [1] to [6].
［１］（Ａ）着色剤、（Ｂ）溶剤、（Ｃ）アルカリ可溶性樹脂、（Ｄ）光重合開始剤、及び（Ｅ）光重合性モノマーを含有する着色樹脂組成物であって、
　前記（Ａ）着色剤が、下記一般式（１）で表される化学構造を有するフタロシアニン化合物を含み、
　前記（Ｅ）光重合性モノマーが、下記一般式（Ｉ）で表される部分構造を有する光重合性モノマー（ｅ１）を含むことを特徴とする着色樹脂組成物。 [1] A colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer.
The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1).
A colored resin composition, wherein the photopolymerizable monomer (E) contains a photopolymerizable monomer (e1) having a partial structure represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
（式（１）中、Ａ1～Ａ16は各々独立に、水素原子、ハロゲン原子、又は下記一般式（２）で表される基を表す。ただし、Ａ1～Ａ16のうち１つ以上はフッ素原子を表し、かつ、Ａ1～Ａ16のうち１つ以上は下記一般式（２）で表される基を表す。） (In the formula (1), A 1 to A 16 each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), but one or more of A 1 to A 16 . Represents a fluorine atom, and one or more of A 1 to A 16 represents a group represented by the following general formula (2).)
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（式（２）中、Ｘは２価の連結基を表す。式（２）中のベンゼン環は任意の置換基を有していてもよい。＊は結合手を表す。） (In the formula (2), X represents a divalent linking group. The benzene ring in the formula (2) may have an arbitrary substituent. * Represents a bond.)
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
（式（Ｉ）中、Ｒ1は炭素数２以上のアルキレン基を表す。
　Ｒ2は、水素原子又はメチル基を表す。
　ｎは１以上の整数を表す。
　＊は結合手を表す。） (In the formula (I), R 1 represents an alkylene group having 2 or more carbon atoms.
R 2 represents a hydrogen atom or a methyl group.
n represents an integer of 1 or more.
* Represents a bond. )
［２］前記光重合性モノマー（ｅ１）が、下記一般式（ＩＩ）で表される化合物である、［１］の着色樹脂組成物。 [2] The colored resin composition of [1], wherein the photopolymerizable monomer (e1) is a compound represented by the following general formula (II).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
（式（ＩＩ）中、Ｒ1、Ｒ2及びｎは、前記式（Ｉ）と同義である。
　Ｚは、直接結合、酸素原子、硫黄原子、２～４価の脂肪族炭化水素基、４価の炭素原子、２～４価の非芳香族複素環基、２～４価の芳香族環基、又は下記一般式（ＩＩＩ）で表される部分構造を表す。
　ｐは、２～６の整数を表す。
　なお、一分子中に含まれる複数の下記一般式（ＩＩ’）で表される構造 (In the formula (II), R 1 , R 2 and n are synonymous with the above formula (I).
Z is a direct bond, an oxygen atom, a sulfur atom, a 2- to 4-valent aliphatic hydrocarbon group, a 4-valent carbon atom, a 2- to 4-valent non-aromatic heterocyclic group, and a 2- to 4-valent aromatic ring group. , Or a partial structure represented by the following general formula (III).
p represents an integer of 2 to 6.
In addition, a plurality of structures contained in one molecule and represented by the following general formula (II').
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
は、同じでもよく、また異なっていてもよい。） May be the same or different. )
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（式（ＩＩＩ）中、＊は結合手を表す。） (In formula (III), * represents a bond.)
［３］前記（Ａ）着色剤の含有割合が、全固形分中に１０質量％以上である、［１］又は［２］の着色樹脂組成物。
［４］前記光重合性モノマー（ｅ１）の含有割合が、全固形分中に１質量％以上である、［１］～［３］のいずれかの着色樹脂組成物。
［５］［１］～［４］のいずれかの着色樹脂組成物を用いて作成した画素を有する、カラーフィルタ。
［６］［５］のカラーフィルタを有する、画像表示装置。 [3] The colored resin composition according to [1] or [2], wherein the content ratio of the colorant (A) is 10% by mass or more in the total solid content.
[4] The colored resin composition according to any one of [1] to [3], wherein the content ratio of the photopolymerizable monomer (e1) is 1% by mass or more in the total solid content.
[5] A color filter having pixels created by using the colored resin composition according to any one of [1] to [4].
[6] An image display device having the color filters of [5].
　本発明によれば、現像液溶解性及びパターニング特性に対する、プリベークの温度変化の影響が小さい着色樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a colored resin composition having a small influence of a prebake temperature change on the developer solubility and patterning characteristics.
図１は、本発明のカラーフィルタを有する有機ＥＬ表示素子の一例を示す断面概略図である。FIG. 1 is a schematic cross-sectional view showing an example of an organic EL display element having the color filter of the present invention.
　本発明において、「重量平均分子量」とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量（Ｍｗ）をさす。
　本発明において、「全固形分」とは、着色樹脂組成物における溶剤以外の全成分を意味するものとする。溶剤以外の成分が常温で液体であっても、その成分は溶剤には含めず、全固形分に含める。
　本発明において、「アミン価」とは、特に断りのない限り有効固形分換算のアミン価を表し、分散剤の固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表される値である。
　本発明において、「Ｃ．Ｉ．」とはカラーインデックスを意味する。 In the present invention, the "weight average molecular weight" refers to the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the "total solid content" means all components other than the solvent in the colored resin composition. Even if the components other than the solvent are liquid at room temperature, the components are not included in the solvent and are included in the total solid content.
In the present invention, the "amine value" represents an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH.
In the present invention, "CI" means a color index.
［１］着色樹脂組成物の構成成分
　本発明に係る着色樹脂組成物は、（Ａ）着色剤、（Ｂ）溶剤、（Ｃ）アルカリ可溶性樹脂、（Ｄ）光重合開始剤、及び（Ｅ）光重合性モノマーを含む。さらに要すれば、上記成分以外の他の添加物等が配合されていてもよい。 [1] Components of Colored Resin Composition The colored resin composition according to the present invention comprises (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E). Contains photopolymerizable monomers. Further, if necessary, additives and the like other than the above-mentioned components may be blended.
［１－１］（Ａ）着色剤
　本発明の着色樹脂組成物に含まれる（Ａ）着色剤は、下記一般式（１）で表される化学構造を有するフタロシアニン化合物（以下、「フタロシアニン化合物（１）」と称する場合がある。）を含む。 [1-1] (A) Colorant The (A) colorant contained in the coloring resin composition of the present invention is a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter, "phthalocyanine compound (hereinafter," phthalocyanine compound (hereinafter, "phthalocyanine compound"). It may be referred to as "1)".)
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（１）中、Ａ1～Ａ16は各々独立に、水素原子、ハロゲン原子、又は下記一般式（２）で表される基を表す。ただし、Ａ1～Ａ16のうち１つ以上はフッ素原子を表し、かつ、Ａ1～Ａ16のうち１つ以上は下記一般式（２）で表される基を表す。 In the formula (1), A 1 to A 16 independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A 1 to A 16 represents a fluorine atom, and one or more of A 1 to A 16 represents a group represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（２）中、Ｘは２価の連結基を表す。式（２）中のベンゼン環は任意の置換基を有していてもよい。＊は結合手を表す。 In formula (2), X represents a divalent linking group. The benzene ring in the formula (2) may have an arbitrary substituent. * Represents a bond.
　本発明の着色樹脂組成物における（Ａ）着色剤はフタロシアニン化合物（１）を含む。フタロシアニン化合物（１）はフタロシアニン骨格を構成する水素原子の１つ以上が原子半径の小さいフッ素原子で置換されており、フタロシアニン化合物（１）同士の会合を阻害しにくい構造であることから、加熱等で分子間距離が縮まった際に会合体を形成する事によって、加熱による輝度低下を抑制できると考えられる。また、会合後においても、その粒子径は顔料よりも小さくなっていると考えられ、熱硬化処理後のパターンにおいて輝度が高くなると考えられる。 The (A) colorant in the colored resin composition of the present invention contains a phthalocyanine compound (1). Since one or more of the hydrogen atoms constituting the phthalocyanine skeleton of the phthalocyanine compound (1) are replaced with fluorine atoms having a small atomic radius and the structure does not easily inhibit the association between the phthalocyanine compounds (1), heating or the like is performed. It is considered that the decrease in brightness due to heating can be suppressed by forming an aggregate when the intermolecular distance is shortened. Further, it is considered that the particle size is smaller than that of the pigment even after the association, and the brightness is considered to be high in the pattern after the thermosetting treatment.
　本発明の着色樹脂組成物をプリベークした後の塗膜において、フタロシアニン化合物（１）は粒子径の小さい会合体となって密に存在していると考えられ、それに続く現像工程において現像液の塗膜への浸透と溶解が抑制されやすい状態になると考えられる。そのため、残留溶媒の量によって得られるパターン形状が変化しやすく、例えば、ホール径のプリベーク温度依存性が悪化しやすいと考えられる。 It is considered that the phthalocyanine compound (1) is densely present as an aggregate having a small particle size in the coating film after prebaking the colored resin composition of the present invention, and the developer is applied in the subsequent developing step. It is considered that the penetration and dissolution into the membrane are likely to be suppressed. Therefore, it is considered that the pattern shape obtained is likely to change depending on the amount of the residual solvent, and for example, the prebake temperature dependence of the hole diameter is likely to be deteriorated.
（Ａ1～Ａ16）
　前記式（１）中、Ａ1～Ａ16は各々独立に、水素原子、ハロゲン原子、又は下記一般式（２）で表される基を表す。ただし、Ａ1～Ａ16のうち１つ以上はフッ素原子を表し、かつ、Ａ1～Ａ16のうち１つ以上は下記一般式（２）で表される基を表す。 (A 1 to A 16 )
In the above formula (1), A 1 to A 16 independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A 1 to A 16 represents a fluorine atom, and one or more of A 1 to A 16 represents a group represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（２）中、Ｘは２価の連結基を表す。式（２）中のベンゼン環は任意の置換基を有していてもよい。＊は結合手を表す。 In formula (2), X represents a divalent linking group. The benzene ring in the formula (2) may have an arbitrary substituent. * Represents a bond.
　Ａ1～Ａ16におけるハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子が挙げられる。高輝度化の観点からフッ素原子が好ましい。
　また、Ａ1～Ａ16のうち６つ以上はフッ素原子であることが好ましく、７つ以上がより好ましく、８つ以上がさらに好ましく、また、１５以下であり、１２以下が好ましく、１０以下がより好ましい。前記下限値以上とすることでフタロシアニン化合物（１）の安定性が向上する傾向があり、また、前記上限値以下とすることで着色樹脂組成物中の分散剤や溶剤との親和性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、Ａ1～Ａ16のうちフッ素原子を表す置換基の個数は、１～１５であり、６～１２が好ましく、７～１２がより好ましく、８～１０がさらに好ましい。 Examples of the halogen atom in A 1 to A 16 include a fluorine atom, a chlorine atom, and a bromine atom. Fluorine atoms are preferable from the viewpoint of increasing brightness.
Further, 6 or more of A 1 to A 16 are preferably fluorine atoms, 7 or more are more preferable, 8 or more are further preferable, 15 or less, 12 or less are preferable, and 10 or less is preferable. More preferred. When it is at least the above lower limit value, the stability of the phthalocyanine compound (1) tends to be improved, and when it is at least the above upper limit value, the affinity with the dispersant and the solvent in the colored resin composition is improved. Tend. The above upper and lower limits can be combined arbitrarily. For example, the number of substituents representing a fluorine atom in A 1 to A 16 is 1 to 15, preferably 6 to 12, more preferably 7 to 12, and even more preferably 8 to 10.
（Ｘ）
　式（２）中のＸは２価の連結基を表す。２価の連結基としては特に限定されないが、酸素原子、硫黄原子、又は－Ｎ（Ｒa1）－基（Ｒa1は水素原子、又は炭素数１～６の脂肪族炭化水素基を表す。）が挙げられる。焼成時の安定性の観点から、酸素原子又は硫黄原子が好ましく、酸素原子がより好ましい。 (X)
X in the formula (2) represents a divalent linking group. The divalent linking group is not particularly limited, but is an oxygen atom, a sulfur atom, or a -N (R a1 ) -group (R a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms). Can be mentioned. From the viewpoint of stability during calcination, an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.
（ベンゼン環が有していてもよい置換基）
　式（２）中のベンゼン環は任意の置換基を有していてもよい。置換基としては特に限定されないが、例えば、ハロゲン原子、アルキル基（－ＲA基）、アルコキシ基（－ＯＲA基（ただし、ＲAはアルキル基を表す。））、アルコキシカルボニル基（－ＣＯＯＲA基（ただし、ＲAはアルキル基を表す。））、アリール基（－ＲB基）、アリールオキシ基（－ＯＲB基（ただし、ＲBはアリール基を表す。））、アリールオキシカルボニル基（－ＣＯＯＲB基（ただし、ＲBはアリール基を表す。））が挙げられる。現像溶解性や輝度の観点から、アルコキシカルボニル基が好ましい。 (Substituents that the benzene ring may have)
The benzene ring in the formula (2) may have an arbitrary substituent. The substituent is not particularly limited, but is, for example, a halogen atom, an alkyl group ( -RA group), an alkoxy group (-OR A group (where RA represents an alkyl group)), an alkoxycarbonyl group (-COOR). A group (where RA represents an alkyl group)), aryl group (-RB group), aryloxy group (-OR B group (where RB represents an aryl group )), aryloxycarbonyl A group (-COOR B group (where RB represents an aryl group)) is mentioned. An alkoxycarbonyl group is preferable from the viewpoint of development solubility and brightness.
　これらの基に含まれるアルキル基は、直鎖状でも、分岐鎖状でも、環状でもよいが、有機溶剤との親和性の観点から直鎖状であることが好ましい。
　アルキル基の炭素数は特に限定されないが、通常１以上、２以上が好ましく、また、６以下が好ましく、５以下がより好ましく、４以下がさらに好ましい。前記下限値以上とすることで、凝集を抑制し、異物抑制となる傾向があり、また、前記上限値以下とすることで、溶媒親和性が向上し、経時安定性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、アルキル基の炭素数は１～６が好ましく、１～５がより好ましく、２～４がさらに好ましい。
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基などが挙げられ、凝集抑制の観点から、メチル基又はエチル基が好ましく、エチル基がより好ましい。 The alkyl group contained in these groups may be linear, branched or cyclic, but is preferably linear from the viewpoint of affinity with an organic solvent.
The number of carbon atoms of the alkyl group is not particularly limited, but is usually preferably 1 or more, 2 or more, preferably 6 or less, more preferably 5 or less, still more preferably 4 or less. When it is set to the lower limit value or more, aggregation tends to be suppressed and foreign matter is suppressed, and when it is set to the upper limit value or less, the solvent affinity tends to be improved and the stability with time tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 5, and even more preferably 2 to 4.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like. From the viewpoint of suppressing aggregation, a methyl group or an ethyl group is preferable, and an ethyl group is more preferable.
　これらの基に含まれるアリール基は、芳香族炭化水素環基であってもよく、芳香族複素環基であってもよい。
　アリール基の炭素数は特に限定されないが、通常４以上、６以上が好ましく、また、１２以下が好ましく、１０以下がより好ましく、８以下がさらに好ましい。前記下限値以上とすることで立体反発による凝集を抑制する傾向があり、また、前記上限値以下とすることで溶媒親和性が向上し、経時安定性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができ、例えば、アリール基の炭素数は４～１２が好ましく、４～１０がより好ましく、６～８がさらに好ましい。 The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
The number of carbon atoms of the aryl group is not particularly limited, but is usually preferably 4 or more and 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When it is at least the above lower limit value, there is a tendency to suppress agglutination due to steric repulsion, and when it is at least the above upper limit value, solvent affinity is improved and stability over time tends to be improved. The above upper limit and lower limit can be arbitrarily combined. For example, the aryl group preferably has 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms.
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。芳香族炭化水素環基としては、例えば、１個の遊離原子価を有する、ベンゼン環、ナフタレン環、ペンタレン環、インデン環、アズレン環、ヘプタレン環が挙げられる。
　芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、１個の遊離原子価を有する、フラン環、チオフェン環、ピロール環、２Ｈ－ピラン環、４Ｈ－チオピラン環、ピリジン環、１，３－オキサゾール環、イソオキサゾール環、１，３－チアゾール環、イソチアゾール環、イミダゾール環、ピラゾール環、フラザン環、ピラジン環、ピリミジン環、ピリダジン環、１，３，５－トリアジン環、ベンゾフラン環 、２－ベンゾフラン環、ベンゾチオフェン環、２－ベンゾチオフェン環、１Ｈ－ピロリジン環、インドール環、イソインドール環、インドリジン環、２Ｈ－１－ベンゾピラン環、１Ｈ－２－ベンゾピラン環、キノリン環、イソキノリン環、４Ｈ－キノリジン環、ベンゾイミダゾール環、１Ｈ－インダゾール環、キノキサリン環、キナゾリン環、シンノリン環、フタラジン環、１，８－ナフチリジン環、プリン環、プテリジン環が挙げられる。 The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring having one free valence.
The aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, and an isooxazole having one free valence. Ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, frazane ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene Ring, 2-benzothiophene ring, 1H-pyrrolidin ring, indole ring, isoindole ring, indridin ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, benzo Examples thereof include an imidazole ring, a 1H-imidazole ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a 1,8-naphthylidine ring, a purine ring, and a pteridine ring.
　式（２）中のベンゼン環が任意の置換基を有する場合、その置換数は特に限定されないが、染料分子同士でπ－πスタッキングして耐熱性が向上し、染料の分解による輝度低下が抑制されるとの観点から、ベンゼン環１つに対して置換数が１であることが好ましい。
　式（２）中のベンゼン環が任意の置換基を有する場合、その置換位置は、ｏ－位でも、ｍ－位でも、ｐ－位でもよいが、最密構造をとるスタッキングが可能になるとの観点から、ｐ－位が好ましい。 When the benzene ring in the formula (2) has an arbitrary substituent, the number of substitutions is not particularly limited, but the heat resistance is improved by π-π stacking between the dye molecules, and the decrease in brightness due to the decomposition of the dye is suppressed. From the viewpoint of this, it is preferable that the number of substitutions is 1 for one benzene ring.
When the benzene ring in the formula (2) has an arbitrary substituent, the substitution position may be the o-position, the m-position, or the p-position, but stacking having a close-packed structure is possible. From the viewpoint, the p-position is preferable.
　Ａ1～Ａ16のうち１つ以上はフッ素原子を表すが、フタロシアニン化合物（１）の二分子間の会合体形成による輝度向上の観点から、Ａ1～Ａ4のうち１つ以上がフッ素原子であり、Ａ5～Ａ8のうち１つ以上がフッ素原子であり、Ａ9～Ａ12のうち１つ以上がフッ素原子であり、かつ、Ａ13～Ａ16のうち１つ以上がフッ素原子であることが好ましく；Ａ1～Ａ4のうち２つ以上がフッ素原子であり、Ａ5～Ａ8のうち２つ以上がフッ素原子であり、Ａ9～Ａ12のうち２つ以上がフッ素原子であり、かつ、Ａ13～Ａ16のうち２つ以上がフッ素原子であることがより好ましい。 One or more of A 1 to A 16 represent a fluorine atom, but one or more of A 1 to A 4 is a fluorine atom from the viewpoint of improving brightness by forming an aggregate between two molecules of the phthalocyanine compound (1). At least one of A 5 to A 8 is a fluorine atom, one or more of A 9 to A 12 is a fluorine atom, and one or more of A 13 to A 16 is a fluorine atom. 2 or more of A 1 to A 4 are fluorine atoms, two or more of A 5 to A 8 are fluorine atoms, and two or more of A 9 to A 12 are fluorine atoms. It is more preferable that the atom is an atom and two or more of A 13 to A 16 are fluorine atoms.
　Ａ1～Ａ16のうち１つ以上は式（２）で表される基を表すが、有機溶剤への溶解性や輝度の観点から、Ａ1～Ａ4のうち１つ以上が式（２）で表される基であり、Ａ5～Ａ8のうち１つ以上が式（２）で表される基であり、Ａ9～Ａ12のうち１つ以上が式（２）で表される基であり、かつ、Ａ13～Ａ16のうち１つ以上が式（２）で表される基であることが好ましく；Ａ1～Ａ4のうち２つ以上が式（２）で表される基であり、Ａ5～Ａ8のうち２つ以上が式（２）で表される基であり、Ａ9～Ａ12のうち２つ以上が式（２）で表される基であり、かつ、Ａ13～Ａ16のうち２つ以上が式（２）で表される基であることがより好ましい。
　効率的なスタッキングにより輝度低下が抑制されるとの観点から、Ａ2、Ａ3、Ａ6、Ａ7、Ａ10、Ａ11、Ａ14、及びＡ15が式（２）で表される基であり、かつ、Ａ1、Ａ4、Ａ5、Ａ8、Ａ9、Ａ12、Ａ13、及びＡ16がハロゲン原子であることが好ましく；Ａ2、Ａ3、Ａ6、Ａ7、Ａ10、Ａ11、Ａ14、及びＡ15が式（２）で表される基であり、かつ、Ａ1、Ａ4、Ａ5、Ａ8、Ａ9、Ａ12、Ａ13、及びＡ16がフッ素原子であることが特に好ましい。 One or more of A 1 to A 16 represents a group represented by the formula (2), but one or more of A 1 to A 4 represents a group represented by the formula (2) from the viewpoint of solubility in an organic solvent and brightness. ), One or more of A 5 to A 8 is a group represented by the formula (2), and one or more of A 9 to A 12 is represented by the formula (2). It is preferable that one or more of A 13 to A 16 is a group represented by the formula (2); two or more of A 1 to A 4 are represented by the formula (2). Two or more of A 5 to A 8 are groups represented by the formula (2), and two or more of A 9 to A 12 are groups represented by the formula (2). It is more preferable that two or more of A 13 to A 16 are groups represented by the formula (2).
From the viewpoint that the decrease in brightness is suppressed by efficient stacking, A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 and A 15 are represented by the formula (2). And preferably A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 are halogen atoms; A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 and A 15 are the groups represented by the formula (2), and A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 and A. It is particularly preferred that 16 is a fluorine atom.
　フタロシアニン系染料（１）の具体例としては、例えば以下の化合物が挙げられる。 Specific examples of the phthalocyanine dye (1) include the following compounds.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　なお、上記式中、Ｅｔはエチルを表す。 In the above formula, Et represents ethyl.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　フタロシアニン系染料（１）の製造方法としては公知の方法を採用することができ、例えば、日本国特開平０５－３４５８６１号公報に記載の方法を採用することができる。 As a method for producing the phthalocyanine dye (1), a known method can be adopted, and for example, the method described in Japanese Patent Application Laid-Open No. 05-345861 can be adopted.
　（Ａ）着色剤は、フタロシアニン化合物（１）以外に、その他の着色剤を含んでいてもよい。その他の着色剤としては、顔料や染料が挙げられる。緑色画素用途に用いる場合には、例えば、緑色顔料、緑色染料、黄色顔料、黄色染料を用いることが好ましい。
　緑色顔料としては、例えば、Ｃ．Ｉ．ピグメントグリーン７、３６、５８、５９、６２、６３が挙げられ、輝度の観点からＣ．Ｉ．ピグメントグリーン５８が好ましい。
　緑色染料としては、カラーインデックスで染料に分類されているものの中で、Ｃ．Ｉ．ソルベント染料として、例えば、Ｃ．Ｉ．ソルベントグリーン１、３、４、５、７、２８、２９、３２、３３、３４、３５が挙げられる。Ｃ．Ｉ．アシッド染料として、例えば、Ｃ．Ｉ．アシッド・グリーン１、３、５、９、１６、２５、２７、５０、５８、６３、６５、８０、１０４、１０５、１０６、１０９、Ｃ．Ｉ．モーダント・グリーン１、３、４、５、１０、１５、１９、２６、２９、３３、３４、３５、４１、４３、５３が挙げられる。熱焼成時の染料分解抑制の観点からＣ．Ｉ．ソルベントグリーン１、３、４、５、７、２８、２９、３２、３３、３４、３５が好ましい。 (A) The colorant may contain other colorants in addition to the phthalocyanine compound (1). Examples of other colorants include pigments and dyes. When used for green pixel applications, it is preferable to use, for example, green pigments, green dyes, yellow pigments, and yellow dyes.
Examples of the green pigment include C.I. I. Pigment Greens 7, 36, 58, 59, 62, 63, and C.I. I. Pigment Green 58 is preferred.
Among the green dyes classified as dyes by the color index, C.I. I. As a solvent dye, for example, C.I. I. Solvent greens 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 can be mentioned. C. I. As an acid dye, for example, C.I. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53. From the viewpoint of suppressing dye decomposition during heat firing, C.I. I. Solvent greens 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 are preferred.
　黄色顔料としては、例えば、Ｃ．Ｉ．ピグメントイエロー１、１：１、２、３、４、５、６、９、１０、１２、１３、１４、１６、１７、２０、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４１、４２、４３、４８、５３、５５、６１、６２、６２：１、６３、６５、７３、７４、７５，８１、８３、８６、８７、９３、９４、９５、９７、１００、１０１、１０４、１０５、１０８、１０９、１１０、１１１、１１６、１１７、１１９、１２０、１２５、１２６、１２７、１２７：１、１２８、１２９、１３３、１３４、１３６、１３７、１３８、１３９、１４２、１４７、１４８、１５０、１５１、１５３、１５４、１５５、１５７、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１８０、１８１、１８２、１８３、１８４、１８５、１８８、１８９、１９０、１９１、１９１：１、１９２、１９３、１９４、１９５、１９６、１９７、１９８、１９９、２００、２０２、２０３、２０４、２０５、２０６、２０７、２０８、及び下記式（ｉ）で表されるアゾバルビツール酸のニッケルとの１：１錯体又はその互換異性体に、他の化合物が挿入されてなる化合物（以下、「式（ｉ）で表されるニッケルアゾ錯体」と称する場合がある。）が挙げられる。 Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1, 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,86,87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127: 1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and other compounds in a 1: 1 complex of azobarbituric acid represented by the following formula (i) with nickel or a compatible isomer thereof. (Hereinafter, it may be referred to as a "nickel azo complex represented by the formula (i)") in which is inserted.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　式（ｉ）で表されるニッケルアゾ錯体において挿入される他の化合物としては、例えば、下記式（ｉｉ）で表される化合物が挙げられる。 Examples of the other compound inserted in the nickel azo complex represented by the formula (i) include a compound represented by the following formula (ii).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　この中でも、高輝度および高色域の観点から、Ｃ．Ｉ．ピグメントイエロー８３、１１７、１２９、１３８、１３９、１５４、１５５、１８０、１８５、及び式（ｉ）で表されるニッケルアゾ錯体が好ましく、Ｃ．Ｉ．ピグメントイエロー８３、１３８、１３９、１８０、１８５及び式（ｉ）で表されるニッケルアゾ錯体がより好ましい。 Among these, from the viewpoint of high brightness and high color gamut, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and the nickel azo complex represented by the formula (i) are preferable. I. Pigment Yellow 83, 138, 139, 180, 185 and the nickel azo complex represented by the formula (i) are more preferable.
　黄色染料としては、例えば、バルビツール酸アゾ系染料、ピリドンアゾ系染料、ピラゾロンアゾ系染料、キノフタロン系染料、シアニン系染料が挙げられる。その具体例としては、日本国特開２０１０－１６８５３１号公報に記載の具体的化合物が挙げられる。
　黄色染料としては、カラーインデックスで染料に分類されているものの中で、Ｃ．Ｉ．ソルベント染料として、例えば、Ｃ．Ｉ．ソルベント・イエロー４、１４、１５、２３、２４、３８、６２、６３、６８、７９、８２、９４、９８、９９、１６２、１６３などが挙げられる。Ｃ．Ｉ．アシッド染料として、例えば、Ｃ．Ｉ．アシッド・グリーン１、３、５、９、１６、２５、２７、５０、５８、６３、６５、８０、１０４、１０５、１０６、１０９、Ｃ．Ｉ．アシッド・イエロー１、３、７、９、１１、１７、２３、２５、２９、３４、３６、３８、４０、４２、５４、６５、７２、７３、７６、７９、９８、９９、１１１、１１２、１１３、１１４、１１６、１１９、１２３、１２８、１３４、１３５、１３８、１３９、１４０、１４４、１５０、１５５、１５７、１６０、１６１、１６３、１６８、１６９、１７２、１７７、１７８、１７９、１８４、１９０、１９３、１９６、１９７、１９９、２０２、２０３、２０４、２０５、２０７、２１２、２１４、２２０、２２１、２２８、２３０、２３２、２３５、２３８、２４０、２４２、２４３、２５１やその誘導体が挙げられる。Ｃ．Ｉ．ダイレクト染料として、例えば、Ｃ．Ｉ．ダイレクト・イエロー２、３３、３４、３５、３８、３９、４３、４７、５０、５４、５８、６８、６９、７０、７１、８６、９３、９４、９５、９８、１０２、１０８、１０９、１２９、１３６、１３８、１４１の染料が挙げられる。Ｃ．Ｉ．モーダント染料として、例えば、Ｃ．Ｉ．モーダント・イエロー５、８、１０、１６、２０、２６、３０、３１、３３、４２、４３、４５、５６、６１、６２、６５の染料が挙げられる。好ましくは、Ｃ．Ｉ．ソルベント・イエロー４、１４、１５、２３、２４、３８、６２、６３、６８、８２、９４、９８、９９、１６２、Ｃ．Ｉ．アシッド・イエロー１、３、７、９、１１、１７、２３、２５、２９、３４、３６、３８、４０、４２、５４、６５、７２、７３、７６、７９、９８、９９、１１１、１１２、１１３、１１４、１１６、１１９、１２３、１２８、１３４、１３５、１３８、１３９、１４０、１４４、１５０、１５５、１５７、１６０、１６１、１６３、１６８、１６９、１７２、１７７、１７８、１７９、１８４、１９０、１９３、１９６、１９７、１９９、２０２、２０３、２０４、２０５、２０７、２１２、２１４、２２０、２２１、２２８、２３０、２３２、２３５、２３８、２４０、２４２、２４３、２５１、２３、２５、２９、３４、４０、４２、７２、７６、９９、１１１、１１２、１１４、１１６、１６３、２４３やその誘導体が挙げられる。
　熱焼成時の染料分解抑制の観点から、Ｃ．Ｉ．ソルベント・イエロー４、１４、１５、２３、２４、３８、６２、６３、６８、７９、８２、９４、９８、９９、１６２、１６３が好ましい。 Examples of the yellow dye include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples thereof include the specific compounds described in Japanese Patent Application Laid-Open No. 2010-168531.
Among the yellow dyes classified as dyes by the color index, C.I. I. As a solvent dye, for example, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 and the like can be mentioned. C. I. As an acid dye, for example, C.I. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184. , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and their derivatives. Can be mentioned. C. I. As a direct dye, for example, C.I. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129. Examples include the dyes 136, 138 and 141. C. I. As a modern dye, for example, C.I. I. Examples include dyes of Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65. Preferably, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184. , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, 23, 25. , 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243 and derivatives thereof.
From the viewpoint of suppressing dye decomposition during heat firing, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 are preferred.
　顔料の平均一次粒子径は、通常０．２μｍ以下、好ましくは０．１μｍ以下、より好ましくは０．０４μｍ以下である。顔料の微粒化に際しては、ソルベントソルトミリングのような手法が好適に用いられる。 The average primary particle size of the pigment is usually 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.04 μm or less. When atomizing the pigment, a method such as solvent salt milling is preferably used.
　本発明の着色樹脂組成物における（Ａ）着色剤の含有割合は特に限定されないが、着色樹脂組成物の全固形分中に１０質量％以上が好ましく、１５質量％以上がより好ましく、２０質量％以上がさらに好ましく、２５質量％以上がよりさらに好ましく、３０質量％以上が特に好ましく、また、８０質量％以下が好ましく、６０質量％以下がより好ましく、５０質量％以下がさらに好ましく、４０質量％以下が特に好ましい。前記下限値以上とすることで広い色相を再現できる傾向があり、また、前記上限値以下とすることで経時安定性を担保できる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物における（Ａ）着色剤の含有割合は、着色樹脂組成物の全固形分中に１０～８０質量％が好ましく、１５～８０質量％より好ましく、２０～６０質量％がさらに好ましく、２５～５０質量％がよりさらに好ましく、３０～４０質量％が特に好ましい。 The content ratio of the (A) colorant in the colored resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, and 20% by mass in the total solid content of the colored resin composition. The above is further preferable, 25% by mass or more is further preferable, 30% by mass or more is particularly preferable, 80% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, and 40% by mass is 40% by mass. The following are particularly preferred. When it is set to the lower limit value or more, a wide hue tends to be reproduced, and when it is set to the upper limit value or less, the stability with time tends to be ensured. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the (A) colorant in the colored resin composition is preferably 10 to 80% by mass, more preferably 15 to 80% by mass, and further 20 to 60% by mass in the total solid content of the colored resin composition. Preferably, 25 to 50% by mass is even more preferable, and 30 to 40% by mass is particularly preferable.
　本発明の着色樹脂組成物におけるフタロシアニン化合物（１）の含有割合は特に限定されないが、着色樹脂組成物の全固形分中に１質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上がさらに好ましく、１０質量％以上がよりさらに好ましく、１５質量％以上が特に好ましく、また、５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下がさらに好ましく、２０質量％以下が特に好ましい。前記下限値以上とすることで輝度を向上させる傾向があり、また、前記上限値以下とすることで経時安定性を担保できる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物におけるフタロシアニン化合物（１）の含有割合は、着色樹脂組成物の全固形分中に３～５０質量％がより好ましく、５～５０質量％がさらに好ましく、１０～４０質量％がよりさらに好ましく、１５～３０質量％が特に好ましい。 The content ratio of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass in the total solid content of the colored resin composition. The above is further preferable, 10% by mass or more is further preferable, 15% by mass or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is further preferable, and 20% by mass is 20% by mass. The following are particularly preferred. When it is set to the lower limit value or more, the brightness tends to be improved, and when it is set to the upper limit value or less, the stability with time tends to be ensured. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the phthalocyanine compound (1) in the colored resin composition is more preferably 3 to 50% by mass, still more preferably 5 to 50% by mass, and 10 to 40% by mass in the total solid content of the colored resin composition. Is even more preferable, and 15 to 30% by mass is particularly preferable.
　本発明の着色樹脂組成物がその他の着色剤を含む場合、その含有割合は特に限定されないが、着色樹脂組成物の全固形分中に１質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上がさらに好ましく、７質量％以上がよりさらに好ましく、１０質量％以上が特に好ましく、また、３０質量％以下が好ましく、２５質量％以下がより好ましく、２０質量％以下がさらに好ましい。前記下限値以上とすることで広い色相を再現できる傾向があり、また、前記上限値以下とすることで経時安定性を担保できる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物がその他の着色剤を含む場合における、その含有割合は、着色樹脂組成物の全固形分中に１～３０質量％が好ましく、３～３０質量％がより好ましく、５～２５質量％がさらに好ましく、７～２５質量％がよりさらに好ましく、１０～２９質量％が特に好ましい。 When the colored resin composition of the present invention contains other colorants, the content thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more in the total solid content of the colored resin composition. 5% by mass or more is further preferable, 7% by mass or more is further preferable, 10% by mass or more is particularly preferable, 30% by mass or less is more preferable, 25% by mass or less is more preferable, and 20% by mass or less is further preferable. When it is set to the lower limit value or more, a wide hue tends to be reproduced, and when it is set to the upper limit value or less, the stability with time tends to be ensured. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains other colorants, the content ratio thereof is preferably 1 to 30% by mass, more preferably 3 to 30% by mass, and 5 to 5 to 30% by mass in the total solid content of the colored resin composition. 25% by mass is further preferable, 7 to 25% by mass is further preferable, and 10 to 29% by mass is particularly preferable.
［１－２］（Ｂ）溶剤
　（Ｂ）溶剤は、本発明の着色樹脂組成物や顔料分散液において、着色剤、アルカリ可溶性樹脂、光重合開始剤、光重合性モノマー、その他の成分を溶解又は分散させ、粘度を調節する機能を有する。
　（Ｂ）溶剤としては、各成分を溶解または分散させることができるものであればよい。 [1-2] (B) Solvent The (B) solvent dissolves a colorant, an alkali-soluble resin, a photopolymerization initiator, a photopolymerizable monomer, and other components in the colored resin composition and pigment dispersion of the present invention. Alternatively, it has a function of dispersing and adjusting the viscosity.
(B) The solvent may be any solvent that can dissolve or disperse each component.
　このような溶剤としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコール－ｔ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、メトキシメチルペンタノール、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、３－メチル－３－メトキシブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテルのようなグリコールモノアルキルエーテル類； Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether. Propropylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl Glycol monoalkyl ethers such as -3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
　エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類；
　エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、メトキシブチルアセテート、３－メトキシブチルアセテート、メトキシペンチルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブ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、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、３－メチル－３－メトキシブチルアセテートのようなグリコールアルキルエーテルアセテート類； Glycoldialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;
　エチレングリコールジアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサノールジアセテートなどのグリコールジアセテート類；
　シクロヘキサノールアセテートなどのアルキルアセテート類；
アミルエーテル、プロピルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類；
　アセトン、メチルエチルケトン、メチルアミルケトン、メチルイソプロピルケトン、メチルイソアミルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチルアミルケトン、メチルブチルケトン、メチルヘキシルケトン、メチルノニルケトン、メトキシメチルペンタノンのようなケトン類；
　エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような１価又は多価アルコール類；
　ｎ－ペンタン、ｎ－オクタン、ジイソブチレン、ｎ－ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類；
　シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類； Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamil ether, ethylisobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone. Ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
　ベンゼン、トルエン、キシレン、クメンのような芳香族炭化水素類；
　アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、γ－ブチロラクトンのような鎖状又は環状エステル類；
　３－メトキシプロピオン酸、３－エトキシプロピオン酸のようなアルコキシカルボン酸類；
　ブチルクロライド、アミルクロライドのようなハロゲン化炭化水素類；
　メトキシメチルペンタノンのようなエーテルケトン類；
　アセトニトリル、ベンゾニトリルのようなニトリル類が挙げられる。 Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methylisobutyrate, ethylene glycol acetate, ethylpropionate, propylpropionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amilk chloride;
Etheretones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.
　上記に該当する市販の溶剤としては、例えば、ミネラルスピリット、バルソル＃２、アプコ＃１８ソルベント、アプコシンナー、ソーカルソルベントＮｏ．１及びＮｏ．２、ソルベッソ＃１５０、シェルＴＳ２８　ソルベント、カルビトール、エチルカルビトール、ブチルカルビトール、メチルセロソルブ、エチルセロソルブ、エチルセロソルブアセテート、メチルセロソルブアセテート、ジグライム（いずれも商品名）が挙げられる。これらの溶媒は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of commercially available solvents corresponding to the above include mineral spirit, balsol # 2, apco # 18 solvent, apco thinner, and socal solvent No. 1 and No. 2. Solvento # 150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all are trade names). These solvents may be used alone or in combination of two or more.
　フォトリソグラフィ法にてカラーフィルタの画素を形成する場合、溶剤としては沸点が１００～２００℃（圧力１０１３．２５［ｈＰａ］条件下。以下、沸点に関しては全て同様。）の範囲の溶剤を選択するのが好ましい。より好ましくは１２０～１７０℃の沸点をもつ溶剤である。
　上記溶剤中、塗布性、表面張力などのバランスが良く、組成物中の構成成分の溶解度が比較的高い点からは、グリコールアルキルエーテルアセテート類が好ましい。 When forming the pixels of the color filter by the photolithography method, a solvent having a boiling point in the range of 100 to 200 ° C. (pressure 1013.25 [hPa] conditions; hereinafter, the boiling points are all the same) is selected as the solvent. Is preferable. More preferably, it is a solvent having a boiling point of 120 to 170 ° C.
Glycol alkyl ether acetates are preferable because they have a good balance of coatability, surface tension, etc. in the solvent and the solubility of the constituents in the composition is relatively high.
　グリコールアルキルエーテルアセテート類は、単独で使用してもよいが、他の溶剤を併用してもよい。併用する溶剤として、特に好ましいのはグリコールモノアルキルエーテル類である。中でも、特に組成物中の構成成分の溶解性の観点からプロピレングリコールモノメチルエーテルが好ましい。なお、グリコールモノアルキルエーテル類は極性が高く、添加量が多すぎると顔料が凝集しやすく、後に得られる着色樹脂組成物の粘度が上がっていくなどの保存安定性が低下する傾向があるので、グリコールモノアルキルエーテル類を併用する場合には、（Ｂ）溶剤中のグリコールモノアルキルエーテル類の割合は５質量％～３０質量％が好ましく、５質量％～２０質量％がより好ましい。 Glycol alkyl ether acetates may be used alone or in combination with other solvents. Glycol monoalkyl ethers are particularly preferable as the solvent to be used in combination. Of these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of the constituents in the composition. Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the colored resin composition obtained later tends to increase, and the storage stability tends to decrease. When the glycol monoalkyl ethers are used in combination, the proportion of the glycol monoalkyl ethers in the solvent (B) is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.
　別の態様として、１５０℃以上の沸点をもつ溶剤を併用することができる。１５０℃以上の沸点をもつ溶剤を併用することにより、着色樹脂組成物は乾燥しにくくなるが、急激に乾燥することによる顔料分散液中の構成成分の相互関係の破壊を起こし難くする効果がある。１５０℃以上の沸点をもつ溶剤を併用する場合には、（Ｂ）溶剤中の１５０℃以上の沸点をもつ溶剤の含有割合は３質量％～５０質量％が好ましく、５質量％～４０質量％がより好ましく、５質量％～３０質量％が特に好ましい。前記下限値以上とすることで、例えばスリットノズル先端で色材成分などが析出・固化して異物欠陥を惹き起こすことを回避しやすい傾向があり、また前記上限値以下とすることで組成物の乾燥速度が遅くなって減圧乾燥プロセスのタクト不良や、プリベークのピン跡といった問題を惹き起こすことを回避しやすい傾向がある。
　沸点１５０℃以上の溶剤が、グリコールアルキルエーテルアセテート類であっても、またグリコールアルキルエーテル類であってもよく、この場合は、沸点１５０℃以上の溶剤を別途含有させる必要はない。
　沸点１５０℃以上の溶剤として、好ましくは、例えば、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサノールジアセテート、トリアセチンが挙げられる。 As another embodiment, a solvent having a boiling point of 150 ° C. or higher can be used in combination. By using a solvent having a boiling point of 150 ° C. or higher in combination, the colored resin composition becomes difficult to dry, but it has an effect of making it difficult to destroy the mutual relationship of the constituents in the pigment dispersion liquid due to rapid drying. .. When a solvent having a boiling point of 150 ° C. or higher is used in combination, the content ratio of the solvent having a boiling point of 150 ° C. or higher in (B) is preferably 3% by mass to 50% by mass, preferably 5% by mass to 40% by mass. Is more preferable, and 5% by mass to 30% by mass is particularly preferable. By setting it to the above lower limit value or more, for example, it tends to be easy to prevent colorant components and the like from precipitating and solidifying at the tip of the slit nozzle to cause foreign matter defects, and by setting it to the above upper limit value or less, the composition It tends to avoid slowing down the drying process and causing problems such as poor tact in the vacuum drying process and pin marks on the prebake.
The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers, and in this case, it is not necessary to separately contain a solvent having a boiling point of 150 ° C. or higher.
The solvent having a boiling point of 150 ° C. or higher is preferably, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate. , Triacetin.
　インクジェット法にてカラーフィルタの画素を形成する場合、溶剤としては、沸点が、通常１３０℃以上３００℃以下、好ましくは１５０℃以上２８０℃以下のものが適当である。前記下限値以上とすることで、得られる塗膜の均一性が良好となる傾向があり、前記上限値以下とすることで、焼成時の残留溶剤を低減しやすい傾向がある。
　溶剤の蒸気圧は、得られる塗膜の均一性の観点から、通常１０ｍｍＨｇ以下、好ましくは５ｍｍＨｇ以下、より好ましくは１ｍｍＨｇ以下のものが使用できる。 When the pixels of the color filter are formed by the inkjet method, a solvent having a boiling point of usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower is suitable. When it is at least the above lower limit value, the uniformity of the obtained coating film tends to be good, and when it is at least the above upper limit value, there is a tendency that the residual solvent at the time of firing is easily reduced.
From the viewpoint of the uniformity of the obtained coating film, the vapor pressure of the solvent is usually 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less.
　インクジェット法によるカラーフィルタ製造において、ノズルから発せられるインクは数～数十ｐＬと非常に微細であるため、ノズル口周辺あるいは画素バンク内に着弾する前に、溶剤が蒸発してインクが濃縮・乾固する傾向がある。これを回避するためには、（Ｂ）溶剤が沸点の高い溶剤を含むことが好ましく、具体的には、沸点１８０℃以上の溶剤を含むことが好ましい。沸点が２００℃以上の溶剤を含むことがより好ましく、沸点が２２０℃以上の溶剤を含むことが特に好ましい。沸点１８０℃以上である溶剤の（Ｂ）溶剤中の含有割合は５０質量％以上であることが好ましく、７０質量％以上がより好ましく、９０質量％以上が最も好ましい。前記下限値以上とすることで、液滴からの溶剤の蒸発防止効果が十分に発揮されやすい傾向がある。 In the manufacture of color filters by the inkjet method, the ink emitted from the nozzle is extremely fine, ranging from several to several tens of pL, so the solvent evaporates and the ink concentrates and dries before landing around the nozzle opening or in the pixel bank. Tends to harden. In order to avoid this, it is preferable that the solvent (B) contains a solvent having a high boiling point, and specifically, it is preferable to contain a solvent having a boiling point of 180 ° C. or higher. It is more preferable to contain a solvent having a boiling point of 200 ° C. or higher, and it is particularly preferable to contain a solvent having a boiling point of 220 ° C. or higher. The content ratio of the solvent having a boiling point of 180 ° C. or higher in the solvent (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more. By setting the value to the lower limit or more, the effect of preventing evaporation of the solvent from the droplets tends to be sufficiently exhibited.
　沸点１８０℃以上の溶剤として、例えば前述の各種溶剤の中ではジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサノールジアセテート、トリアセチンなどが挙げられる。
　着色樹脂組成物の粘度調整や固形分の溶解度調整のために、沸点が１８０℃より低い溶剤を含んでもよい。このような溶剤としては、低粘度で溶解性が高く、低表面張力である溶剤が好ましく、例えば、エーテル類、エステル類、ケトン類が好ましい。中でも、例えば、シクロヘキサノン、ジプロピレングリコールジメチルエーテル、シクロヘキサノールアセテートが好ましい。 As a solvent having a boiling point of 180 ° C. or higher, for example, among the various solvents mentioned above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6- Hexanol diacetate, triacetin and the like can be mentioned.
A solvent having a boiling point lower than 180 ° C. may be contained for adjusting the viscosity of the colored resin composition and adjusting the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and for example, ethers, esters, and ketones are preferable. Of these, for example, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferable.
　一方、溶剤がアルコール類を含有すると、インクジェット法における吐出安定性が劣化する場合がある。アルコール類を併用する場合には、（Ｂ）溶剤中のアルコール類の含有割合は２０質量％以下とすることが好ましく、１０質量％以下がより好ましく、５質量％以下が特に好ましい。 On the other hand, if the solvent contains alcohols, the ejection stability in the inkjet method may deteriorate. When alcohols are used in combination, the content ratio of alcohols in the solvent (B) is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
　本発明の着色樹脂組成物に占める溶剤の含有割合は特に限定されないが、その上限は、通常９９質量％以下、好ましくは９０質量％以下、より好ましくは８５質量％以下である。前記上限値以下とすることで塗布膜を形成しやすくなる傾向がある。一方で、溶剤含有割合の下限は、塗布に適した粘性などを考慮して、通常７０質量％以上、好ましくは７５質量％以上、より好ましくは８０質量％以上である。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物に占める溶剤の含有割合は７０～９９質量％が好ましく、７５～９０質量％がより好ましく、８０～８５質量％がさらに好ましい。 The content ratio of the solvent in the colored resin composition of the present invention is not particularly limited, but the upper limit thereof is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. When the value is not more than the upper limit, the coating film tends to be easily formed. On the other hand, the lower limit of the solvent content ratio is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more in consideration of viscosity suitable for coating. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the solvent in the colored resin composition is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, still more preferably 80 to 85% by mass.
［１－３］（Ｃ）アルカリ可溶性樹脂
　本発明の着色樹脂組成物は、（Ｃ）アルカリ可溶性樹脂を含有する。（Ｃ）アルカリ可溶性樹脂を含有することで、光重合による膜硬化性と現像液による溶解性を両立することができる。
　（Ｃ）アルカリ可溶性樹脂としては、例えば日本国特開平７－２０７２１１号公報、日本国特開平８－２５９８７６号公報、日本国特開平１０－３００９２２号公報、日本国特開平１１－１４０１４４号公報、日本国特開平１１－１７４２２４号公報、日本国特開２０００－５６１１８号公報、日本国特開２００３－２３３１７９号公報に記載される公知の高分子化合物を使用することができる。中でも好ましくは下記（Ｃ－１）～（Ｃ－５）の樹脂が挙げられる。
　（Ｃ－１）：エポキシ基含有（メタ）アクリレートと、他のラジカル重合性単量体との共重合体に対し、該共重合体が有するエポキシ基の少なくとも一部に不飽和一塩基酸を付加させてなる樹脂、或いは該付加反応により生じた水酸基の少なくとも一部に多塩基酸無水物を付加させて得られる、アルカリ可溶性樹脂（以下「樹脂（Ｃ－１）」と称する場合がある。）
　（Ｃ－２）主鎖にカルボキシル基を含有する直鎖状アルカリ可溶性樹脂（以下、「樹脂（Ｃ－２）」と称する場合がある。）
　（Ｃ－３）前記樹脂（Ｃ－２）のカルボキシル基部分に、エポキシ基含有不飽和化合物を付加させた樹脂（以下、「樹脂（Ｃ－３）」と称する場合がある。）
　（Ｃ－４）（メタ）アクリル系樹脂（以下、「樹脂（Ｃ－４）」と称する場合がある。）
　（Ｃ－５）カルボキシル基を有するエポキシ（メタ）アクリレート樹脂（以下、「樹脂（Ｃ－５）」と称する場合がある。）
　このうち特に好ましくは樹脂（Ｃ－１）が挙げられる。 [1-3] (C) Alkali-soluble resin The colored resin composition of the present invention contains (C) an alkali-soluble resin. (C) By containing the alkali-soluble resin, it is possible to achieve both film curability by photopolymerization and solubility by a developing solution.
Examples of the alkali-soluble resin include Japanese Patent Laid-Open No. 7-2072111, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, and Japanese Patent Application Laid-Open No. 11-140144. Known polymer compounds described in Japanese Patent Laid-Open No. 11-174224, Japanese Patent Application Laid-Open No. 2000-563118, and Japanese Patent Application Laid-Open No. 2003-233179 can be used. Of these, the following resins (C-1) to (C-5) are preferable.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. It may be referred to as an alkali-soluble resin (hereinafter referred to as "resin (C-1)") obtained by adding a polybasic acid anhydride to at least a part of the added resin or the hydroxyl group generated by the addition reaction. )
(C-2) A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter, may be referred to as "resin (C-2)").
(C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter, may be referred to as "resin (C-3)").
(C-4) (Meta) acrylic resin (hereinafter, may be referred to as "resin (C-4)")
(C-5) Epoxy (meth) acrylate resin having a carboxyl group (hereinafter, may be referred to as "resin (C-5)").
Of these, resin (C-1) is particularly preferable.
　樹脂（Ｃ－２）～（Ｃ－５）は、アルカリ性の現像液によって溶解され、目的とする現像処理が遂行される程度に溶解性を有するものであればよく、各々、特開２００９－０２５８１３号公報に同項目として記載されている樹脂を好ましく採用することができる。 The resins (C-2) to (C-5) may be dissolved in an alkaline developer and have solubility to the extent that the desired developing treatment can be carried out, and each of them may be Japanese Patent Application Laid-Open No. 2009-025813. The resin described as the same item in Japanese Patent Publication No. can be preferably adopted.
（Ｃ－１）エポキシ基含有（メタ）アクリレートと、他のラジカル重合性単量体との共重合体に対し、該共重合体が有するエポキシ基の少なくとも一部に不飽和一塩基酸を付加させてなる樹脂、或いは該付加反応により生じた水酸基の少なくとも一部に多塩基酸無水物を付加させて得られるアルカリ可溶性樹脂
　樹脂（Ｃ－１）の好ましい態様の１つとして、「エポキシ基含有（メタ）アクリレート５～９０モル％と、他のラジカル重合性単量体１０～９５モル％との共重合体に対し、該共重合体が有するエポキシ基の１０～１００モル％に不飽和一塩基酸を付加させてなる樹脂、或いは該付加反応により生じた水酸基の１０～１００モル％に多塩基酸無水物を付加させて得られるアルカリ可溶性樹脂」が挙げられる。 (C-1) An unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer of the epoxy group-containing (meth) acrylate and another radically polymerizable monomer. As one of the preferred embodiments of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, the resin is "containing an epoxy group". The (meth) acrylate is unsaturated with 10 to 100 mol% of the epoxy group of the copolymer with respect to the polymer of 5 to 90 mol% of the acrylate and 10 to 95 mol% of the other radically polymerizable monomer. Examples thereof include a resin obtained by adding a basic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.
　エポキシ基含有（メタ）アクリレートとしては、例えば、グリシジル（メタ）アクリレート、３，４－エポキシブチル（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、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテルが例示できる。中でもグリシジル（メタ）アクリレートが好ましい。これらのエポキシ基含有（メタ）アクリレートは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate glycidyl ether can be exemplified. Of these, glycidyl (meth) acrylate is preferable. One of these epoxy group-containing (meth) acrylates may be used alone, or two or more thereof may be used in combination.
　エポキシ基含有（メタ）アクリレートと共重合させる他のラジカル重合性単量体としては、下記一般式（Ｖ）で表される構造を有するモノ（メタ）アクリレートが好ましい。 As the other radically polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate, a mono (meth) acrylate having a structure represented by the following general formula (V) is preferable.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（Ｖ）中、Ｒ91～Ｒ98は各々独立して、水素原子、又は炭素数１～３のアルキル基を表す。なお、Ｒ96とＲ98、又はＲ95とＲ97とが、互いに連結して環を形成していてもよい。
　式（Ｖ）において、Ｒ96とＲ98、又はＲ95とＲ97とが連結して形成される環は、脂肪族環であるのが好ましく、飽和又は不飽和の何れでもよく、又、炭素数が５～６であるのが好ましい。 In the formula (V), R 91 to R 98 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, R 96 and R 98 , or R 95 and R 97 may be connected to each other to form a ring.
In the formula (V), the ring formed by connecting R 96 and R 98 or R 95 and R 97 is preferably an aliphatic ring, which may be saturated or unsaturated, and may be carbon. The number is preferably 5-6.
　中でも、式（Ｖ）で表される構造としては、下記一般式（Ｖａ）、（Ｖｂ）、又は（Ｖｃ）で表される構造が好ましい。
　アルカリ可溶性樹脂にこれらの構造を導入することによって、本発明の着色樹脂組成物をカラーフィルタ形成用に使用する場合に、該着色樹脂組成物の耐熱性が向上し、該着色樹脂組成物を用いて形成された画素の強度が増す傾向がある。 Among them, as the structure represented by the formula (V), the structure represented by the following general formula (Va), (Vb), or (Vc) is preferable.
By introducing these structures into the alkali-soluble resin, when the colored resin composition of the present invention is used for forming a color filter, the heat resistance of the colored resin composition is improved, and the colored resin composition is used. The strength of the formed pixels tends to increase.
　式（Ｖ）で表される構造を有するモノ（メタ）アクリレートは、１種を単独で用いてもよく、２種以上を併用してもよい。 As the mono (meth) acrylate having the structure represented by the formula (V), one type may be used alone, or two or more types may be used in combination.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（Ｖ）で表される構造を有するモノ（メタ）アクリレートとしては、式（Ｖ）で表される構造を有する限り公知の各種のモノ（メタ）アクリレートが使用できるが、特に下記一般式（ＶＩ）で表されるモノ（メタ）アクリレートが好ましい。 As the mono (meth) acrylate having the structure represented by the formula (V), various known mono (meth) acrylates can be used as long as they have the structure represented by the formula (V), and in particular, the following general formula ( The mono (meth) acrylate represented by VI) is preferable.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　式（ＶＩ）中、Ｒ89は水素原子又はメチル基を表し、Ｒ90は式（Ｖ）で表される構造を表す。 In the formula (VI), R 89 represents a hydrogen atom or a methyl group, and R 90 represents a structure represented by the formula (V).
　エポキシ基含有（メタ）アクリレートと他のラジカル重合性単量体との共重合体において式（ＶＩ）で表されるモノ（メタ）アクリレートに由来する繰り返し単位が含まれる場合、式（ＶＩ）で表されるモノ（メタ）アクリレートに由来する繰り返し単位の含有割合は、他のラジカル重合性単量体に由来する繰り返し単位中、５～９０モル％が好ましく、１０～７０モル％がさらに好ましく、１５～５０モル％が特に好ましい。 When a repeating unit derived from a mono (meth) acrylate represented by the formula (VI) is contained in a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, the formula (VI) is used. The content ratio of the repeating unit derived from the represented mono (meth) acrylate is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, among the repeating units derived from other radically polymerizable monomers. 15-50 mol% is particularly preferred.
　式（ＶＩ）で表されるモノ（メタ）アクリレート以外の他のラジカル重合性単量体としては、特に限定されるものではないが具体的には、例えば、スチレン、スチレンのα－、ｏ－、ｍ－、ｐ－アルキル、ニトロ、シアノ、アミド、エステル誘導体等のビニル芳香族類；ブタジエン、２，３－ジメチルブタジエン、イソプレン、クロロプレン等のジエン類；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸－ｎ－プロピル、（メタ）アクリル酸－ｉｓｏ－プロピル、（メタ）アクリル酸－ｎ－ブチル、（メタ）アクリル酸－ｓｅｃ－ブチル、（メタ）アクリル酸－ｔｅｒｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸イソアミル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸－２－エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸－２－メチルシクロヘキシル、（メタ）アクリル酸ジシクロヘキシル、（メタ）アクリル酸イソボロニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸プロパギル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ナフチル、（メタ）アクリル酸アントラセニル、（メタ）アクリル酸アントラニノニル、（メタ）アクリル酸ピペロニル、（メタ）アクリル酸サリチル、（メタ）アクリル酸フリル、（メタ）アクリル酸フルフリル、（メタ）アクリル酸テトラヒドロフリル、（メタ）アクリル酸ピラニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸フェネチル、（メタ）アクリル酸クレジル、（メタ）アクリル酸－１，１，１－トリフルオロエチル、（メタ）アクリル酸パーフルオルエチル、（メタ）アクリル酸パーフルオロ－ｎ－プロピル、（メタ）アクリル酸パーフルオロ－ｉｓｏ－プロピル、（メタ）アクリル酸トリフェニルメチル、（メタ）アクリル酸クミル、（メタ）アクリル酸３－（Ｎ，Ｎ－ジメチルアミノ）プロピル、（メタ）アクリル酸－２－ヒドロキシエチル、（メタ）アクリル酸－２－ヒドロキシプロピル等の（メタ）アクリル酸エステル類；（メタ）アクリル酸アミド、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミド、（メタ）アクリル酸Ｎ，Ｎ－ジエチルアミド、（メタ）アクリル酸Ｎ，Ｎ－ジプロピルアミド、（メタ）アクリル酸Ｎ，Ｎ－ジ－ｉｓｏ－プロピルアミド、（メタ）アクリル酸アントラセニルアミド等の（メタ）アクリル酸アミド；（メタ）アクリル酸アニリド、（メタ）アクリロイルニトリル、アクロレイン、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、Ｎ－ビニルピロリドン、ビニルピリジン、酢酸ビニル等のビニル化合物類；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不飽和ジカルボン酸ジエステル類；Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ラウリルマレイミド、Ｎ－（４－ヒドロキシフェニル）マレイミド等のモノマレイミド類；Ｎ－（メタ）アクリロイルフタルイミドが挙げられる。 The radically polymerizable monomer other than the mono (meth) acrylate represented by the formula (VI) is not particularly limited, but specifically, for example, styrene and α- and o- of styrene. , M-, p-alkyl, nitro, cyano, amide, ester derivatives and other vinyl aromatics; butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene and other dienes; (meth) methyl acrylate, (meth) Ethyl acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid- tert-butyl, (meth) pentyl acrylate, (meth) neo-pentyl acrylate, (meth) isoamyl acrylate, (meth) hexyl acrylate, (meth) -2-ethyl hexyl acrylate, (meth) lauryl acrylate, ( Dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, -2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, (meth) acrylate Adamanthyl, propagil (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthrasenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, (meth) acrylic Salicyl Acid, (Meta) Frill Acrylate, (Meta) Flufuryl Acrylate, (Meta) Tetrahydrofuryl Acrylate, (Meta) Pyranyl Acrylate, (Meta) benzyl Acrylate, (Meta) Penetyl Acrylic, (Meta) Acrylic Cresyl acid, (meth) acrylic acid-1,1,1-trifluoroethyl, (meth) acrylic acid perfluorethyl, (meth) acrylic acid perfluoro-n-propyl, (meth) acrylic acid perfluoro-iso -Propyl, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (N, N-dimethylamino) propyl (meth) acrylate, -2-hydroxyethyl (meth) acrylate, (meth) (Meta) acrylic acid esters such as acrylic acid-2-hydroxypropyl; (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) Acrylic acid N, N-dipropylamide, (meth) acrylic acid (Meta) acrylic acid amides such as N, N-di-iso-propylamides, (meth) acrylic acid anthracenylamides; (meth) acrylic acid anilides, (meth) acryloylnitrile, achlorine, vinyl chloride, vinylidene chloride, Vinyl compounds such as vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itaconate; N- Monomaleimides such as phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide; N- (meth) acryloylphthalimide can be mentioned.
　これら他のラジカル重合性単量体の中でも、着色樹脂組成物に優れた耐熱性及び強度を付与させるとの観点からは、スチレン、ベンジル（メタ）アクリレート、モノマレイミドが好ましい。
　エポキシ基含有（メタ）アクリレートと他のラジカル重合性単量体との共重合体においてスチレン、ベンジル（メタ）アクリレート、又はモノマレイミドに由来するいずれかの繰り返し単位が含まれる場合、他のラジカル重合性単量体に由来する繰り返し単位中、スチレンに由来する繰り返し単位、ベンジル（メタ）アクリレートに由来する繰り返し単位、及びモノマレイミドに由来する繰り返し単位の含有割合の合計は、１～７０モル％が好ましく、３～５０モル％がさらに好ましい。 Among these other radically polymerizable monomers, styrene, benzyl (meth) acrylate, and monomaleimide are preferable from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition.
If the copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer contains any repeating unit derived from styrene, benzyl (meth) acrylate, or monomaleimide, the other radical polymerization. The total content of the repeating unit derived from styrene, the repeating unit derived from benzyl (meth) acrylate, and the repeating unit derived from monomaleimide among the repeating units derived from the sex monomer is 1 to 70 mol%. It is preferable, 3 to 50 mol% is more preferable.
　エポキシ基含有（メタ）アクリレートと他のラジカル重合性単量体との共重合反応には、公知の溶液重合法が適用できる。使用する溶剤はラジカル重合に不活性なものであれば特に限定されるものではなく、通常用いられている有機溶剤を使用することができる。
　溶液重合法に用いられる溶剤としては、例えば、酢酸エチル、酢酸イソプロピル、セロソルブアセテート、ブチルセロソルブアセテート等のエチレングリコールモノアルキルエーテルアセテート類；ジエチレングリコールモノメチルエーテルアセテート、カルビトールアセテート、ブチルカルビトールアセテート等のジエチレングリコールモノアルキルエーテルアセテート類；プロピレングリコールモノアルキルエーテルアセテート類；ジプロピレングリコールモノアルキルエーテルアセテート類等の酢酸エステル類；エチレングリコールジアルキルエーテル類；メチルカルビトール、エチルカルビトール、ブチルカルビトール等のジエチレングリコールジアルキルエーテル類；トリエチレングリコールジアルキルエーテル類；プロピレングリコールジアルキルエーテル類；ジプロピレングリコールジアルキルエーテル類；１，４－ジオキサン、テトラヒドロフラン等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；ベンゼン、トルエン、キシレン、オクタン、デカン等の炭化水素類；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤；乳酸メチル、乳酸エチル、乳酸ブチル等の乳酸エステル類；ジメチルホルムアミド、Ｎ－メチルピロリドンが挙げられる。これらの溶剤は単独で用いてもよく、２種以上を併用してもよい。 A known solution polymerization method can be applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and another radically polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Examples of the solvent used in the solution polymerization method include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; and diethylene glycol mono such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate. Alkyl ether acetates; Propropylene glycol monoalkyl ether acetates; Acetate esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methylcarbitol, ethylcarbitol, butylcarbitol, etc. Triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; benzene and toluene , Xylene, octane, decane and other hydrocarbons; petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, butyl lactate; dimethylformamide, N- Methylpyrrolidone may be mentioned. These solvents may be used alone or in combination of two or more.
　溶液重合法に用いられる溶剤の使用量は、得られる共重合体１００質量部に対し、通常３０～１０００質量部、好ましくは５０～８００質量部である。溶剤の使用量を前記範囲内とすることで共重合体の分子量の制御が容易となる傾向がある。
　共重合反応に使用されるラジカル重合開始剤は、ラジカル重合を開始できるものであれば特に限定されるものではなく、通常用いられている有機過酸化物触媒やアゾ化合物触媒を使用することができる。有機過酸化物触媒としては、公知のケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアリルパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、パーオキシジカーボネートに分類される触媒が挙げられる。 The amount of the solvent used in the solution polymerization method is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass with respect to 100 parts by mass of the obtained copolymer. By keeping the amount of the solvent used within the above range, it tends to be easy to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst can be used. .. Examples of the organic peroxide catalyst include catalysts classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.
　共重合反応に使用されるラジカル重合開始剤としては、例えば、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ジイソプロピルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ｔ－ヘキシルパーオキシベンゾエート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－ヘキシルパーオキシ－２－エチルヘキサノエート、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキシル－３、３－イソプロピルヒドロパーオキサイド、ｔ－ブチルヒドロパーオキサイド、ジクミルパーオキサイド、ジクミルヒドロパーオキサイド、アセチルパーオキサイド、ビス（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、イソブチルパーオキサイド、３，３，５－トリメチルヘキサノイルパーオキサイド、ラウリルパーオキサイド、１，１－ビス（ｔ－ブチルパーオキシ）３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔ－ヘキシルパーオキシ）３，３，５－トリメチルシクロヘキサンが挙げられる。 Examples of the radical polymerization initiator used in the copolymerization reaction include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, and t-hexyl peroxybenzoate. , T-Butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2 , 5-Dimethyl-2,5-bis (t-butylperoxy) hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl peroxide, dicumylhydroperoxide, acetyl peroxide, Bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylper) Oxy) 3,3,5-trimethylcyclohexane and 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane can be mentioned.
　アゾ化合物触媒としては、例えば、アゾビスイソブチロニトリル、アゾビスカルボンアミドが挙げられる。
　これらの中から、重合温度に応じて、適当な半減期のラジカル重合開始剤が１種又は２種以上使用される。
　ラジカル重合開始剤の使用量は、共重合反応に使用される単量体の合計１００質量部に対して、通常０．５～２０質量部、好ましくは１～１０質量部である。 Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarboxylicamide.
From these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature.
The amount of the radical polymerization initiator used is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomers used in the copolymerization reaction.
　共重合反応は、共重合反応に使用される単量体及びラジカル重合開始剤を溶剤に溶解し、攪拌しながら昇温して行ってもよいし、ラジカル重合開始剤を添加した単量体を、昇温、攪拌した溶剤中に滴下して行ってもよいし、溶剤中にラジカル重合開始剤を添加し昇温した中に単量体を滴下してもよい。
　反応条件は目標とする分子量に応じて設定することができる。 The copolymerization reaction may be carried out by dissolving the monomer used in the polymerization reaction and the radical polymerization initiator in a solvent and raising the temperature with stirring, or using a monomer to which the radical polymerization initiator is added. , The temperature may be dropped in the stirred solvent, or the monomer may be dropped in the temperature obtained by adding the radical polymerization initiator to the solvent.
The reaction conditions can be set according to the target molecular weight.
　本発明において、エポキシ基含有（メタ）アクリレートと他のラジカル重合性単量体との共重合体としては、エポキシ基含有（メタ）アクリレートに由来する繰り返し単位５～９０モル％と他のラジカル重合性単量体に由来する繰り返し単位１０～９５モル％とからなるものが好ましく；エポキシ基含有（メタ）アクリレートに由来する繰り返し単位２０～８０モル％と他のラジカル重合性単量体に由来する繰り返し単位８０～２０モル％とからなるものがさらに好ましく；エポキシ基含有（メタ）アクリレートに由来する繰り返し単位３０～７０モル％と他のラジカル重合性単量体に由来する繰り返し単位７０～３０モル％とからなるものが特に好ましい。 In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and another radically polymerizable monomer includes 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate and other radical polymerization. It is preferably composed of 10 to 95 mol% of repeating units derived from sex monomers; 20 to 80 mol% of repeating units derived from epoxy group-containing (meth) acrylates and other radically polymerizable monomers. More preferably, it consists of 80-20 mol% repeating units; 30-70 mol% repeating units derived from epoxy group-containing (meth) acrylates and 70-30 mol repeating units derived from other radically polymerizable monomers. The one consisting of% is particularly preferable.
　エポキシ基含有（メタ）アクリレートに由来する繰り返し単位の含有割合を前記下限値以上とすることで、後述する不飽和一塩基酸や多塩基酸無水物の付加量が十分となる傾向がある。
　他のラジカル重合性単量体に由来する繰り返し単位の含有割合を前記下限値以上とすることで、耐熱性や強度が十分となる傾向がある。
　続いて、エポキシ樹脂含有（メタ）アクリレートと、他のラジカル重合性単量体との共重合体のエポキシ基に、不飽和一塩基酸（重合性成分）と、多塩基酸無水物（アルカリ可溶性成分）とを反応させる。 By setting the content ratio of the repeating unit derived from the epoxy group-containing (meth) acrylate to the above lower limit value or more, the amount of unsaturated monobasic acid or polybasic acid anhydride described later tends to be sufficient.
By setting the content ratio of the repeating unit derived from the other radically polymerizable monomer to the above lower limit value or more, the heat resistance and the strength tend to be sufficient.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble) are added to the epoxy group of the copolymer of the epoxy resin-containing (meth) acrylate and another radically polymerizable monomer. Ingredient) and react.
　エポキシ基に付加させる不飽和一塩基酸としては、公知の不飽和一塩基酸を使用することができ、例えば、エチレン性不飽和二重結合を有する不飽和カルボン酸が挙げられる。
　エポキシ基に付加させる不飽和一塩基酸としては、例えば、（メタ）アクリル酸；クロトン酸；ｏ－、ｍ－、ｐ－ビニル安息香酸；α－位がハロアルキル基、アルコキシル基、ハロゲン原子、ニトロ基、又はシアノ基などで置換された（メタ）アクリル酸等のモノカルボン酸；が挙げられる。中でも（メタ）アクリル酸が好ましい。これらの不飽和一塩基酸は１種を単独で用いてもよく、２種以上を併用してもよい。 As the unsaturated monobasic acid added to the epoxy group, a known unsaturated monobasic acid can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Examples of the unsaturated monobasic acid to be added to the epoxy group include (meth) acrylic acid; crotonic acid; o-, m-, and p-vinylbenzoic acid; the α-position is a haloalkyl group, an alkoxyl group, a halogen atom, and a nitro. Examples thereof include monocarboxylic acids such as (meth) acrylic acid substituted with a group or a cyano group. Of these, (meth) acrylic acid is preferable. One of these unsaturated monobasic acids may be used alone, or two or more thereof may be used in combination.
　不飽和一塩基酸をエポキシ基に付加させることにより、樹脂（Ｃ－１）に重合性を付与することができる。
　不飽和一塩基酸は、共重合体が有するエポキシ基の通常１０～１００モル％、好ましくは３０～１００モル％、より好ましくは５０～１００モル％に付加させる。前記下限値以上とすることで、着色樹脂組成物の経時安定性が良好となる傾向がある。
　共重合体のエポキシ基に不飽和一塩基酸を付加させる方法としては、公知の方法を採用することができる。 By adding an unsaturated monobasic acid to the epoxy group, the resin (C-1) can be imparted with polymerizable properties.
The unsaturated monobasic acid is added to usually 10 to 100 mol%, preferably 30 to 100 mol%, more preferably 50 to 100 mol% of the epoxy group contained in the copolymer. By setting the value to the lower limit or more, the stability of the colored resin composition with time tends to be good.
As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.
　さらに、共重合体のエポキシ基に不飽和一塩基酸を付加させたときに生じる水酸基に付加させる多塩基酸無水物としては、公知の多塩基酸無水物が使用できる。
　多塩基酸無水物としては、例えば、無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水クロレンド酸等の二塩基酸無水物；無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、ビフェニルテトラカルボン酸無水物等の三塩基以上の酸の無水物が挙げられる。中でも、テトラヒドロ無水フタル酸、無水コハク酸が好ましい。これらの多塩基酸無水物は１種を単独で用いてもよく、２種以上を併用してもよい。 Further, as the polybasic acid anhydride added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, a known polybasic acid anhydride can be used.
Examples of the polybasic acid anhydride include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, and chlorendic anhydride; Trimerit anhydride. Examples thereof include anhydrates of three or more bases such as an acid, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and succinic anhydride are preferable. One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.
　多塩基酸無水物を共重合体のエポキシ基に不飽和一塩基酸を付加させたときに生じる水酸基に付加させることにより、樹脂（Ｃ－１）にアルカリ可溶性を付与することができる。
　多塩基酸無水物は、共重合体が有するエポキシ基に不飽和一塩基酸を付加させることにより生じる水酸基の通常１０～１００モル％、好ましくは２０～９０モル％、より好ましくは３０～８０モル％に付加させる。前記上限値以下とすることで、現像時の残膜率が良好となる傾向があり、また、前記下限値以上とすることで溶解性が十分となる傾向がある。
　共重合体が有するエポキシ基に不飽和一塩基酸を付加させることにより生じる水酸基に多塩基酸無水物を付加させる方法としては、公知の方法を採用することができる。 Alkali solubility can be imparted to the resin (C-1) by adding the polybasic acid anhydride to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer.
The polybasic acid anhydride is usually 10 to 100 mol%, preferably 20 to 90 mol%, more preferably 30 to 80 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer. Add to%. When it is set to the upper limit value or less, the residual film ratio at the time of development tends to be good, and when it is set to the lower limit value or more, the solubility tends to be sufficient.
As a method for adding a polybasic acid anhydride to a hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.
　さらに、光感度を向上させるために、多塩基酸無水物を付加させた後、生成したカルボキシル基の一部にグリシジル（メタ）アクリレートや重合性不飽和基を有するグリシジルエーテル化合物を付加させてもよい。
　現像性を向上させるために、生成したカルボキシル基の一部に、重合性不飽和基を有さないグリシジルエーテル化合物を付加させてもよい。 Further, in order to improve the photosensitivity, even if a polybasic acid anhydride is added and then a glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl groups. good.
In order to improve the developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl groups.
　又、この両方を付加させてもよい。
　重合性不飽和基を有さないグリシジルエーテル化合物としては、例えば、フェニル基やアルキル基を有するグリシジルエーテル化合物が挙げられる。
　市販品として、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－１１１」、「デナコールＥＸ－１２１」、「デナコールＥＸ－１４１」、「デナコールＥＸ－１４５」、「デナコールＥＸ－１４６」、「デナコールＥＸ－１７１」、「デナコールＥＸ－１９２」が挙げられる。 Further, both of them may be added.
Examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group and an alkyl group.
As commercial products, for example, the product names "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol EX-146", and "Denacol EX-146" manufactured by Nagase ChemteX Corporation. Examples thereof include "Denacol EX-171" and "Denacol EX-192".
　樹脂（Ｃ－１）の構造は、例えば日本国特開平８－２９７３６６号公報や日本国特開２００１－８９５３３号公報に記載されている。
　樹脂（Ｃ－１）のＧＰＣで測定したポリスチレン換算の重量平均分子量は特に限定されないが、３０００～１０００００が好ましく、５０００～５００００が特に好ましい。前記下限値以上とすることで、耐熱性や膜強度が良好となる傾向があり、また、前記上限値以下とすることで現像液に対する溶解性が良好となる傾向がある。
　分子量分布の目安として、樹脂（Ｃ－１）の重量平均分子量（Ｍｗ）の数平均分子量に対する比（Ｍｗ／Ｍｎ）は、２．０～５．０が好ましい。 The structure of the resin (C-1) is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.
The polystyrene-equivalent weight average molecular weight measured by GPC of the resin (C-1) is not particularly limited, but is preferably 3000 to 100,000, and particularly preferably 5000 to 50,000. When it is at least the above lower limit value, the heat resistance and film strength tend to be good, and when it is at least the above upper limit value, the solubility in a developing solution tends to be good.
As a guideline for the molecular weight distribution, the ratio (Mw / Mn) of the weight average molecular weight (Mw) of the resin (C-1) to the number average molecular weight is preferably 2.0 to 5.0.
　紫外線露光時の塗膜硬化性の観点から、（Ｃ）アルカリ可溶性樹脂の中でも、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂が好ましい。
　（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂が有する、エチレン性不飽和基を有する側鎖を含む部分構造は特に限定されないが、紫外線露光時の塗膜硬化性とアルカリ現像時のアルカリ溶解性の両立の観点から、例えば、下記一般式（ＣＩ）で表される部分構造を有することが好ましい。 From the viewpoint of coating film curability during exposure to ultraviolet rays, among the (C) alkali-soluble resins, the (c1) acrylic copolymer resin having an ethylenically unsaturated group in the side chain is preferable.
(C1) The partial structure of the acrylic copolymer resin having an ethylenically unsaturated group in the side chain including the side chain having an ethylenically unsaturated group is not particularly limited, but the coating film curability and alkali development during ultraviolet exposure are not particularly limited. From the viewpoint of achieving both alkali solubility at the time, for example, it is preferable to have a partial structure represented by the following general formula (CI).
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　式（ＣＩ）中、Ｒ1及びＲ2は各々独立に、水素原子又はメチル基を表す。＊は結合手を表す。 In formula (CI), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. * Represents a bond.
　また、式（ＣＩ）で表される部分構造の中でも、感度やアルカリ現像性の観点から、下記一般式（ＣＩ’）で表される部分構造が好ましい。 Further, among the partial structures represented by the formula (CI), the partial structure represented by the following general formula (CI') is preferable from the viewpoint of sensitivity and alkali developability.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　式（ＣＩ’）中、Ｒ1及びＲ2は各々独立に、水素原子又はメチル基を表す。ＲXは水素原子又は多塩基酸残基を表す。 In formula (CI'), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. RX represents a hydrogen atom or a polybasic acid residue.
　多塩基酸残基とは、多塩基酸又はその無水物からＯＨ基を１つ除した１価の基を意味する。多塩基酸としては、例えば、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸が挙げられる。
　パターニング特性の観点から、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸が好ましく、テトラヒドロフタル酸、ビフェニルテトラカルボン酸がより好ましい。
　これらの多塩基酸は１種単独で用いてもよく、２種以上を併用してもよい。 The polybasic acid residue means a monovalent group obtained by subtracting one OH group from the polybasic acid or its anhydride. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid and endomethylene. Examples thereof include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid.
From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferable. Is more preferable.
These polybasic acids may be used alone or in combination of two or more.
　（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂が式（ＣＩ）で表される部分構造を有する場合、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂に含まれる、式（ＣＩ）で表される部分構造の含有割合は特に限定されないが１０モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上がさらに好ましく、４０モル％以上がよりさらに好ましく、５０モル％以上が特に好ましく、６５モル％以上が最も好ましく、また、９５モル％以下が好ましく、９０モル％以下がより好ましく、８５モル％以下がさらに好ましく、８０モル％以下がよりさらに好ましく、７５モル％以下が特に好ましく、７０モル％以下が最も好ましい。前記下限値以上とすることで紫外線露光時の塗膜硬化性が向上する傾向があり、また、前記上限値以下とすることでアルカリ現像時のアルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂に含まれる、式（ＣＩ）で表される部分構造の含有割合は１０～９５モル％が好ましく、２０～９０モル％がより好ましく、３０～８５モル％がさらに好ましく、４０～８０モル％がよりさらに好ましく、５０～７５モル％が特に好ましく、６５～７０モル％が最も好ましい。 When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure represented by the formula (CI), the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) can be used. The content ratio of the partial structure represented by the formula (CI) contained is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, still more preferably 40 mol% or more. More preferably, 50 mol% or more is particularly preferable, 65 mol% or more is most preferable, 95 mol% or less is preferable, 90 mol% or less is more preferable, 85 mol% or less is further preferable, and 80 mol% or less is more preferable. More preferably, 75 mol% or less is particularly preferable, and 70 mol% or less is most preferable. When it is at least the above lower limit value, the coating film curability at the time of exposure to ultraviolet rays tends to be improved, and when it is at least the above upper limit value, the alkali solubility at the time of alkaline development tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by the formula (CI) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is preferably 10 to 95 mol%, preferably 20 to 90 mol%. More preferably, 30 to 85 mol% is further preferable, 40 to 80 mol% is further preferable, 50 to 75 mol% is particularly preferable, and 65 to 70 mol% is most preferable.
　（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂が式（ＣＩ’）で表される部分構造を有する場合、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂に含まれる、式（ＣＩ’）で表される部分構造の含有割合は特に限定されないが、１０モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上がさらに好ましく、４０モル％以上がよりさらに好ましく、５０モル％以上が特に好ましく、６５モル％以上が最も好ましく、また、９５モル％以下が好ましく、９０モル％以下がより好ましく、８５モル％以下がさらに好ましく、８０モル％以下がよりさらに好ましく、７５モル％以下が特に好ましく、７０モル％以下が最も好ましい。前記下限値以上とすることで紫外線露光時の塗膜硬化性が向上する傾向があり、また、前記上限値以下とすることでアルカリ現像時のアルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂に含まれる、式（ＣＩ）で表される部分構造の含有割合は１０～９５モル％が好ましく、２０～９０モル％がより好ましく、３０～８５モル％がさらに好ましく、４０～８０モル％がよりさらに好ましく、５０～７５モル％が特に好ましく、６５～７０モル％が最も好ましい。 (C1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the formula (CI'), the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain. The content of the partial structure represented by the formula (CI') contained in is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and even more preferably 40 mol%. The above is even more preferable, 50 mol% or more is particularly preferable, 65 mol% or more is most preferable, 95 mol% or less is preferable, 90 mol% or less is more preferable, 85 mol% or less is further preferable, and 80 mol% is more preferable. The following is even more preferable, 75 mol% or less is particularly preferable, and 70 mol% or less is most preferable. When it is at least the above lower limit value, the coating film curability at the time of exposure to ultraviolet rays tends to be improved, and when it is at least the above upper limit value, the alkali solubility at the time of alkaline development tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by the formula (CI) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is preferably 10 to 95 mol%, preferably 20 to 90 mol%. More preferably, 30 to 85 mol% is further preferable, 40 to 80 mol% is further preferable, 50 to 75 mol% is particularly preferable, and 65 to 70 mol% is most preferable.
　（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂が式（ＣＩ）で表される部分構造を含む場合、他に含まれる部分構造は特に限定されないが、アルカリ現像時のアルカリ溶解性の観点から、例えば、下記一般式（ＣＩＩ）で表される部分構造を有することも好ましい。 (C1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains a partial structure represented by the formula (CI), the other partial structure is not particularly limited, but alkali dissolution during alkaline development. From the viewpoint of sex, it is also preferable to have a partial structure represented by the following general formula (CII), for example.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　式（ＣＩＩ）中、Ｒ3は水素原子又はメチル基を表し、Ｒ4は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族環基、又は置換基を有していてもよいアルケニル基を表す。 In formula (CII), R 3 represents a hydrogen atom or a methyl group, and R 4 is an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent. Represents an alkenyl group that may have.
（Ｒ4）
　式（ＣＩＩ）において、Ｒ4は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族環基、又は置換基を有していてもよいアルケニル基を表す。
　Ｒ4におけるアルキル基としては直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上が好ましく、３以上がより好ましく、５以上がさらに好ましく、８以上が特に好ましく、また、２０以下が好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。前記下限値以上とすることで親油性が向上し、溶剤への溶解性が向上する傾向があり、また、前記上限値以下とすることで親水性が向上し、アルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、アルキル基の炭素数は１～２０が好ましく、１～１８がより好ましく、３～１６がさらに好ましく、５～１４がよりさらに好ましく、８～１２が特に好ましい。 (R 4 )
In formula (CII), R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.
Examples of the alkyl group in R 4 include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, still preferably 20 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less. Even more preferably, 12 or less is particularly preferable. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, still more preferably 5 to 14, and particularly preferably 8 to 12.
　アルキル基としては、例えば、メチル基、エチル基、シクロヘキシル基、ジシクロペンタニル基、ドデカニル基が挙げられる。現像性の観点から、ジシクロペンタニル基、ドデカニル基が好ましく、ジシクロペンタニル基がより好ましい。
　アルキル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基が挙げられる。現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group and a dodecanyl group. From the viewpoint of developability, a dicyclopentanyl group and a dodecanyl group are preferable, and a dicyclopentanyl group is more preferable.
Examples of the substituent that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, and methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒ4における芳香族環基としては、１価の芳香族炭化水素環基及び１価の芳香族複素環基が挙げられる。その炭素数は６以上が好ましく、また、２４以下が好ましく、２２以下がより好ましく、２０以下がさらに好ましく、１８以下が特に好ましい。前記下限値以上とすることで親油性が向上し、溶剤への溶解性が向上する傾向があり、また、前記上限値以下とすることで親水性が向上し、アルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、芳香族環基の炭素数は６～２４が好ましく、６～２２がより好ましく、６～２０がさらに好ましく、６～１８が特に好ましい。
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよく、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。
　芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよく、例えば、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。
　現像性の観点から、ベンゼン環基、ナフタレン環基が好ましく、ベンゼン環基がより好ましい。
　芳香族環基が有していてもよい置換基としては、例えば、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基が挙げられる。現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the aromatic ring group in R 4 include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the aromatic ring group preferably has 6 to 24 carbon atoms, more preferably 6 to 22 carbon atoms, still more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 18 carbon atoms.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, or pyrene. Examples thereof include a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
The aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, or an imidazole ring. , Oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrazole ring, thienothiophene ring, flopyrol ring, floran ring, thienoflan ring, benzoisoxazole ring, benzoisothiazole ring, Examples thereof include a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a synolin ring, a quinoxalin ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. ..
From the viewpoint of developability, a benzene ring group and a naphthalene ring group are preferable, and a benzene ring group is more preferable.
Examples of the substituent that the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group and an epoxy group. , Oligoethylene glycol group, phenyl group, carboxyl group and examples. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒ4におけるアルケニル基としては、直鎖状、分岐鎖状又は環状のアルケニル基が挙げられる。その炭素数は、２以上が好ましく、また、２２以下が好ましく、２０以下がより好ましく、１８以下がさらに好ましく、１６以下がよりさらに好ましく、１４以下が特に好ましい。前記下限値以上とすることで親油性が向上し、溶剤への溶解性が向上する傾向があり、また、前記上限値以下とすることで親水性が向上し、アルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、アルケニル基の炭素数は２～２２が好ましく、２～２０がより好ましく、２～１８がさらに好ましく、２～１６がよりさらに好ましく、２～１４が特に好ましい。 Examples of the alkenyl group in R 4 include a linear, branched or cyclic alkenyl group. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably 2 to 18 carbon atoms, still more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.
　アルケニル基としては、例えば、ビニル基、アリル基、２－プロペン－２－イル基、２－ブテン－１－イル基、３－ブテン－１－イル基、２－ペンテン－１－イル基、３－ペンテン－２－イル基、ヘキセニル基、シクロブテニル基、シクロペンテニル基、シクロヘキセニルが挙げられる。現像性の観点から、ビニル基、アリル基が好ましく、ビニル基がより好ましい。 Examples of the alkenyl group include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-butene-1-yl group, a 3-butene-1-yl group, a 2-pentene-1-yl group, and 3 -Pentene-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl can be mentioned. From the viewpoint of developability, a vinyl group and an allyl group are preferable, and a vinyl group is more preferable.
　アルケニル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基が挙げられる。現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the substituent that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. Can be mentioned. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒ4は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族環基、又は置換基を有していてもよいアルケニル基を表し、現像性と膜強度の観点から、アルキル基又はアルケニル基が好ましく、アルキル基がより好ましい。 R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent, and has a developability and a film strength. From the viewpoint, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.
　（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂が式（ＣＩＩ）で表される部分構造を有する場合、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂における式（ＣＩＩ）で表される部分構造の含有割合は特に限定されないが、１モル％以上が好ましく、５モル％以上がより好ましく、１０モル％以上がさらに好ましく、２０モル％以上が特に好ましく、また、７０モル％以下が好ましく、６０モル％以下がより好ましく、５０モル％以下がさらに好ましく、４０モル％以下が特に好ましい。前記下限値以上とすることでアルカリ溶解性が向上する傾向があり、また、前記上限値以下とすることで着色樹脂組成物の保存安定性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂における式（ＣＩＩ）で表される部分構造の含有割合は１～７０モル％が好ましく、５～６０モル％がより好ましく、１０～５０モル％がさらに好ましく、２０～４０モル％が特に好ましい。 When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure represented by the formula (CII), the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure. The content ratio of the partial structure represented by the formula (CII) is not particularly limited, but 1 mol% or more is preferable, 5 mol% or more is more preferable, 10 mol% or more is further preferable, and 20 mol% or more is particularly preferable. Further, 70 mol% or less is preferable, 60 mol% or less is more preferable, 50 mol% or less is further preferable, and 40 mol% or less is particularly preferable. When it is at least the above lower limit value, the alkali solubility tends to be improved, and when it is at least the above upper limit value, the storage stability of the colored resin composition tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by the formula (CII) in the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is preferably 1 to 70 mol%, more preferably 5 to 60 mol%. 10 to 50 mol% is more preferable, and 20 to 40 mol% is particularly preferable.
　（ｃ１）アクリル共重合樹脂が式（ＣＩ）で表される部分構造を含む場合、他に含まれる部分構造として、耐熱性向上による輝度低下抑制の観点から下記一般式（ＣＩＩＩ）で表される部分構造が含まれることが好ましい。 (C1) When the acrylic copolymer resin contains a partial structure represented by the formula (CI), it is represented by the following general formula (CIII) from the viewpoint of suppressing the decrease in brightness due to the improvement of heat resistance as the other partial structure contained. It is preferable that a partial structure is included.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　式（ＣＩＩＩ）中、Ｒ5は水素原子又はメチル基を表し、Ｒ6は置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、ヒドロキシル基、カルボキシル基、ハロゲン原子、置換基を有していてもよいアルコキシ基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表す。ｔは０～５の整数を表す。 In formula (CIII), R 5 represents a hydrogen atom or a methyl group, and R 6 has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. It represents an alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent. t represents an integer from 0 to 5.
（Ｒ6）
　式（ＣＩＩＩ）においてＲ6は置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、ヒドロキシル基、カルボキシル基、ハロゲン原子、置換基を有していてもよいアルコキシ基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表す。
　Ｒ6におけるアルキル基としては、直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上が好ましく、３以上がより好ましく、５以上がさらに好ましく、また、２０以下好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。前記下限値以上とすることで親油性が向上し、溶剤への溶解性が向上する傾向があり、また、前記上限値以下とすることで親水性が向上し、アルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、アルキル基の炭素数は１～２０が好ましく、１～１８がより好ましく、３～１６がさらに好ましく、３～１４がよりさらに好ましく、５～１２が特に好ましい。 (R 6 )
In formula (CIII), R 6 has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, and the like. Represents a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
Examples of the alkyl group in R 6 include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, still more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and even more preferably 12 or less. Especially preferable. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, still more preferably 3 to 14, and particularly preferably 5 to 12.
　アルキル基としては、例えば、メチル基、エチル基、シクロヘキシル基、ジシクロペンタニル基、ドデカニル基が挙げられる。耐熱性の観点から、ジシクロペンタニル基、ドデカニル基が好ましく、ジシクロペンタニル基がより好ましい。
　アルキル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基が挙げられる。現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group and a dodecanyl group. From the viewpoint of heat resistance, a dicyclopentanyl group and a dodecanyl group are preferable, and a dicyclopentanyl group is more preferable.
Examples of the substituent that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, and methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒ6におけるアルケニル基としては、直鎖状、分岐鎖状又は環状のアルケニル基が挙げられる。その炭素数は、２以上が好ましく、また、２２以下が好ましく、２０以下がより好ましく、１８以下がさらに好ましく、１６以下がよりさらに好ましく、１４以下が特に好ましい。前記下限値以上とすることで親油性が向上し、溶剤への溶解性が向上する傾向があり、また、前記上限値以下とすることで親水性が向上し、アルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、アルケニル基の炭素数は２～２２が好ましく、２～２０がより好ましく、２～１８がさらに好ましく、２～１６がよりさらに好ましく、２～１４が特に好ましい。 Examples of the alkenyl group in R 6 include a linear, branched or cyclic alkenyl group. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably 2 to 18 carbon atoms, still more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.
　アルケニル基としては、例えば、ビニル基、アリル基、２－プロペン－２－イル基、２－ブテン－１－イル基、３－ブテン－１－イル基、２－ペンテン－１－イル基、３－ペンテン－２－イル基、ヘキセニル基、シクロブテニル基、シクロペンテニル基、シクロヘキセニルが挙げられる。紫外線露光時の露光感度の観点から、ビニル基、アリル基が好ましく、ビニル基がより好ましい。 Examples of the alkenyl group include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-butene-1-yl group, a 3-butene-1-yl group, a 2-pentene-1-yl group, and 3 -Pentene-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl can be mentioned. From the viewpoint of exposure sensitivity during ultraviolet exposure, a vinyl group and an allyl group are preferable, and a vinyl group is more preferable.
　アルケニル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基が挙げられる。現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the substituent that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. Can be mentioned. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒ6におけるアルキニル基としては、直鎖状、分岐鎖状又は環状のアルキニル基が挙げられる。その炭素数は、２以上が好ましく、また、２２以下が好ましく、２０以下がより好ましく、１８以下がさらに好ましく、１６以下がよりさらに好ましく、１４以下が特に好ましい。前記下限値以上とすることで親油性が向上し、溶剤への溶解性が向上する傾向があり、また、前記上限値以下とすることで親水性が向上し、アルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、アルキニル基の炭素数は２～２２が好ましく、２～２０がより好ましく、２～１８がさらに好ましく、２～１６がよりさらに好ましく、２～１４が特に好ましい。 Examples of the alkynyl group in R 6 include a linear, branched or cyclic alkynyl group. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the alkynyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably 2 to 18 carbon atoms, still more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.
　アルキニル基としては、例えば、１－プロピン－３－イル基、１－ブチン－４－イル基、１－ペンチン－５－イル基、２－メチル－３－ブチン－２－イル基、１，４－ペンタジイン－３－イル基、１，３－ペンタジイン－５－イル基、１－ヘキシン－６－イル基が挙げられる。 Examples of the alkynyl group include 1-propyne-3-yl group, 1-butyne-4-yl group, 1-pentyne-5-yl group, 2-methyl-3-butin-2-yl group, 1,4. Examples thereof include -pentadiyne-3-yl group, 1,3-pentadiyne-5-yl group and 1-hexin-6-yl group.
　アルキニル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基が挙げられる。現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the substituent that the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. Can be mentioned. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒ6におけるハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。アクリル共重合樹脂の保存安定性の観点からフッ素原子が好ましい。 Examples of the halogen atom in R 6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Fluorine atoms are preferable from the viewpoint of storage stability of the acrylic copolymer resin.
　Ｒ6におけるアルコキシ基としては、直鎖状、分岐鎖状又は環状のアルコキシ基が挙げられる。その炭素数は、１以上が好ましく、また、２０以下が好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。前記下限値以上とすることで親油性が向上し、溶剤への溶解性が向上する傾向があり、また、前記上限値以下とすることで親水性が向上し、アルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、アルコキシ基の炭素数は１～２０が好ましく、１～１８がより好ましく、１～１６がさらに好ましく、１～１４がよりさらに好ましく、１～１２が特に好ましい。 Examples of the alkoxy group in R 6 include a linear, branched or cyclic alkoxy group. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, further preferably 1 to 16 carbon atoms, still more preferably 1 to 14 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
　アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基が挙げられる。 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group.
　アルコキシ基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基が挙げられる。現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the substituent that the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, and methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒ6におけるアルキルスルフィド基としては、直鎖状、分岐鎖状又は環状のアルキルスルフィド基が挙げられる。その炭素数は、１以上が好ましく、また、２０以下が好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。前記下限値以上とすることで親油性が向上し、溶剤への溶解性が向上する傾向があり、また、前記上限値以下とすることで親水性が向上し、アルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、アルキルスルフィド基の炭素数は１～２０が好ましく、１～１８がより好ましく、１～１６がさらに好ましく、１～１４がよりさらに好ましく、１～１２が特に好ましい。 Examples of the alkyl sulfide group in R 6 include linear, branched or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, further preferably 1 to 16, further preferably 1 to 14, and particularly preferably 1 to 12.
　アルキルスルフィド基としては、例えば、メチルスルフィド基、エチルスルフィド基、プロピルスルフィド基、ブチルスルフィド基が挙げられる。現像性の観点から、メチルスルフィド基、エチルスルフィド基が好ましい。 Examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group. From the viewpoint of developability, a methyl sulfide group and an ethyl sulfide group are preferable.
　アルキルスルフィド基におけるアルキル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基が挙げられる。現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the substituent that the alkyl group in the alkyl sulfide group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group and a phenyl group. Examples thereof include a group, a carboxyl group, an acryloyl group and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒ6は置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、ヒドロキシル基、カルボキシル基、ハロゲン原子、アルコキシ基、ヒドロキシアルキル基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表し、現像性の観点から、ヒドロキシル基又はカルボキシル基が好ましく、カルボキシル基がより好ましい。 R 6 has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom and an alkoxy group. , A hydroxyalkyl group, a thiol group, or an alkyl sulfide group which may have a substituent, and from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.
　式（ＣＩＩＩ）においてｔは０～５の整数を表す。製造容易性の観点からはｔが０であることが好ましい。 In equation (CIII), t represents an integer from 0 to 5. From the viewpoint of ease of manufacture, t is preferably 0.
　（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂が式（ＣＩＩＩ）で表される部分構造を有する場合、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂における式（ＣＩＩＩ）で表される部分構造の含有割合は特に限定されないが、１モル％以上が好ましく、２モル％以上がより好ましく、５モル％以上がさらに好ましく、８モル％以上が特に好ましく、また、５０モル％以下が好ましく、４０モル％以下がより好ましく、３０モル％以下がさらに好ましく、２０モル％以下が特に好ましい。前記下限値以上とすることで耐熱性が向上し輝度低下を抑制する傾向があり、また、前記上限値以下とすることでその他部分構造の含有割合が増え、アルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂における式（ＣＩＩＩ）で表される部分構造の含有割合は１～５０モル％が好ましく、２～４０モル％がより好ましく、５～３０モル％がさらに好ましく、８～２０モル％が特に好ましい。 When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure represented by the formula (CIII), the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure. The content ratio of the partial structure represented by the formula (CIII) is not particularly limited, but 1 mol% or more is preferable, 2 mol% or more is more preferable, 5 mol% or more is further preferable, and 8 mol% or more is particularly preferable. Further, 50 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is further preferable, and 20 mol% or less is particularly preferable. When it is set to the lower limit value or more, the heat resistance tends to be improved and the decrease in brightness tends to be suppressed, and when it is set to the upper limit value or less, the content ratio of other partial structures tends to increase and the alkali solubility tends to be improved. .. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by the formula (CIII) in the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is preferably 1 to 50 mol%, more preferably 2 to 40 mol%. 5 to 30 mol% is more preferable, and 8 to 20 mol% is particularly preferable.
　（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂が式（ＣＩ）で表される部分構造を有する場合、他に含まれる部分構造として、現像性の観点から下記一般式（ＣＩＶ）で表される部分構造を有することも好ましい。 (C1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the formula (CI), the following general formula (CIV) is used as the other partial structure contained from the viewpoint of developability. It is also preferable to have a partial structure represented by).
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　式（ＩＶ）中、Ｒ7は水素原子又はメチル基を表す。 In formula (IV), R 7 represents a hydrogen atom or a methyl group.
　（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂における式（ＣＩＶ）で表される部分構造を含有する場合、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂における式（ＣＩＶ）で表される部分構造の含有割合は特に限定されないが、５モル％以上が好ましく、１０モル％以上がより好ましく、２０モル％以上がさらに好ましく、また、８０モル％以下が好ましく７０モル％以下がより好ましく、６０％モル以下がさらに好ましい。前記下限値以上とすることでアルカリ溶解性が向上する傾向があり、また、前記上限値以下とすることで着色樹脂組成物の保存安定性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、（ｃ１）側鎖にエチレン性不飽和基を有するアクリル共重合樹脂における式（ＣＩＶ）で表される部分構造の含有割合は５～８０モル％が好ましく１０～７０モル％がより好ましく、２０～６０％モルがさらに好ましい。 When the partial structure represented by the formula (CIV) in the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is contained, the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is contained. The content ratio of the partial structure represented by the formula (CIV) in the above is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and 80 mol% or less. It is preferably 70 mol% or less, more preferably 60% mol or less. When it is at least the above lower limit value, the alkali solubility tends to be improved, and when it is at least the above upper limit value, the storage stability of the colored resin composition tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by the formula (CIV) in the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is preferably 5 to 80 mol%, more preferably 10 to 70 mol%. 20-60% mol is more preferred.
　（Ｃ）アルカリ可溶性樹脂の酸価は特に限定されないが、１０ｍｇＫＯＨ／ｇ以上が好ましく、３０ｍｇＫＯＨ／ｇ以上がより好ましく、４０ｍｇＫＯＨ／ｇ以上がさらに好ましく、５０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、６０ｍｇＫＯＨ／ｇ以上が特に好ましく、また、３００ｍｇＫＯＨ／ｇ以下が好ましく、２５０ｍｇＫＯＨ／ｇ以下がより好ましく、２００ｍｇＫＯＨ／ｇ以下がさらに好ましく、１５０ｍｇＫＯＨ／ｇ以下がよりさらに好ましい。前記下限値以上とすることでアルカリ溶解性が向上する傾向があり、また、前記上限値以下とすることで着色樹脂組成物の保存安定性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、（Ｃ）アルカリ可溶性樹脂の酸価は１０～３００ｍｇＫＯＨ／ｇが好ましく、３０～３００ｍｇＫＯＨ／ｇがより好ましく、４０～２５０ｍｇＫＯＨ／ｇがさらに好ましく、５０～２００ｍｇＫＯＨ／ｇがよりさらに好ましく、６０～１５０ｍｇＫＯＨ／ｇが特に好ましい。 The acid value of the alkali-soluble resin (C) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 40 mgKOH / g or more, still more preferably 50 mgKOH / g or more, and 60 mgKOH / g. The above is particularly preferable, and 300 mgKOH / g or less is preferable, 250 mgKOH / g or less is more preferable, 200 mgKOH / g or less is further preferable, and 150 mgKOH / g or less is further preferable. When it is at least the above lower limit value, the alkali solubility tends to be improved, and when it is at least the above upper limit value, the storage stability of the colored resin composition tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the acid value of the alkali-soluble resin (C) is preferably 10 to 300 mgKOH / g, more preferably 30 to 300 mgKOH / g, even more preferably 40 to 250 mgKOH / g, still more preferably 50 to 200 mgKOH / g, and even more preferably 60 to 200 mgKOH / g. 150 mgKOH / g is particularly preferable.
　（Ｃ）アルカリ可溶性樹脂の重量平均分子量は特に限定されないが、通常１０００以上、好ましくは２０００以上、より好ましくは４０００以上、さらに好ましくは６０００以上、よりさらに好ましくは７０００以上、特に好ましくは８０００以上であり、また、通常３００００以下、好ましくは２００００以下、より好ましくは１５０００以下、さらに好ましくは１００００以下である。前記下限値以上とすることで耐熱性や塗膜硬化性が向上する傾向があり、また、前記上限値以下とすることでアルカリ溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、（Ｃ）アルカリ可溶性樹脂の重量平均分子量は１０００～３００００が好ましく、２０００～３００００がより好ましく、４０００～２００００がさらに好ましく、６０００～２００００がよりさらに好ましく、７０００～１５０００がことさら好ましく、８０００～１００００が特に好ましい。 The weight average molecular weight of the alkali-soluble resin (C) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, still more preferably 6000 or more, still more preferably 7000 or more, and particularly preferably 8000 or more. Also, it is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less. When it is at least the above lower limit value, heat resistance and coating film curability tend to be improved, and when it is at least the above upper limit value, alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the weight average molecular weight of the alkali-soluble resin (C) is preferably 1000 to 30000, more preferably 2000 to 30000, still more preferably 4000 to 20000, further preferably 6000 to 20000, particularly preferably 7000 to 15000, and 8000 to 8000. 10000 is particularly preferable.
　本発明の着色樹脂組成物における（Ｃ）アルカリ可溶性樹脂の含有割合は特に限定されないが、着色樹脂組成物の全固形分中に５質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上がさらに好ましく、３０質量％以上がよりさらに好ましく、４０質量％以上が特に好ましく、また、８０質量％以下が好ましく、７０質量％以下がより好ましく、６０質量％以下がさらに好ましく、５０質量％以下が特に好ましい。前記下限値以上とすることで紫外線露光時の塗膜硬化性が向上する傾向があり、また、前記上限値以下とすることで現像液溶解性が向上し、残渣を抑制する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物における（Ｃ）アルカリ可溶性樹脂の含有割合は、着色樹脂組成物の全固形分中に、５～８０質量％が好ましく、１０～８０質量％がより好ましく、２０～７０質量％がさらに好ましく、３０～６０質量％がよりさらに好ましく、４０～５０質量％が特に好ましい。 The content ratio of the (C) alkali-soluble resin in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass in the total solid content of the colored resin composition. % Or more is further preferable, 30% by mass or more is further preferable, 40% by mass or more is particularly preferable, 80% by mass or less is more preferable, 70% by mass or less is more preferable, 60% by mass or less is further preferable, and 50% by mass is more preferable. % Or less is particularly preferable. When it is at least the above lower limit value, the curability of the coating film at the time of exposure to ultraviolet rays tends to be improved, and when it is at least the above upper limit value, the solubility of the developer is improved and the residue tends to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the (C) alkali-soluble resin in the colored resin composition is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, and 20 to 70% by mass in the total solid content of the colored resin composition. % Is even more preferable, 30 to 60% by mass is even more preferable, and 40 to 50% by mass is particularly preferable.
［１－４］（Ｄ）光重合開始剤
　本発明の着色樹脂組成物は（Ｄ）光重合開始剤を含有する。（Ｄ）光重合開始剤を含有することで光重合による膜硬化性を付与することができる。
　（Ｄ）光重合開始剤は、加速剤（連鎖移動剤）及び必要に応じて添加される増感色素等の付加剤との混合物（光重合開始系）として用いることもできる。光重合開始系は、光を直接吸収し、或いは光増感されて分解反応又は水素引き抜き反応を起こし、重合活性ラジカルを発生する機能を有する成分である。 [1-4] (D) Photopolymerization Initiator The colored resin composition of the present invention contains (D) a photopolymerization initiator. (D) By containing a photopolymerization initiator, film curability by photopolymerization can be imparted.
(D) The photopolymerization initiator can also be used as a mixture (photopolymerization initiator) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye added as needed. The photopolymerization initiation system is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.
　光重合開始剤としては、例えば、日本国特開昭５９－１５２３９６号、日本国特開昭６１－１５１１９７号各公報に記載のチタノセン化合物を含むメタロセン化合物や、日本国特開平１０－３９５０３号公報に記載のヘキサアリールビイミダゾール誘導体、ハロメチル－ｓ－トリアジン誘導体、Ｎ－フェニルグリシン等のＮ－アリール－α－アミノ酸類、Ｎ－アリール－α－アミノ酸塩類、Ｎ－アリール－α－アミノ酸エステル類等のラジカル活性剤、α-アミノアルキルフェノン系化合物、日本国特開２０００－８００６８号公報に記載されているオキシムエステル系開始剤が挙げられる。 Examples of the photopolymerization initiator include metallocene compounds containing titanosen compounds described in Japanese Patent Laid-Open Nos. 59-152396 and Japanese Patent Laid-Open No. 61-151197, and Japanese Patent Application Laid-Open No. 10-39503. N-aryl-α-amino acids such as hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, etc. Examples thereof include a radical activator of the above, an α-aminoalkylphenone-based compound, and an oxime ester-based initiator described in Japanese Patent Application Laid-Open No. 2000-80068.
　本発明で用いることができる光重合開始剤の具体的な例を以下に列挙する。
　２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシカルボニルナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン等のハロメチル化トリアジン誘導体； Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4) Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
　２－トリクロロメチル－５－（２′－ベンゾフリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２′－ベンゾフリル）ビニル〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２′－（６″－ベンゾフリル）ビニル）〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５一フリル－１，３，４－オキサジアゾール等のハロメチル化オキサジアゾール誘導体；
　２－（２′－クロロフェニル）－４，５－ジフェニルイミダソール２量体、２－（２′－クロロフェニル）－４，５－ビス（３′－メトキシフェニル）イミダゾール２量体、２－（２′－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２′－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体、（４′－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体等のイミダゾール誘導体；
　ベンゾインメチルエーテル、ベンゾインフェニルエーテル、ベンゾインイソブチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインアルキルエーテル類；
　２－メチルアントラキノン、２－エチルアントラキノン、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誘導体； 2-Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-benzofuryl) vinyl] -1,3,4-oxa Diazol, 2-trichloromethyl-5-[β- (2'-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-one frill-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2'-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2-( 2'-Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenyl Imidazole derivatives such as imidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
　ベンゾフェノン、ミヒラーズケトン、２－メチルベンゾフェノン、３－メチルベンゾフェノン、４－メチルベンゾフェノン、２－クロロベンゾフェノン、４－ブロモベンゾフェノン、２－カルボキシベンゾフェノン等のベンゾフェノン誘導体；
　２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシアセトフェノン、１－ヒドロキシシクロへキシルフェニルケトン、α－ヒドロキシ－２－メチルフェニルプロパノン、１－ヒドロキシ－１－メチルエチル－（ｐ－イソプロピルフェニル）ケトン、１－ヒドロキシ－１－（ｐ－ドデシルフェニル）ケトン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、１，１，１－トリクロロメチル－（ｐ一ブチルフェニル）ケトン等のアセトフェノン誘導体；
　チオキサントン、２－エチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントン、２，４－ジメチルチオキサントン、２、４－ジエ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等のチオキサントン誘導体； Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanol, 1-hydroxy-1-methylethyl- (p) -Isopropylphenyl) Ketone, 1-Hydroxy-1- (p-dodecylphenyl) Ketone, 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 1,1,1 -Acetophenone derivatives such as trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
　ｐ－ジメチルアミノ安息香酸エチル、Ｐ－ジエチルアミノ安息香酸エチル等の安息香酸エステル誘導体；
　９－フェニルアクリジン、９－（ｐ－メトキシフェニル）アクリジン等のアクリジン誘導体；
　９，１０－ジメチルベンズフェナジン等のフェナジン誘導体；
　ベンズアンスロン等のアンスロン誘導体；
　ジシクロペンタジエニル－Ｔｉ－ジクロライド、ジシクロペンタジェニル－Ｔｉ－ビス－フェニル、ジシクロペンタジェニル－Ｔｉ－ビス－２，３，４，５，６－ペンタフルオロフェニル－１－イル、ジシクロペンタジェニル－Ｔｉ－ビス－２，３，５，６－テトラフルオロフェニル－１－イル、ジシクロペンタジェニル－Ｔｉ－ビス－２，４，６－トリフルオロフェニ－１－イル、ジシクロペンタジェニル－Ｔｉ－２，６－ジプルオロフェニ－１－イル、ジシクロペンタジェニル－Ｔｉ－２，４－ジフルオロフェニ－１－イル、ジメチルシクロペンタジェニル－Ｔｉ－ビス－２，３，４，５，６－ペンタフルオロフェニ－１－イル、ジメチルシクロペンタジェニル－Ｔｉ－ビス－２，６－ジフルオロフェニ－１－イル、ジシクロペンタジェニル－Ｔｉ－２，６－ジフルオロ－３－（ピル－１－イル）－フェニ－１－イル等のチタノセン誘導体； Ethyl benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as Benz anthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentagenyl-Ti-bis-phenyl, dicyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentagenyl-Ti-bis-2,4,6-trifluoropheni-1-yl, Dicyclopentagenyl-Ti-2,6-diprulopheni-1-yl, dicyclopentagenyl-Ti-2,4-difluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,3 , 4,5,6-pentafluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,6-difluoropheni-1-yl, dicyclopentagenyl-Ti-2,6-difluoro- Titanocene derivatives such as 3- (pill-1-yl) -pheni-1-yl;
　２－メチル－１［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、４－ジメチルアミノエチルベンゾエ－ト、４－ジメチルアミノイソアミルベンゾエ－ト、４－ジエチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン、２－エチルヘキシル－１，４－ジメチルアミノベンゾエート、２，５－ビス（４－ジエチルアミノベンザル）シクロヘキサノン、７－ジエチルアミノ－３－（４－ジエチルアミノベンゾイル）クマリン、４－（ジエチルアミノ）カルコン等のα－アミノアルキルフェノン系化合物；
　１，２－オクタンジオン－１－［４－（フェニルチオ）フェニル］－２－（Ｏ－ベンゾイルオキシム）エタノン、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）等のオキシムエステル系化合物。 2-Methyl-1 [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-Aminoalkylphenone compounds such as;
1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) esterone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-3 Oxime ester compounds such as -1- (O-acetyloxime).
　感度及び表面性状の観点から、オキシムエステル系化合物（オキシムエステル系光重合開始剤）が好ましい。
　オキシムエステル系化合物は、その構造の中に紫外線を吸収する構造と光エネルギーを伝達する構造とラジカルを発生する構造を併せ持っているために、少量で感度が高く、かつ熱反応に対しては安定であり、少量で高感度な着色樹脂組成物の設計が可能である。特に、露光光源のｉ線（３６５ｎｍ）に対する光吸収性の観点から、置換基を有していてもよいカルバゾール環を有するオキシムエステル系化合物が好ましい。 From the viewpoint of sensitivity and surface properties, an oxime ester-based compound (oxime ester-based photopolymerization initiator) is preferable.
Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in their structure, so that they are highly sensitive in a small amount and stable against thermal reactions. Therefore, it is possible to design a highly sensitive colored resin composition with a small amount. In particular, an oxime ester-based compound having a carbazole ring, which may have a substituent, is preferable from the viewpoint of light absorption of the exposure light source for i-ray (365 nm).
　オキシムエステル系化合物としては、例えば、下記一般式（Ｉ－１）で表される化合物が挙げられる。 Examples of the oxime ester compound include compounds represented by the following general formula (I-1).
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　式（Ｉ－１）中、Ｒ21aは、水素原子、置換基を有していてもよいアルキル基、又は、置換基を有していてもよい芳香族環基を表す。
　Ｒ21bは芳香環又はヘテロ芳香環を含む任意の置換基を表す。
　Ｒ22aは、置換基を有していてもよいアルカノイル基、又は、置換基を有していてもよいアリーロイル基を表す。 In formula (I-1), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R 21b represents any substituent, including aromatic or heteroaromatic rings.
R 22a represents an alkanoyl group which may have a substituent or an allyloyl group which may have a substituent.
　Ｒ21aにおけるアルキル基の炭素数は特に限定されないが、溶剤への溶解性や露光に対する感度の観点から、通常１以上、好ましくは２以上、また、通常２０以下、好ましくは１５以下、より好ましくは１０以下、さらに好ましくは５以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、アルキル基の炭素数は１～２０が好ましく、１～１５がより好ましく、１～１０がさらに好ましく、１～５がよりさらに好ましく、２～５が特に好ましい。
　アルキル基としては、例えば、メチル基、エチル基、プロピル基、シクロペンチルエチル基、プロピル基が挙げられる。
　アルキル基が有していてもよい置換基としては、例えば、芳香族環基、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、４－（２－メトキシ－１－メチル）エトキシ－２－メチルフェニル基又はＮ－アセチル－Ｎ－アセトキシアミノ基が挙げられる。合成容易性の観点から、無置換であることが好ましい。 The number of carbon atoms of the alkyl group in R 21a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent and sensitivity to exposure. It is 10 or less, more preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group and a propyl group.
Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-. Examples thereof include a methylphenyl group or an N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
　Ｒ21aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、着色樹脂組成物への溶解性の観点から５以上であることが好ましい。また、現像性の観点から３０以下であることが好ましく、２０以下であることがより好ましく、１２以下であることがさらに好ましく、８以下であることが特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、芳香族環基の炭素数は、５～３０が好ましく、５～２０がより好ましく、５～１２がさらに好ましく、５～８が特に好ましい。 Examples of the aromatic ring group in R 21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored resin composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, further preferably 12 or less, and particularly preferably 8 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the aromatic ring group is preferably 5 to 30, more preferably 5 to 20, further preferably 5 to 12, and particularly preferably 5 to 8.
　芳香族環基としては、例えば、フェニル基、ナフチル基、ピリジル基、フリル基、フルオレニル基が挙げられる。現像性の観点から、フェニル基、ナフチル基、フルオレニル基が好ましく、フェニル基、フルオレニル基がより好ましい。
　芳香族環基が有していてもよい置換基としては、例えば、水酸基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、アルキル基が挙げられる。現像性の観点から水酸基、カルボキシ基が好ましく、カルボキシ基がより好ましい。置換基を有していてもよいアルキル基や置換基を有していてもよいアルコキシ基における置換基としては、例えば、水酸基、アルコキシ基、ハロゲン原子、ニトロ基が挙げられる。
　現像性の観点から、Ｒ21aとしては置換基を有していてもよいアルキル基が好ましく、無置換のアルキル基がより好ましく、メチル基がさらに好ましい。 Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a frill group and a fluorenyl group. From the viewpoint of developability, a phenyl group, a naphthyl group and a fluorenyl group are preferable, and a phenyl group and a fluorenyl group are more preferable.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a carboxy group, and a halogen atom. Examples thereof include an amino group, an amide group and an alkyl group. From the viewpoint of developability, a hydroxyl group and a carboxy group are preferable, and a carboxy group is more preferable. Examples of the substituent in the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group, a halogen atom and a nitro group.
From the viewpoint of developability, as R 21a , an alkyl group which may have a substituent is preferable, an unsubstituted alkyl group is more preferable, and a methyl group is further preferable.
　Ｒ21bは芳香環又はヘテロ芳香環を含む任意の置換基である。溶剤への溶解性や露光に対する感度の観点から、置換基を有していてもよいカルバゾリル基、置換基を有していてもよいチオキサントニル基、置換基を有していてもよいジフェニルスルフィド基又は置換基を有してもよいフルオレニル基、これらの基とカルボニル基とを連結した基が好ましい。露光光源のｉ線（３６５ｎｍ）に対する光吸収性の観点から、置換基を有していてもよいカルバゾリル基、又は置換基を有していてもよいカルバゾリル基とカルボニル基を連結した基が好ましい。 R 21b is any substituent, including aromatic or heteroaromatic rings. From the viewpoint of solubility in a solvent and sensitivity to exposure, a carbazolyl group which may have a substituent, a thioxanthonyl group which may have a substituent, a diphenylsulfide group which may have a substituent or A fluorenyl group which may have a substituent and a group in which these groups and a carbonyl group are linked are preferable. From the viewpoint of light absorption of the exposure light source for i-ray (365 nm), a carbazolyl group which may have a substituent or a group in which a carbazolyl group and a carbonyl group which may have a substituent are linked is preferable.
　カルバゾリル基が有していてもよい置換基としては、例えば、メチル基、エチル基等の炭素数１～１０のアルキル基；メトキシ基、エトキシ基などの炭素数１～１０のアルコキシ基；Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子；炭素数１～１０のアシル基；炭素数１～１０のアルキルエステル基；炭素数１～１０のアルコキシカルボニル基；炭素数１～１０のハロゲン化アルキル基；炭素数４～１０の芳香族環基；アミノ基；炭素数１～１０のアミノアルキル基；水酸基；ニトロ基；ＣＮ基；置換基を有していてもよいアリーロイル基；置換基を有していてもよいヘテロアリーロイル基；置換基を有していてもよいテノイル基が挙げられる。 Examples of the substituent that the carbazolyl group may have include an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; F, Halogen atoms such as Cl, Br, I; acyl group with 1 to 10 carbon atoms; alkyl ester group with 1 to 10 carbon atoms; alkoxycarbonyl group with 1 to 10 carbon atoms; alkyl halide group with 1 to 10 carbon atoms; An aromatic ring group having 4 to 10 carbon atoms; an amino group; an aminoalkyl group having 1 to 10 carbon atoms; a hydroxyl group; a nitro group; a CN group; an allylloyl group which may have a substituent; Heteroaryloyl groups may be; examples include tenoyl groups which may have substituents.
　Ｒ22aにおけるアルカノイル基の炭素数は特に限定されないが、溶剤への溶解性や感度の観点から、通常２以上、好ましくは３以上、また、通常２０以下、好ましくは１５以下、より好ましくは１０以下、さらに好ましくは５以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、アルカノイル基の炭素数は２～２０が好ましく、２～１５がより好ましく、２～１０がさらに好ましく、２～５がよりさらに好ましく、３～５が特に好ましい。
　アルカノイル基としては、例えば、アセチル基、エチロイル基、プロパノイル基、ブタノイル基が挙げられる。
　アルカノイル基が有していてもよい置換基としては、例えば、芳香族環基、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基が挙げられ、合成容易性の観点からは、無置換であることが好ましい。 The carbon number of the alkanoyl group in R 22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. , More preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the alkanoyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 10 carbon atoms, still more preferably 2 to 5 carbon atoms, and particularly preferably 3 to 5 carbon atoms.
Examples of the alkanoyl group include an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group and an amide group, which are unsubstituted from the viewpoint of ease of synthesis. Is preferable.
　Ｒ22aにおけるアリーロイル基の炭素数は特に限定されないが、溶剤への溶解性や感度の観点から、通常７以上、好ましくは８以上、また、通常２０以下、好ましくは１５以下、より好ましくは１０以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、アリーロイル基の炭素数は７～２０が好ましく、７～１５がより好ましく、７～１０がさらに好ましく、８～１０が特に好ましい。
　アリーロイル基としては、例えば、ベンゾイル基、ナフトイル基が挙げられる。
　アリーロイル基が有していてもよい置換基としては、例えば、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、アルキル基が挙げられ、合成容易性の観点からは、無置換であることが好ましい。 The carbon number of the allylloyl group in R 22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Is. The above upper and lower limits can be combined arbitrarily. For example, the allylloyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 15, still more preferably 7 to 10, and particularly preferably 8 to 10.
Examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group, which may be unsubstituted from the viewpoint of easiness of synthesis. preferable.
　式（Ｉ－１）で表される化合物として、露光光源のｉ線（３６５ｎｍ）に対する光吸収性の観点から、下記一般式（Ｉ－２）又は（Ｉ－３）で表される化合物が挙げられる。 Examples of the compound represented by the formula (I-1) include compounds represented by the following general formula (I-2) or (I-3) from the viewpoint of light absorption of the exposure light source for i-line (365 nm). Be done.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　式（Ｉ－２）及び式（Ｉ－３）中、Ｒ21a及びＲ22aは、式（Ｉ－１）と同義である。
　Ｒ23aは、置換基を有していてもよいアルキル基を表す。
　Ｒ24aは、置換基を有していてもよいアルキル基、置換基を有していてもよいアリーロイル基、置換基を有していてもよいヘテロアリーロイル基、又はニトロ基を表す。
　カルバゾール環を構成するベンゼン環は、さらに芳香族環によって縮合されて多環芳香族環となっていてもよい。 In formula (I-2) and formula (I-3), R 21a and R 22a are synonymous with formula (I-1).
R 23a represents an alkyl group which may have a substituent.
R 24a represents an alkyl group which may have a substituent, an allylloyl group which may have a substituent, a heteroallyloyl group which may have a substituent, or a nitro group.
The benzene ring constituting the carbazole ring may be further condensed by an aromatic ring to form a polycyclic aromatic ring.
　Ｒ23aにおけるアルキル基の炭素数は特に限定されないが、溶剤への溶解性の観点から、通常１以上、好ましくは２以上、また、通常２０以下、好ましくは１５以下、より好ましくは１０以下、さらに好ましくは５以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、アルキル基の炭素数は１～２０が好ましく、１～１５がより好ましく、１～１０がさらに好ましく、１～５がよりさらに好ましく、２～５が特に好ましい。
　アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、シクロヘキシル基が挙げられる。
　アルキル基が有していてもよい置換基としては、例えば、カルボニル基、カルボキシ基、ヒドロキシル基、フェニル基、ベンジル基、シクロヘキシル基、ニトロ基が挙げられる。合成容易性の観点から、無置換であることが好ましい。
　Ｒ23aとしては、溶剤への溶解性と合成容易性の観点から、エチル基であることがより好ましい。 The number of carbon atoms of the alkyl group in R 23a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further. It is preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and a cyclohexyl group.
Examples of the substituent that the alkyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group and a nitro group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
R 23a is more preferably an ethyl group from the viewpoint of solubility in a solvent and easiness of synthesis.
　Ｒ24aにおけるアルキル基の炭素数は特に限定されないが、溶剤への溶解性の観点から、通常１以上、好ましくは２以上、また、通常２０以下、好ましくは１５以下、より好ましくは１０以下、さらに好ましくは５以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、アルキル基の炭素数は１～２０が好ましく、１～１５がより好ましく、１～１０がさらに好ましく、１～５がよりさらに好ましく、２～５が特に好ましい。
　アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、シクロヘキシル基が挙げられる。
　アルキル基が有していてもよい置換基としては、例えば、カルボニル基、カルボキシ基、ヒドロキシル基、フェニル基、ベンジル基、シクロヘキシル基、ニトロ基が挙げられる。合成容易性の観点から、無置換であることが好ましい。 The number of carbon atoms of the alkyl group in R 24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further. It is preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and a cyclohexyl group.
Examples of the substituent that the alkyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group and a nitro group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
　Ｒ24aにおけるアリーロイル基の炭素数は特に限定されないが、溶剤への溶解性の観点から、通常７以上、好ましくは８以上、より好ましくは９以上、また、通常２０以下、好ましくは１５以下、より好ましくは１０以下、さらに好ましくは９以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、アリーロイル基の炭素数は７～２０が好ましく、８～１５がより好ましく、９～１０がさらに好ましく、９が特に好ましい。
　アリーロイル基としては、例えば、ベンゾイル基、ナフトイル基が挙げられる。
　アリーロイル基が有していてもよい置換基としては、例えば、カルボニル基、カルボキシ基、ヒドロキシル基、フェニル基、ベンジル基、シクロヘキシル基、ニトロ基が挙げられる。合成容易性の観点から、エチル基であることが好ましい。 The carbon number of the allylloyl group in R 24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. It is preferably 10 or less, more preferably 9 or less. The above upper and lower limits can be combined arbitrarily. For example, the allylloyl group preferably has 7 to 20 carbon atoms, more preferably 8 to 15, still more preferably 9 to 10, and particularly preferably 9.
Examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group and a nitro group. From the viewpoint of ease of synthesis, an ethyl group is preferable.
　Ｒ24aにおけるヘテロアリーロイル基の炭素数は特に限定されないが、溶剤への溶解性の観点から、通常７以上、好ましくは８以上、より好ましくは９以上、また、通常２０以下、好ましくは１５以下、より好ましくは１０以下、さらに好ましくは９以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、ヘテロアリーロイル基の炭素数は７～２０が好ましく、８～１５がより好ましく、９～１０がさらに好ましく、９が特に好ましい。
　ヘテロアリール基としては、例えば、フルオロベンゾイル基、クロロベンゾイル基、ブロモベンゾイル基、フルオロナフトイル基、クロロナフトイル基、ブロモナフトイル基が挙げられる。
　ヘテロアリーロイル基が有していてもよい置換基としては、例えば、カルボニル基、カルボキシ基、ヒドロキシル基、フェニル基、ベンジル基、シクロヘキシル基、ニトロ基が挙げられる。合成容易性の観点から、無置換であることが好ましい。
　Ｒ24aとしては、感度の観点から、置換基を有していてもよいアリーロイル基が好ましく、ベンゾイル基がより好ましい。 The number of carbon atoms of the heteroallyloyl group in R 24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. , More preferably 10 or less, still more preferably 9 or less. The above upper and lower limits can be combined arbitrarily. For example, the heteroallyloyl group preferably has 7 to 20 carbon atoms, more preferably 8 to 15, still more preferably 9 to 10, and particularly preferably 9.
Examples of the heteroaryl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group, and a bromonaphthoyl group.
Examples of the substituent that the heteroarylloyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group and a nitro group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
As R 24a , an allylloyl group which may have a substituent is preferable, and a benzoyl group is more preferable, from the viewpoint of sensitivity.
　カルバゾール環を構成するベンゼン環は、さらに芳香族環によって縮合されて多環芳香族環となっていてもよい。 The benzene ring constituting the carbazole ring may be further condensed by an aromatic ring to form a polycyclic aromatic ring.
　オキシムエステル系化合物の市販品として、例えば、ＢＡＳＦ社製のＯＸＥ－０２、ＯＸＥ－０３、常州強力電子新材料社製のＴＲ－ＰＢＧ－３０４、ＴＲ－ＰＢＧ－３１４、ＡＤＥＫＡ社製のＮ－１９１９、ＮＣＩ－９３０、ＮＣＩ－８３１が挙げられる。 Commercially available oxime ester compounds include, for example, OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Joshu Strong Electronics New Materials Co., Ltd., and N-1919 manufactured by ADEKA Corporation. , NCI-930, NCI-831.
　オキシムエステル系化合物として、具体的には以下の化合物が挙げられる。 Specific examples of the oxime ester compound include the following compounds.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　これらの光重合開始剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 These photopolymerization initiators may be used alone or in combination of two or more.
　（Ｄ）光重合開始剤に加えて、さらに連鎖移動剤を用いてもよい。連鎖移動剤とは、発生したラジカルを受け取り、受け取ったラジカルを他の化合物に受け渡す機能を有する化合物である。
　連鎖移動剤としては、上記機能を有する化合物であれば種々の連鎖移動剤を用いることができるが、例えば、メルカプト基含有化合物や、四塩化炭素等が挙げられ、連鎖移動効果が高い傾向があることからメルカプト基含有化合物を用いることがより好ましい。Ｓ－Ｈ結合エネルギーが小さいことによって結合開裂が起こりやすく、水素引きぬき反応や連鎖移動反応を起こしやすいためであると考えられる。感度向上や表面硬化性に有効である。 (D) In addition to the photopolymerization initiator, a chain transfer agent may be further used. The chain transfer agent is a compound having a function of receiving a generated radical and transferring the received radical to another compound.
As the chain transfer agent, various chain transfer agents can be used as long as they are compounds having the above functions, and examples thereof include mercapto group-containing compounds and carbon tetrachloride, which tend to have a high chain transfer effect. Therefore, it is more preferable to use a mercapto group-containing compound. It is considered that this is because the bond cleavage is likely to occur due to the small SH binding energy, and a hydrogen drawing reaction or a chain transfer reaction is likely to occur. It is effective for improving sensitivity and surface hardening.
　メルカプト基含有化合物としては、例えば、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾール、２－メルカプトベンゾオキサゾール、３－メルカプト－１，２，４－トリアゾール、２－メルカプト－４（３Ｈ）－キナゾリン、β－メルカプトナフタレン、１，４－ジメチルメルカプトベンゼン等の芳香族環を有するメルカプト基含有化合物；へキサンジチオール、デカンジチオール、ブタンジオールビス（３－メルカプトプロピオネート）、ブタンジオールビスチオグリコレート、エチレングリコールビス（３－メルカプトプロピオネート）、エチレングリコールビスチオグリコレート、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリメチロールプロパントリスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、ブタンジオールビス（３－メルカプトブチレート）、エチレングリコールビス（３－メルカプトブチレート）、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン等の脂肪族系のメルカプト基含有化合物が挙げられる。表面平滑性の観点から、メルカプト基を複数有する化合物が好ましい。 Examples of the mercapto group-containing compound include 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline. Mercapto group-containing compounds having an aromatic ring such as β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene; hexanedithiol, decandithiol, butanediolbis (3-mercaptopropionate), butanediolbisthioglycolate, Ethethyleneglycolbis (3-mercaptopropionate), ethyleneglycolbisthioglycolate, trimethylolpropanetris (3-mercaptopropionate), trimethylolpropanetristhioglycolate, trishydroxyethyltristhiopropionate, penta Erislitholtetrakis (3-mercaptopropionate), pentaerythritoltris (3-mercaptopropionate), butanediolbis (3-mercaptobutyrate), ethyleneglycolbis (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptobutyrate) 3-Mercaptobutyrate), Pentaerythritoltetrakis (3-Mercaptobutyrate), Pentaerythritol Tris (3-Mercaptobutyrate), 1,3,5-Tris (3-Mercaptobutyloxyethyl) -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -Trione and other aliphatic mercapto group-containing compounds can be mentioned. From the viewpoint of surface smoothness, a compound having a plurality of mercapto groups is preferable.
　芳香族環を有するメルカプト基含有化合物としては、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾールが好ましく、脂肪族系のメルカプト基含有化合物としては、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンが好ましい。 As the mercapto group-containing compound having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzoimidazole are preferable, and as the aliphatic mercapto group-containing compound, trimethylolpropanthris (3-mercaptopropionate), Pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylol propanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-Mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione are preferred.
　感度の面からは、脂肪族系のメルカプト基含有化合物が好ましく、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンが好ましく、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）がより好ましい。
　これらの連鎖移動剤は１種を単独で用いてもよく、２種以上を併用してもよい。 From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferable, such as trimethylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritoltris (3-mercaptopro). Pionate), Trimethylol Propantris (3-Mercaptobutyrate), Pentaerythritol Tetrakis (3-Mercaptobutyrate), Pentaerythritol Tris (3-Mercaptobutyrate), 1,3,5-Tris (3-Mercaptobutylate) Oxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion is preferred, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate). ) Is more preferable.
One of these chain transfer agents may be used alone, or two or more thereof may be used in combination.
　本発明の着色樹脂組成物において、（Ｄ）光重合開始剤の含有割合は特に限定されないが、着色樹脂組成物の全固形分中に０．５質量％以上が好ましく、０．８質量％以上がより好ましく、１．０質量％以上がさらに好ましく、１．２質量％以上が特に好ましく、また、１０質量％以下が好ましく、８質量％以下がより好ましく、６質量％以下がさらに好ましく、４質量％以下が特に好ましい。前記下限値以上とすることで塗膜の硬化性が向上する傾向があり、また、前記上限値以下とすることで可視光吸収が低減されることで輝度が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物において、（Ｄ）光重合開始剤の含有割合は、着色樹脂組成物の全固形分中に０．５～１０質量％が好ましく、０．８～８質量％がより好ましく、１．０～６質量％がさらに好ましく、１．２～４質量％が特に好ましい。 In the colored resin composition of the present invention, the content ratio of the (D) photopolymerization initiator is not particularly limited, but is preferably 0.5% by mass or more, preferably 0.8% by mass or more in the total solid content of the colored resin composition. Is more preferable, 1.0% by mass or more is further preferable, 1.2% by mass or more is particularly preferable, 10% by mass or less is more preferable, 8% by mass or less is more preferable, and 6% by mass or less is further preferable. Mass% or less is particularly preferable. When it is at least the lower limit value, the curability of the coating film tends to be improved, and when it is at least the upper limit value, visible light absorption is reduced and the brightness tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, in the colored resin composition, the content ratio of the (D) photopolymerization initiator is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass in the total solid content of the colored resin composition. , 1.0 to 6% by mass is more preferable, and 1.2 to 4% by mass is particularly preferable.
　本発明の着色樹脂組成物が連鎖移動剤を含有する場合、その含有割合は特に限定されないが、着色樹脂組成物の全固形分中に０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．３質量％以上がさらに好ましく、０．４質量％以上が特に好ましく、また、３質量％以下が好ましく、２．５質量％以下がより好ましく、２質量％以下がさらに好ましく、１．５質量％以下が特に好ましい。前記下限値以上とすることで耐溶剤性が向上する傾向があり、また、前記上限値以下とすることで保存安定性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物が連鎖移動剤を含有する場合、その含有割合は、着色樹脂組成物の全固形分中に０．１～３質量％が好ましく、０．２～２．５質量％がより好ましく、０．３～２質量％がさらに好ましく、０．４～１．５質量％が特に好ましい。 When the colored resin composition of the present invention contains a chain transfer agent, the content ratio thereof is not particularly limited, but is preferably 0.1% by mass or more, preferably 0.2% by mass or more in the total solid content of the colored resin composition. Is more preferable, 0.3% by mass or more is further preferable, 0.4% by mass or more is particularly preferable, 3% by mass or less is more preferable, 2.5% by mass or less is more preferable, and 2% by mass or less is further preferable. , 1.5% by mass or less is particularly preferable. When it is at least the above lower limit value, the solvent resistance tends to be improved, and when it is at least the above upper limit value, the storage stability tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains a chain transfer agent, the content ratio is preferably 0.1 to 3% by mass, and 0.2 to 2.5% by mass in the total solid content of the colored resin composition. More preferably, 0.3 to 2% by mass is further preferable, and 0.4 to 1.5% by mass is particularly preferable.
［１－５］（Ｅ）光重合性モノマー
　本発明の着色樹脂組成物は、（Ｅ）光重合性モノマーを含有する。光重合性モノマーは、重合可能な低分子化合物であれば特に制限はないが、エチレン性二重結合を少なくとも１つ有する付加重合可能な化合物（以下、「エチレン性化合物」と称す。）が好ましい。エチレン性化合物とは、本発明の着色樹脂組成物が活性光線の照射を受けた場合、光重合開始剤の作用により付加重合し、硬化するようなエチレン性二重結合を有する化合物である。なお、本発明における単量体は、いわゆる高分子物質に相対する概念を意味し、狭義の単量体以外に二量体、三量体、オリゴマーも含有する概念を意味する。 [1-5] (E) Photopolymerizable Monomer The colored resin composition of the present invention contains (E) a photopolymerizable monomer. The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular weight compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”) is preferable. .. The ethylenic compound is a compound having an ethylenic double bond such that when the colored resin composition of the present invention is irradiated with active light, it is addition-polymerized by the action of a photopolymerization initiator and cured. The monomer in the present invention means a concept opposite to a so-called polymer substance, and means a concept containing a dimer, a trimer, and an oligomer in addition to the monomer in a narrow sense.
　本発明の着色樹脂組成物における（Ｅ）光重合性モノマーは、下記一般式（Ｉ）で表される部分構造を有する光重合性モノマー（ｅ１）（以下、「光重合性モノマー（ｅ１）」と称する場合がある。）を含む。 The (E) photopolymerizable monomer in the colored resin composition of the present invention is a photopolymerizable monomer (e1) having a partial structure represented by the following general formula (I) (hereinafter, “photopolymerizable monomer (e1)””. May be referred to as).
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
（式（Ｉ）中、Ｒ1は炭素数２以上のアルキレン基を表す。
　Ｒ2は、水素原子又はメチル基を表す。
　ｎは１以上の整数を表す。
　＊は結合手を表す。） (In the formula (I), R 1 represents an alkylene group having 2 or more carbon atoms.
R 2 represents a hydrogen atom or a methyl group.
n represents an integer of 1 or more.
* Represents a bond. )
　光重合性モノマー（ｅ１）は、アルキレンオキサイド鎖を有するものであることにより、１００℃のような残留溶媒の少ない塗膜状態であったとしても現像液浸透性を良好に保つ事で、フタロシアニン化合物（１）を含む着色樹脂組成物であってもホール径のプリベーク温度依存性の低下が抑制できると考えられる。 Since the photopolymerizable monomer (e1) has an alkylene oxide chain, the phthalocyanine compound can maintain good developer permeability even in a coating film state having a small residual solvent such as 100 ° C. It is considered that even the colored resin composition containing (1) can suppress the decrease in the prebake temperature dependence of the hole diameter.
（Ｒ1）
　式（Ｉ）中、Ｒ1は炭素数２以上のアルキレン基を表す。アルキレン基は置換基を有さない。
　アルキレン基は、直鎖状でも、分岐鎖状でも、環状でも、それらの組み合わせでもよい。溶剤溶解性、耐溶剤性の観点から直鎖状のアルキレン基が好ましい。
　アルキレン基の炭素数は２以上であれば特に限定されないが、４以下が好ましく、３以下がより好ましく、２がさらに好ましい。前記上限値以下とすることで塗膜感度、耐溶剤性が向上する傾向がある。例えば、アルキレン基の炭素数は２～４が好ましく、２～３がより好ましく、２がさらに好ましい。 (R 1 )
In formula (I), R 1 represents an alkylene group having 2 or more carbon atoms. The alkylene group has no substituent.
The alkylene group may be linear, branched, cyclic, or a combination thereof. A linear alkylene group is preferable from the viewpoint of solvent solubility and solvent resistance.
The number of carbon atoms of the alkylene group is not particularly limited as long as it is 2 or more, but it is preferably 4 or less, more preferably 3 or less, still more preferably 2. By setting the value to the upper limit or less, the coating film sensitivity and solvent resistance tend to be improved. For example, the alkylene group preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms, and even more preferably 2.
　アルキレン基としては、例えば、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、イソプロピレン基が挙げられる。塗膜硬化性の観点から、ｎ－プロピレン基、エチレン基が好ましく、エチレン基がより好ましい。 Examples of the alkylene group include an ethylene group, an n-propylene group, an n-butylene group, and an isopropylene group. From the viewpoint of coating film curability, an n-propylene group and an ethylene group are preferable, and an ethylene group is more preferable.
（ｎ）
　式（Ｉ）において、ｎは１以上の整数を表すが、４以下が好ましく、３以下がより好ましく、２以下がさらに好ましい。前記上限値以下とすることで塗膜硬化性が向上する傾向がある。例えば、ｎは１～４が好ましく、１～３がより好ましく、１～２がさらに好ましい。 (N)
In the formula (I), n represents an integer of 1 or more, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less. When the value is not more than the upper limit, the curability of the coating film tends to be improved. For example, n is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2.
　光重合性モノマー（ｅ１）としては、塗膜硬化性の観点から、下記一般式（ＩＩ）で表される化合物が好ましい。 As the photopolymerizable monomer (e1), a compound represented by the following general formula (II) is preferable from the viewpoint of coating film curability.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
（式（ＩＩ）中、Ｒ1、Ｒ2及びｎは、式（Ｉ）と同義である。
　Ｚは、直接結合、酸素原子、硫黄原子、２～４価の脂肪族炭化水素基、４価の炭素原子、２～４価の非芳香族複素環基、２～４価の芳香族環基、又は下記一般式（ＩＩＩ）で表される部分構造を表す。
　ｐは、２～６の整数を表す。
　なお、一分子中に含まれる複数の下記一般式（ＩＩ’）で表される構造は、同じでもよく、また異なっていてもよい。） (In formula (II), R 1 , R 2 and n are synonymous with formula (I).
Z is a direct bond, an oxygen atom, a sulfur atom, a 2- to 4-valent aliphatic hydrocarbon group, a 4-valent carbon atom, a 2- to 4-valent non-aromatic heterocyclic group, and a 2- to 4-valent aromatic ring group. , Or a partial structure represented by the following general formula (III).
p represents an integer of 2 to 6.
The structures represented by the following general formula (II') contained in one molecule may be the same or different. )
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
（式（ＩＩＩ）中、＊は結合手を表す。） (In formula (III), * represents a bond.)
（Ｚ）
　式（ＩＩ）において、Ｘは、直接結合、酸素原子、硫黄原子、２～４価の脂肪族炭化水素基、４価の炭素原子、２～４価の非芳香族複素環基、２～４価の芳香族環基、又は式（ＩＩＩ）で表される部分構造を表す。 (Z)
In formula (II), X is a direct bond, an oxygen atom, a sulfur atom, a 2- to 4-valent aliphatic hydrocarbon group, a 4-valent carbon atom, a 2- to 4-valent non-aromatic heterocyclic group, 2 to 4 It represents an aromatic ring group of valence or a partial structure represented by the formula (III).
　２～４価の脂肪族炭化水素基は、直鎖状でも、分岐鎖状でも、環状でも、それらの組み合わせでもよい。２～４価の脂肪族炭化水素基の炭素数は特に限定されないが、１０以下が好ましく、９以下がより好ましく、８以下がさらに好ましく、また、通常１以上である。前記上限値以下とすることで塗膜硬化性が向上し、耐溶剤性が改善する傾向がある。例えば、２～４価の脂肪族炭化水素基の炭素数は１～１０が好ましく、１～９がより好ましく、１～８がさらに好ましい。
　２～４価の脂肪族炭化水素基としては、例えば、２～４個の遊離原子価を有する、メタン、エタン、プロパン、ブタンが挙げられる。 The 2- to tetravalent aliphatic hydrocarbon group may be linear, branched-chain, cyclic, or a combination thereof. The number of carbon atoms of the 2- to tetravalent aliphatic hydrocarbon group is not particularly limited, but is preferably 10 or less, more preferably 9 or less, further preferably 8 or less, and usually 1 or more. When the value is not more than the upper limit, the curability of the coating film is improved and the solvent resistance tends to be improved. For example, the number of carbon atoms of the 2- to tetravalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 9, and even more preferably 1 to 8.
Examples of the 2- to 4-valent aliphatic hydrocarbon group include methane, ethane, propane and butane having 2 to 4 free valences.
　２～４価の非芳香族複素環基における非芳香族複素環としては、単環であっても縮合環であってもよい。非芳香族複素環は、ヘテロ原子として窒素原子、硫黄原子及び酸素原子のいずれか一つを含む非芳香族環である。非芳香族複素環にヘテロ原子が複数含まれる場合、これらは同一であっても異なっていてもよい。
　２～４価の非芳香族複素環基の炭素数は特に限定されないが、３以上が好ましく、４以上がより好ましく、また、８以下が好ましく、６以下がより好ましい。前記下限値以上とすることで耐熱性が向上する傾向があり、また、前記上限値以下とすることで溶媒溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、２～４価の非芳香族複素環基の炭素数は３～８が好ましく、３～６がより好ましく、４～６がさらに好ましい。
　２～４価の非芳香族複素環基としては、例えば、２～４個の遊離原子価を有する、ピペリジン環、ピロリジン環が挙げられる。 The non-aromatic heterocycle in the 2- to tetravalent non-aromatic heterocyclic group may be a monocyclic ring or a condensed ring. The non-aromatic heterocycle is a non-aromatic ring containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom. When a plurality of heteroatoms are contained in a non-aromatic heterocycle, they may be the same or different.
The number of carbon atoms of the 2- to tetravalent non-aromatic heterocyclic group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, preferably 8 or less, and more preferably 6 or less. When it is at least the above lower limit value, the heat resistance tends to be improved, and when it is at least the above upper limit value, the solvent solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the 2- to tetravalent non-aromatic heterocyclic group is preferably 3 to 8, more preferably 3 to 6, and even more preferably 4 to 6.
Examples of the 2- to 4-valent non-aromatic heterocyclic group include a piperidine ring and a pyrrolidine ring having 2 to 4 free valences.
　２～４価の芳香族環基としては、２～４価の芳香族炭化水素環基、及び２～４価の芳香族複素環基が挙げられる。
　２～４価の芳香族炭化水素環基における芳香族炭化水素環は、単環であっても縮合環であってもよい。芳香族炭化水素環基の炭素数は特に限定されないが、３以上が好ましく、４以上がより好ましく、５以上がさらに好ましく、また、１５以下が好ましく、１２以下がより好ましく、９以下がさらに好ましい。前記下限値以上とすることで耐熱性が向上する傾向があり、また、前記上限値以下とすることで輝度が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、２～４価の芳香族炭化水素環基の炭素数は３～１５が好ましく、４～１２がより好ましく、５～９がさらに好ましい。
　２～４価の芳香族炭化水素環基としては、例えば、２～４個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。 Examples of the 2- to 4-valent aromatic ring group include a 2- to 4-valent aromatic hydrocarbon ring group and a 2- to 4-valent aromatic heterocyclic group.
The aromatic hydrocarbon ring in the 2- to tetravalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The number of carbon atoms of the aromatic hydrocarbon ring group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, preferably 15 or less, more preferably 12 or less, still more preferably 9 or less. .. When it is at least the lower limit value, the heat resistance tends to be improved, and when it is at least the upper limit value, the brightness tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the 2- to 4-valent aromatic hydrocarbon ring group is preferably 3 to 15, more preferably 4 to 12, and even more preferably 5 to 9.
Examples of the 2- to 4-valent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, and a benzpyrene ring, which have 2 to 4 free atomic valences. , Chrysene ring, triphenylene ring, acenaphthene ring, fluorene ring, fluorene ring and the like.
　２～４価の芳香族複素環基における芳香族複素環は、単環であっても縮合環であってもよい。芳香族複素環基の炭素数は特に限定されないが、３以上が好ましく、４以上がより好ましく、５以上がさらに好ましく、また、１５以下が好ましく、１２以下がより好ましく、９以下がさらに好ましい。前記下限値以上とすることで耐熱性が向上する傾向があり、また、前記上限値以下とすることで輝度が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、２～４価の芳香族複素環基の炭素数は３～１５が好ましく、４～１２がより好ましく、５～９がさらに好ましい。
　２～４価の芳香族複素環基としては、例えば、２～４個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。 The aromatic heterocycle in the 2- to tetravalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. The number of carbon atoms of the aromatic heterocyclic group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, preferably 15 or less, more preferably 12 or less, still more preferably 9 or less. When it is at least the lower limit value, the heat resistance tends to be improved, and when it is at least the upper limit value, the brightness tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the 2- to tetravalent aromatic heterocyclic group is preferably 3 to 15, more preferably 4 to 12, and even more preferably 5 to 9.
Examples of the 2- to 4-valent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxadi ring having 2 to 4 free atomic valences. Azole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrazole ring, thienothiophene ring, flopyrol ring, flofran ring, thienofran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring , Pyrazole ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring. Will be.
　硬化性、パターニング特性の観点から、Ｚとしては、酸素原子、硫黄原子、４価の炭素原子が好ましく、４価の炭素原子であることがより好ましい。 From the viewpoint of curability and patterning characteristics, Z is preferably an oxygen atom, a sulfur atom, or a tetravalent carbon atom, and more preferably a tetravalent carbon atom.
（ｐ）
　式（ＩＩ）において、ｐは２～６の整数を表す。３以上が好ましく、また、５以下が好ましく、４以下がより好ましい。前記下限値以上とすることで電気信頼性が向上する傾向があり、また、前記上限値以下とすることで塗膜硬化性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、ｐは３～５が好ましく、３～４がより好ましい。 (P)
In formula (II), p represents an integer of 2-6. 3 or more is preferable, 5 or less is preferable, and 4 or less is more preferable. When it is at least the lower limit value, the electrical reliability tends to be improved, and when it is at least the upper limit value, the curability of the coating film tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, p is preferably 3 to 5, and more preferably 3 to 4.
　光重合性モノマー（ｅ１）としては、以下が挙げられる。 Examples of the photopolymerizable monomer (e1) include the following.
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　本発明の着色樹脂組成物における（Ｅ）光重合性モノマーは、光重合性モノマー（ｅ１）以外の光重合性モノマー（以下、「その他の光重合性モノマー（ｅ２）」と称する場合がある。）を含んでもよい。その他の光重合性モノマー（ｅ２）としては、特に、１分子中にエチレン性二重結合を２個以上有する多官能エチレン性単量体を使用することが望ましい。多官能エチレン性単量体が有するエチレン性二重結合の数は特に限定されないが、通常２個以上であり、好ましくは４個以上であり、より好ましくは５個以上であり、また、好ましくは８個以下であり、より好ましくは７個以下である。前記下限値以上とすることで高感度となる傾向があり、前記上限値以下とすることで溶媒への溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、多官能エチレン性単量体が有するエチレン性二重結合の数は２～８個が好ましく、４～８個がより好ましく、５～７個がさらに好ましい。 The (E) photopolymerizable monomer in the colored resin composition of the present invention may be referred to as a photopolymerizable monomer other than the photopolymerizable monomer (e1) (hereinafter, "other photopolymerizable monomer (e2)". ) May be included. As the other photopolymerizable monomer (e2), it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 5 or more. The number is 8 or less, more preferably 7 or less. When it is at least the lower limit value, the sensitivity tends to be high, and when it is at least the upper limit value, the solubility in a solvent tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of ethylenic double bonds contained in the polyfunctional ethylenic monomer is preferably 2 to 8, more preferably 4 to 8, and even more preferably 5 to 7.
　その他の光重合性モノマー（ｅ２）としては、例えば、不飽和カルボン酸、不飽和カルボン酸とモノヒドロキシ化合物とのエステル、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル、芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル、不飽和カルボン酸と多価カルボン酸及び前述の脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物とのエステル化反応により得られるエステル、ポリイソシアネート化合物と（メタ）アクリロイル含有ヒドロキシ化合物とを反応させたウレタン骨格を有するエチレン性化合物が挙げられる。 Examples of the other photopolymerizable monomer (e2) include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and aromatic polyhydroxy compounds. Esters with unsaturated carboxylic acids, esters obtained by esterification reactions between unsaturated carboxylic acids and polyvalent carboxylic acids, and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, polyisocyanates. Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting a compound with a (meth) acryloyl-containing hydroxy compound.
　脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、例えば、エチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールアクリレート等のアクリル酸エステルが挙げられる。また、これらアクリレートのアクリル酸部分を、メタクリル酸部分に代えたメタクリル酸エステル、イタコン酸部分に代えたイタコン酸エステル、クロトン酸部分に代えたクロトン酸エステル、又は、マレイン酸部分に代えたマレイン酸エステルが挙げられる。 Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, trimethylol propanetriacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. Examples thereof include acrylic acid esters such as dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. Further, the acrylic acid moiety of these acrylates is replaced with a methacrylic acid ester instead of a methacrylic acid moiety, an itaconic acid ester substituted with an itaconic acid moiety, a crotonic acid ester substituted with a crotonic acid moiety, or a maleic acid substituted with a maleic acid moiety. Ester can be mentioned.
　芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、例えば、ハイドロキノンジアクリレート、ハイドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート、ピロガロールトリアクリレートが挙げられる。
　不飽和カルボン酸と多価カルボン酸及び多価ヒドロキシ化合物とのエステル化反応により得られるエステルは、必ずしも単一物ではなく、混合物であってもよい。例えば、アクリル酸、フタル酸及びエチレングリコールの縮合物、アクリル酸、マレイン酸及びジエチレングリコールの縮合物、メタクリル酸、テレフタル酸及びペンタエリスリトールの縮合物、アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物が挙げられる。 Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. For example, a condensate of acrylic acid, phthalic acid and ethylene glycol, a condensate of acrylic acid, maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin. Can be mentioned.
　ポリイソシアネート化合物と（メタ）アクリロイル基含有ヒドロキシ化合物とを反応させたウレタン骨格を有するエチレン性化合物としては、例えば、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート；シクロヘキサンジイソシアネート、イソホロンジイソシアネート等の脂環式ジイソシアネート；トリレンジイソシアネート、ジフェニルメタンジイソシアネート等の芳香族ジイソシアネート等と、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、３－ヒドロキシ（１，１，１－トリアクリロイルオキシメチル）プロパン、３－ヒドロキシ（１，１，１－トリメタクリロイルオキシメチル）プロパン等の（メタ）アクリロイル基含有ヒドロキシ化合物との反応物が挙げられる。 Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate. Alicyclic diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloxymethyl) propane, 3- Examples thereof include a reaction product with a (meth) acryloyl group-containing hydroxy compound such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane.
　その他には、例えば、エチレンビスアクリルアミド等のアクリルアミド類；フタル酸ジアリル等のアリルエステル類；ジビニルフタレート等のビニル基含有化合物が挙げられる。
　その他の光重合性モノマー（ｅ２）は酸価を有するモノマーであってもよい。酸価を有するモノマーとしては、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルであり、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシル基に非芳香族カルボン酸無水物を反応させて酸基を持たせた多官能モノマーが好ましく、このエステルにおいて、脂肪族ポリヒドロキシ化合物がペンタエリスリトール及び／又はジペンタエリスリトールである多官能モノマーが特に好ましい。 Other examples thereof include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinylphthalate.
The other photopolymerizable monomer (e2) may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is formed by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The provided polyfunctional monomer is preferable, and in this ester, the polyfunctional monomer in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is particularly preferable.
　これらのモノマーは１種を単独で用いてもよいが、製造上、単一の化合物を用いることは難しいことから、２種以上を混合して用いてもよい。また、必要に応じてモノマーとして酸基を有しない多官能モノマーと酸基を有する多官能モノマーを併用してもよい。
　酸基を有する多官能モノマーの好ましい酸価としては、０．１～４０ｍｇＫＯＨ／ｇであり、特に好ましくは５～３０ｍｇＫＯＨ／ｇである。前記下限値以上とすることで現像溶解特性を良好なものとすることができる傾向があり、前記上限値以下とすることで製造や取扱いが良好になり光重合性能、画素の表面平滑性等の硬化性を良好にしやすい傾向がある。従って、異なる酸基の多官能モノマーを２種以上併用する場合、或いは酸基を有しない多官能モノマーを併用する場合、全体の多官能モノマーとしての酸基が上記範囲に入るように調整することが好ましい。 One of these monomers may be used alone, but since it is difficult to use a single compound in production, two or more of these monomers may be mixed and used. Further, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as the monomer.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When it is set to the lower limit value or more, the development and dissolution characteristics tend to be good, and when it is set to the upper limit value or less, the manufacturing and handling are improved, and the photopolymerization performance, the surface smoothness of the pixel, etc. are improved. It tends to improve the curability. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid group as the whole polyfunctional monomer should be adjusted so as to fall within the above range. Is preferable.
　本発明において、より好ましい酸基を有する多官能モノマーは、東亞合成社製ＴＯ１３８２として市販されているジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタアクリレートのコハク酸エステルを主成分とする混合物である。この多官能モノマーと、他の多官能モノマーを組み合わせて使用することもできる。また、日本国特開２０１３－１４０３４６号公報の段落［００５６］や［００５７］に記載の多官能モノマーを使用することもできる。 In the present invention, the polyfunctional monomer having a more preferable acid group contains a succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate commercially available as TO1382 manufactured by Toagosei Co., Ltd. as a main component. It is a mixture to be used. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Further, the polyfunctional monomer described in paragraphs [0056] and [0057] of Japanese Patent Application Laid-Open No. 2013-140346 can also be used.
　本発明において、画素の耐薬品性や画素のエッジの直線性を良好にするとの観点からは、日本国特開２０１３－１９５９７１号公報に記載の重合性モノマーを用いることが好ましい。
　塗布膜の感度及び現像時間の短縮を両立するとの観点からは、日本国特開２０１３－１９５９７４号公報に記載の重合性モノマーを用いることが好ましい。 In the present invention, from the viewpoint of improving the chemical resistance of the pixel and the linearity of the edge of the pixel, it is preferable to use the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195971.
From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the developing time, it is preferable to use the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195974.
　本発明の着色樹脂組成物における（Ｅ）光重合性モノマーの含有割合は特に限定されないが、着色樹脂組成物の全固形分中に５質量％以上が好ましく、７質量％以上がより好ましく、１０質量％以上がさらに好ましく、１２質量％以上が特に好ましく、また、５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下がさらに好ましく、２０質量％以下が特に好ましい。前記下限値以上とすることで塗膜硬化性が向上する傾向があり、また、前記上限値以下とすることで保存安定性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物における（Ｅ）光重合性モノマーの含有割合は、着色樹脂組成物の全固形分中に５～５０質量％が好ましく、７～４０質量％がより好ましく、１０～３０質量％がさらに好ましく、１２～２０質量％が特に好ましい。 The content ratio of the (E) photopolymerizable monomer in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 7% by mass or more in the total solid content of the colored resin composition. More preferably, it is more preferably mass% or more, 12% by mass or more, particularly preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. When it is at least the above lower limit value, the coating film curability tends to be improved, and when it is at least the above upper limit value, the storage stability tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the (E) photopolymerizable monomer in the colored resin composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and 10 to 30% by mass in the total solid content of the colored resin composition. % Is more preferable, and 12 to 20% by mass is particularly preferable.
　本発明の着色樹脂組成物における光重合性モノマー（ｅ１）の含有割合は特に限定されないが、着色樹脂組成物の全固形分中に５質量％以上が好ましく、７質量％以上がより好ましく、１０質量％以上がさらに好ましく、１２質量％以上が特に好ましく、また、５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下がさらに好ましく、２０質量％以下が特に好ましい。前記下限値以上とすることで現像液溶解性の向上やホットプレート温度上昇時のパターニング形状が良化する傾向があり、また、前記上限値以下とすることで保存安定性、パターン密着性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物における光重合性モノマー（ｅ１）の含有割合は、着色樹脂組成物の全固形分中に５～５０質量％が好ましく、７～４０質量％がより好ましく、１０～３０質量％がさらに好ましく、１２～２０質量％が特に好ましい。 The content ratio of the photopolymerizable monomer (e1) in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 7% by mass or more in the total solid content of the colored resin composition. More preferably, it is more preferably mass% or more, 12% by mass or more, particularly preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. When it is at least the above lower limit, the solubility of the developer tends to be improved and the patterning shape when the hot plate temperature rises tends to be improved, and when it is at least the above upper limit, the storage stability and the pattern adhesion are improved. Tend to do. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the photopolymerizable monomer (e1) in the colored resin composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and 10 to 30% by mass in the total solid content of the colored resin composition. % Is more preferable, and 12 to 20% by mass is particularly preferable.
　本発明の着色樹脂組成物において、（Ｅ）光重合性モノマーに対する光重合性モノマー（ｅ１）の含有割合は特に限定されないが、４０質量％以上が好ましく、４５質量％以上がより好ましく、５０質量％以上がさらに好ましく、５５質量％以上が特に好ましく、また、９８質量％以下が好ましく、９６質量％以下がより好ましく、９４質量％以下がさらに好ましく、９２質量％以下が特に好ましい。前記下限値以上とすることで現像液溶解性が向上する傾向があり、また、前記上限値以下とすることでパターニング特性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、（Ｅ）光重合性モノマーに対する光重合性モノマー（ｅ１）の含有割合は、４０～９８質量％が好ましく、４５～９６質量％がより好ましく、５０～９４質量％がさらに好ましく、５５～９２質量％が特に好ましい。 In the colored resin composition of the present invention, the content ratio of the photopolymerizable monomer (e1) to the (E) photopolymerizable monomer is not particularly limited, but is preferably 40% by mass or more, more preferably 45% by mass or more, and 50% by mass. % Or more is further preferable, 55% by mass or more is particularly preferable, 98% by mass or less is preferable, 96% by mass or less is more preferable, 94% by mass or less is further preferable, and 92% by mass or less is particularly preferable. When it is at least the lower limit value, the solubility of the developer tends to be improved, and when it is at least the upper limit value, the patterning property tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the photopolymerizable monomer (e1) to the (E) photopolymerizable monomer is preferably 40 to 98% by mass, more preferably 45 to 96% by mass, further preferably 50 to 94% by mass, and 55 to 55 to 92% by mass is particularly preferable.
［１－６］その他の固形分
　本発明の着色樹脂組成物には、さらに、必要に応じ上記成分以外の固形分を配合できる。このような成分としては、例えば、分散剤、分散助剤、界面活性剤、密着向上剤が挙げられる。 [1-6] Other solids The colored resin composition of the present invention may further contain solids other than the above components, if necessary. Examples of such a component include a dispersant, a dispersion aid, a surfactant, and an adhesion improver.
［１－６－１］分散剤、分散助剤
　本発明の着色樹脂組成物が（Ａ）着色剤として顔料を含む場合、顔料を安定に分散させる目的で分散剤を含むことが好ましい。分散剤の中でも高分子分散剤を用いると経時の分散安定性に優れるので好ましい。
　高分子分散剤としては、例えば、ウレタン系分散剤、ポリエチレンイミン系分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレングリコールジエステル系分散剤、ソルビタン脂肪族エステル系分散剤、脂肪族変性ポリエステル系分散剤を挙げることができる。
　高分子分散剤としては、商品名で、例えば、ＥＦＫＡ（登録商標、ＢＡＳＦ社製）、ＤｉｓｐｅｒＢＹＫ（登録商標、ビックケミー社製）、ディスパロン（登録商標、楠本化成社製）、ＳＯＬＳＰＥＲＳＥ（登録商標、ルーブリゾール社製）、ＫＰ（信越化学工業社製）、ポリフロー（共栄社化学社製）、特開２０１３－１１９５６８号公報に記載の分散剤を挙げることができる。 [1-6-1] Dispersant, Dispersion Aid When the colored resin composition of the present invention contains a pigment as (A) a colorant, it is preferable to contain a dispersant for the purpose of stably dispersing the pigment. Among the dispersants, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time.
Examples of the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters. A system dispersant can be mentioned.
Examples of the polymer dispersant include EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), and SOLSERSE (registered trademark, manufactured by Rubri). Dispersants described in Japanese Patent Laid-Open No. 2013-119568 (manufactured by Zol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) can be mentioned.
　高分子分散剤としては、分散性や保存安定性の観点から、窒素原子を含む官能基を有するブロック共重合体が好ましく、窒素原子を含む官能基を有するアクリル系ブロック共重合体がより好ましい。
　窒素原子を含む官能基を有するブロック共重合体としては、側鎖に４級アンモニウム塩基及び／又はアミノ基を有するＡブロックと、４級アンモニウム塩基及びアミノ基を有さないＢブロックとからなる、Ａ－Ｂブロック共重合体、Ｂ－Ａ－Ｂブロック共重合体が好ましい。 As the polymer dispersant, a block copolymer having a functional group containing a nitrogen atom is preferable, and an acrylic block copolymer having a functional group containing a nitrogen atom is more preferable from the viewpoint of dispersibility and storage stability.
The block copolymer having a functional group containing a nitrogen atom includes an A block having a quaternary ammonium base and / or an amino group in the side chain, and a B block having no quaternary ammonium base and an amino group. AB block copolymers and BAB block copolymers are preferable.
　窒素原子を含む官能基としては、１～３級アミノ基、４級アンモニウム塩基が挙げられる。分散性や保存安定性の観点から、１～３級アミノ基が好ましく、３級アミノ基がより好ましい。
　ブロック共重合体における、３級アミノ基を有する繰り返し単位の構造は特に限定されないが、分散性や保存安定性の観点から、下記一般式（ｄ１）で表される繰り返し単位であることが好ましい。 Examples of the functional group containing a nitrogen atom include a 1- to tertiary amino group and a quaternary ammonium base. From the viewpoint of dispersibility and storage stability, a primary to tertiary amino group is preferable, and a tertiary amino group is more preferable.
The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but from the viewpoint of dispersibility and storage stability, the repeating unit represented by the following general formula (d1) is preferable.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　式（ｄ１）中、Ｒ1及びＲ2は各々独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基であり、Ｒ1及びＲ2が互いに結合して環状構造を形成してもよい。Ｒ3は水素原子又はメチル基である。Ｘは２価の連結基である。 In formula (d1), R 1 and R 2 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It may be an aralkyl group, and R 1 and R 2 may be bonded to each other to form a cyclic structure. R 3 is a hydrogen atom or a methyl group. X is a divalent linking group.
　式（ｄ１）における、置換基を有していてもよいアルキル基の炭素数は特に限定されないが、通常１以上であり、また、１０以下であることが好ましく、６以下であることがより好ましく、４以下であることがさらに好ましい。例えば、１～１０が好ましく、１～６がより好ましく、１～４がさらに好ましい。
　アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基が挙げられる。メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基が好ましく、メチル基、エチル基、プロピル基、ブチル基がより好ましい。アルキル基は直鎖状、分岐鎖状のいずれであってもよい。アルキル基はシクロヘキシル基、シクロヘキシルメチル基のように環状構造を含んでもよい。 The number of carbon atoms of the alkyl group which may have a substituent in the formula (d1) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. It is more preferably 4 or less. For example, 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is further preferable.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. Methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group are preferable, and methyl group, ethyl group, propyl group and butyl group are more preferable. The alkyl group may be linear or branched. The alkyl group may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.
　式（ｄ１）における、置換基を有していてもよいアリール基の炭素数は特に限定されないが、通常６以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましく、８以下であることがさらに好ましい。例えば、６～１６が好ましく、６～１２がより好ましく、６～８がさらに好ましい。
　アリール基としては、例えば、フェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、ジエチルフェニル基、ナフチル基、アントラセニル基が挙げられる。フェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、ジエチルフェニル基が好ましく、フェニル基、メチルフェニル基、エチルフェニル基がより好ましい。 The number of carbon atoms of the aryl group which may have a substituent in the formula (d1) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. , 8 or less is more preferable. For example, 6 to 16 is preferable, 6 to 12 is more preferable, and 6 to 8 is even more preferable.
Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthrasenyl group. A phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group and a diethylphenyl group are preferable, and a phenyl group, a methylphenyl group and an ethylphenyl group are more preferable.
　式（ｄ１）における、置換基を有していてもよいアラルキル基の炭素数は特に限定されないが、通常７以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましく、９以下であることがさらに好ましい。例えば、７～１６が好ましく、７～１２がより好ましく、７～９がさらに好ましい。
　アラルキル基としては、例えば、フェニルメチレン基、フェニルエチレン基、フェニルプロピレン基、フェニルブチレン基、フェニルイソプロピレン基が挙げられる。フェニルメチレン基、フェニルエチレン基、フェニルプロピレン基、フェニルブチレン基が好ましく、フェニルメチレン基、フェニルエチレン基がより好ましい。 The carbon number of the aralkyl group which may have a substituent in the formula (d1) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. , 9 or less is more preferable. For example, 7 to 16 is preferable, 7 to 12 is more preferable, and 7 to 9 is even more preferable.
Examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. A phenylmethylene group, a phenylethylene group, a phenylpropylene group and a phenylbutylene group are preferable, and a phenylmethylene group and a phenylethylene group are more preferable.
　分散性、保存安定性、電気信頼性、現像性の観点から、Ｒ1及びＲ2としては、各々独立に置換基を有していてもよいアルキル基が好ましく、メチル基、エチル基がより好ましい。 From the viewpoints of dispersibility, storage stability, electrical reliability, and developability, R 1 and R 2 are preferably an alkyl group which may have an independent substituent, and more preferably a methyl group or an ethyl group. ..
　式（ｄ１）におけるアルキル基、アラルキル基、アリール基が有していてもよい置換基としては、例えば、ハロゲン原子、アルコキシ基、ベンゾイル基、水酸基が挙げられる。合成の容易さの観点から、無置換であることが好ましい。 Examples of the substituent that the alkyl group, aralkyl group, and aryl group in the formula (d1) may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
　式（ｄ１）において、Ｒ1及びＲ2が互いに結合して形成する環状構造としては、例えば５～７員環の含窒素複素環単環又はこれらが２個縮合してなる縮合環が挙げられる。含窒素複素環は芳香性を有さないものが好ましく、飽和環であればより好ましい。具体的には、例えば下記（ＩＶ）の環状構造が挙げられる。 In the formula (d1), examples of the cyclic structure formed by bonding R 1 and R 2 to each other include a nitrogen-containing heterocyclic monocycle having a 5- to 7-membered ring or a fused ring formed by condensing two of them. .. The nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring. Specifically, for example, the following cyclic structure (IV) can be mentioned.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
　これらの環状構造は、さらに置換基を有していてもよい。 These cyclic structures may further have a substituent.
　式（ｄ１）において、２価の連結基Ｘとしては、例えば、炭素数１～１０のアルキレン基、炭素数６～１２のアリーレン基、－ＣＯＮＨ－Ｒ13－基、－ＣＯＯＲ14－基（但し、Ｒ13及びＲ14は単結合、炭素数１～１０のアルキレン基、又は炭素数２～１０のエーテル基（アルキルオキシアルキル基）である）が挙げられ、好ましくは－ＣＯＯ－Ｒ14－基である。 In the formula (d1), the divalent linking group X includes, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 13 − group, and a −COOR 14 − group (provided that the divalent linking group X is). , R 13 and R 14 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), preferably -COO-R 14- group. Is.
　ブロック共重合体の全繰り返し単位に占める式（ｄ１）で表される繰り返し単位の含有割合は、１モル％以上が好ましく、５モル％以上がより好ましく、１０モル％以上がさらに好ましく、１５モル％以上がよりさらに好ましく、２０モル％以上がことさら好ましく、２５モル％以上が特に好ましく、また、９０モル％以下が好ましく、７０モル％以下がより好ましく、５０モル％以下がさらに好ましく、４０モル％以下が特に好ましい。前記範囲内の場合には分散安定性と高輝度の両立が可能となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、ブロック共重合体の全繰り返し単位に占める式（ｄ１）で表される繰り返し単位の含有割合は、１～９０モル％が好ましく、５～９０モル％がより好ましく、１０～７０モル％がさらに好ましく、１５～７０モル％がよりさらに好ましく、２０～５０％がことさら好ましく、２５～４０モル％が特に好ましい。 The content ratio of the repeating unit represented by the formula (d1) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and further preferably 15 mol. % Or more is more preferable, 20 mol% or more is particularly preferable, 25 mol% or more is particularly preferable, 90 mol% or less is preferable, 70 mol% or less is more preferable, 50 mol% or less is further preferable, and 40 mol is more preferable. % Or less is particularly preferable. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the repeating unit represented by the formula (d1) in all the repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, and 10 to 70 mol%. Further preferred, 15-70 mol% is even more preferred, 20-50% is particularly preferred, and 25-40 mol% is particularly preferred.
　ブロック共重合体は、分散剤の溶媒等バインダー成分に対する相溶性を高め、分散安定性を向上させるとの観点から、下記一般式（ｄ２）で表される繰り返し単位を有することが好ましい。 The block copolymer preferably has a repeating unit represented by the following general formula (d2) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability.
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
　式（ｄ２）中、Ｒ10はエチレン基又はプロピレン基であり、Ｒ11は置換基を有していてもよいアルキル基であり、Ｒ12は水素原子又はメチル基である。ｎは１～２０の整数である。 In formula (d2), R 10 is an ethylene group or a propylene group, R 11 is an alkyl group which may have a substituent, and R 12 is a hydrogen atom or a methyl group. n is an integer from 1 to 20.
　式（ｄ２）のＲ11における、置換基を有していてもよいアルキル基の炭素数は特に限定されないが、通常１以上であり、２以上であることが好ましく、また、１０以下であることが好ましく、６以下であることがより好ましく、４以下であることがさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、アルキル基の炭素数は１～１０が好ましく、１～６がより好ましく、１～４がさらに好ましく、２～４が特に好ましい。
　アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基が挙げられる。メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基が好ましく、メチル基、エチル基、プロピル基、ブチル基がより好ましい。アルキル基は、直鎖状、分岐鎖状のいずれであってもよい。アルキル基は、シクロヘキシル基、シクロヘキシルメチル基のように環状構造を含んでもよい。
　アルキル基が有していてもよい置換基としては、例えば、ハロゲン原子、アルコキシ基、ベンゾイル基、水酸基が挙げられる。合成の容易さの観点から、無置換であることが好ましい。 The number of carbon atoms of the alkyl group which may have a substituent in R 11 of the formula (d2) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. Is preferable, 6 or less is more preferable, and 4 or less is further preferable. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 2 to 4.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. Methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group are preferable, and methyl group, ethyl group, propyl group and butyl group are more preferable. The alkyl group may be linear or branched. The alkyl group may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.
Examples of the substituent that the alkyl group may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
　式（ｄ２）におけるｎは溶媒等バインダー成分に対する相溶性と分散性の観点から、１以上であることが好ましく、２以上であることがより好ましく、また、１０以下であることが好ましく、５以下であることがより好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、ｎは１～１０が好ましく、２～５がより好ましい。 From the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent, n in the formula (d2) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, and 5 or less. Is more preferable. The above upper and lower limits can be combined arbitrarily. For example, n is preferably 1 to 10, more preferably 2 to 5.
　ブロック共重合体の全繰り返し単位に占める式（ｄ２）で表される繰り返し単位の含有割合は、１モル％以上が好ましく、２モル％以上がより好ましく、４モル％以上がさらに好ましく、また、３０モル％以下が好ましく、２０モル％以下がより好ましく、１０モル％以下がさらに好ましい。前記範囲内の場合には溶媒等バインダー成分に対する相溶性と分散安定性の両立が可能となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、ブロック共重合体の全繰り返し単位に占める式（ｄ２）で表される繰り返し単位の含有割合は、１～３０モル％が好ましく、２～２０モル％がより好ましく、４～１０モル％がさらに好ましい。 The content ratio of the repeating unit represented by the formula (d2) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 4 mol% or more, and further. It is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. Within the above range, it tends to be possible to achieve both compatibility with a binder component such as a solvent and dispersion stability. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the repeating unit represented by the formula (d2) in all the repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 4 to 10 mol%. More preferred.
　ブロック共重合体は、分散剤の溶媒等バインダー成分に対する相溶性を高め、分散安定性を向上させるという観点から、下記一般式（ｄ３）で表される繰り返し単位を有することが好ましい。 The block copolymer preferably has a repeating unit represented by the following general formula (d3) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　式（ｄ３）中、Ｒ8は置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基である。Ｒ9は水素原子又はメチル基である。 In formula (d3), R 8 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R 9 is a hydrogen atom or a methyl group.
　式（ｄ３）のＲ8における、置換基を有していてもよいアルキル基の炭素数は特に限定されないが、通常１以上であり、また、１０以下であることが好ましく、６以下であることがより好ましい。例えば、１～１０が好ましく、１～６がより好ましい。
　アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基が挙げられる。メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基が好ましく、メチル基、エチル基、プロピル基、ブチル基がより好ましい。アルキル基は、直鎖状、分岐鎖状のいずれであってもよい。アルキル基は、シクロヘキシル基、シクロヘキシルメチル基のように環状構造を含んでもよい。 The number of carbon atoms of the alkyl group which may have a substituent in R 8 of the formula (d3) is not particularly limited, but is usually 1 or more, preferably 10 or less, and preferably 6 or less. Is more preferable. For example, 1 to 10 is preferable, and 1 to 6 is more preferable.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. Methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group are preferable, and methyl group, ethyl group, propyl group and butyl group are more preferable. The alkyl group may be linear or branched. The alkyl group may contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.
　式（ｄ３）のＲ8における、置換基を有していてもよいアリール基の炭素数は特に限定されないが、通常６以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましい。例えば、６～１６が好ましく、６～１２がより好ましい。
　アリール基としては、フェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、ジエチルフェニル基、ナフチル基、アントラセニル基が挙げられる。フェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、ジエチルフェニル基が好ましく、フェニル基、メチルフェニル基、エチルフェニル基がより好ましい。 The number of carbon atoms of the aryl group which may have a substituent in R 8 of the formula (d3) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. Is more preferable. For example, 6 to 16 are preferable, and 6 to 12 are more preferable.
Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group and an anthrasenyl group. A phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group and a diethylphenyl group are preferable, and a phenyl group, a methylphenyl group and an ethylphenyl group are more preferable.
　式（ｄ３）のＲ8における、置換基を有していてもよいアラルキル基の炭素数は特に限定されないが、通常７以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましい。例えば、７～１６が好ましく、７～１２がより好ましい。
　アラルキル基としては、フェニルメチレン基、フェニルエチレン基、フェニルプロピレン基、フェニルブチレン基、フェニルイソプロピレン基が挙げられる。フェニルメチレン基、フェニルエチレン基、フェニルプロピレン基、フェニルブチレン基が好ましく、フェニルメチレン基、フェニルエチレン基がより好ましい。 The carbon number of the aralkyl group which may have a substituent in R 8 of the formula (d3) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. Is more preferable. For example, 7 to 16 is preferable, and 7 to 12 is more preferable.
Examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group and a phenylisopropylene group. A phenylmethylene group, a phenylethylene group, a phenylpropylene group and a phenylbutylene group are preferable, and a phenylmethylene group and a phenylethylene group are more preferable.
　溶剤相溶性と分散安定性の観点から、Ｒ8としては、アルキル基、アラルキル基が好ましく、メチル基、エチル基、フェニルメチレン基がより好ましい。
　Ｒ8における、アルキル基が有していてもよい置換基としては、例えば、ハロゲン原子、アルコキシ基が挙げられる。
　アリール基又はアラルキル基が有していてもよい置換基としては、例えば、鎖状のアルキル基、ハロゲン原子、アルコキシ基が挙げられる。
　Ｒ8で示される鎖状のアルキル基には、直鎖状及び分岐鎖状のいずれも含まれる。 From the viewpoint of solvent compatibility and dispersion stability, R 8 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethylene group.
Examples of the substituent that the alkyl group may have in R 8 include a halogen atom and an alkoxy group.
Examples of the substituent that the aryl group or the aralkyl group may have include a chain-like alkyl group, a halogen atom, and an alkoxy group.
The chain-like alkyl group represented by R 8 includes both linear and branched chain-like groups.
　ブロック共重合体の全繰り返し単位に占める式（ｄ３）で表される繰り返し単位の含有割合は、３０モル％以上が好ましく、４０モル％以上がより好ましく、５０モル％以上がさらに好ましく、また、８０モル％以下が好ましく、７０モル％以下がより好ましい。前記範囲内の場合には分散安定性と高輝度の両立が可能となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、ブロック共重合体の全繰り返し単位に占める式（ｄ３）で表される繰り返し単位の含有割合は、３０～８０モル％が好ましく、４０～８０モル％がより好ましく、５０～７０モル％がさらに好ましい。 The content ratio of the repeating unit represented by the formula (d3) in all the repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and further. 80 mol% or less is preferable, and 70 mol% or less is more preferable. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the repeating unit represented by the formula (d3) in all the repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and 50 to 70 mol%. More preferred.
　ブロック共重合体は、式（ｄ１）で表される繰り返し単位、式（ｄ２）で表される繰り返し単位、式（ｄ３）で表される繰り返し単位以外の繰り返し単位を有していてもよい。そのような繰り返し単位としては、例えば、スチレン、α－メチルスチレンなどのスチレン系単量体；（メタ）アクリル酸クロライドなどの（メタ）アクリル酸塩系単量体；（メタ）アクリルアミド、Ｎ－メチロールアクリルアミドなどの（メタ）アクリルアミド系単量体；酢酸ビニル；アクリロニトリル；アリルグリシジルエーテル、クロトン酸グリシジルエーテル；Ｎ－メタクリロイルモルホリンに由来する繰り返し単位が挙げられる。 The block copolymer may have a repeating unit other than the repeating unit represented by the formula (d1), the repeating unit represented by the formula (d2), and the repeating unit represented by the formula (d3). Such repeating units include, for example, styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- Examples thereof include (meth) acrylamide-based monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate ether; and repeating units derived from N-methacryloylmorpholine.
　分散性をより高める観点から、式（ｄ１）で表される繰り返し単位を有するＡブロックと、式（ｄ１）で表される繰り返し単位を有さないＢブロックとを有する、ブロック共重合体であることが好ましい。ブロック共重合体は、Ａ－Ｂブロック共重合体又はＢ－Ａ－Ｂブロック共重合体であることが好ましい。Ｂブロックが式（ｄ２）で表される繰り返し単位及び／又は式（ｄ３）で表される繰り返し単位を有することがより好ましい。 From the viewpoint of further enhancing dispersibility, it is a block copolymer having an A block having a repeating unit represented by the formula (d1) and a B block having no repeating unit represented by the formula (d1). Is preferable. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. It is more preferable that the B block has a repeating unit represented by the formula (d2) and / or a repeating unit represented by the formula (d3).
　式（ｄ１）で表される繰り返し単位以外の繰り返し単位がＡブロック中に含有されていてもよい。そのような繰り返し単位としては、例えば、前述の（メタ）アクリル酸エステル類由来の繰り返し単位が挙げられる。式（ｄ１）で表される繰り返し単位以外の繰り返し単位のＡブロック中の含有量は、好ましくは０～５０モル％、より好ましくは０～２０モル％、さらに好ましくは０モル％である。 A repeating unit other than the repeating unit represented by the formula (d1) may be contained in the A block. Examples of such repeating units include the above-mentioned repeating units derived from (meth) acrylic acid esters. The content of the repeating unit other than the repeating unit represented by the formula (d1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, still more preferably 0 mol%.
　式（ｄ２）で表される繰り返し単位及び式（ｄ３）で表される繰り返し単位以外の繰り返し単位がＢブロック中に含有されていてもよい。そのような繰り返し単位としては、例えば、スチレン、α－メチルスチレンなどのスチレン系単量体；（メタ）アクリル酸クロライドなどの（メタ）アクリル酸塩系単量体；（メタ）アクリルアミド、Ｎ－メチロールアクリルアミドなどの（メタ）アクリルアミド系単量体；酢酸ビニル；アクリロニトリル；アリルグリシジルエーテル、クロトン酸グリシジルエーテル；Ｎ－メタクリロイルモルホリンに由来する繰り返し単位が挙げられる。式（ｄ２）で表される繰り返し単位及び式（ｄ３）で表される繰り返し単位以外の繰り返し単位のＢブロック中の含有量は、好ましくは０～５０モル％、より好ましくは０～２０モル％、さらに好ましくは０モル％である。 A repeating unit other than the repeating unit represented by the formula (d2) and the repeating unit represented by the formula (d3) may be contained in the B block. Such repeating units include, for example, styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- Examples thereof include (meth) acrylamide-based monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate ether; and repeating units derived from N-methacryloylmorpholine. The content of the repeating unit represented by the formula (d2) and the repeating unit other than the repeating unit represented by the formula (d3) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. , More preferably 0 mol%.
　ブロック共重合体の酸価は、分散性の点から、低い方が好ましく、特に０ｍｇＫＯＨ／ｇが好ましい。
　ここで酸価とは、分散剤固形分１ｇを中和するのに必要なＫＯＨのｍｇ数を表す。 The acid value of the block copolymer is preferably low, and particularly preferably 0 mgKOH / g, from the viewpoint of dispersibility.
Here, the acid value represents the number of mg of KOH required to neutralize 1 g of the dispersant solid content.
　ブロック共重合体のアミン価は、分散性と現像性の観点から、３０ｍｇＫＯＨ／ｇ以上が好ましく、５０ｍｇＫＯＨ／ｇ以上がより好ましく、７０ｍｇＫＯＨ／ｇ以上がさらに好ましく、９０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、１００ｍｇＫＯＨ／ｇ以上がことさら好ましく、１０５ｍｇＫＯＨ／ｇ以上が特に好ましく、また、１５０ｍｇＫＯＨ／ｇ以下が好ましく、１３０ｍｇＫＯＨ／ｇ以下がより好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、３０～１５０ｍｇＫＯＨ／ｇが好ましく、５０～１５０ｍｇＫＯＨ／ｇがより好ましく、７０～１５０ｍｇＫＯＨ／ｇがさらに好ましく、９０～１３０ｍｇＫＯＨ／ｇがよりさらに好ましく、１００～１３０ｍｇＫＯＨ／ｇがことさら好ましく、１０５～１３０ｍｇＫＯＨ／ｇが特に好ましい。
　ここでアミン価とは、有効固形分換算のアミン価を表し、分散剤の固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表される値である。 From the viewpoint of dispersibility and developability, the amine value of the block copolymer is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, further preferably 70 mgKOH / g or more, still more preferably 90 mgKOH / g or more. 100 mgKOH / g or more is particularly preferable, 105 mgKOH / g or more is particularly preferable, 150 mgKOH / g or less is preferable, and 130 mgKOH / g or less is more preferable. The above upper and lower limits can be combined arbitrarily. For example, 30 to 150 mgKOH / g is preferable, 50 to 150 mgKOH / g is more preferable, 70 to 150 mgKOH / g is further preferable, 90 to 130 mgKOH / g is more preferable, 100 to 130 mgKOH / g is particularly preferable, and 105 to 130 mgKOH is particularly preferable. / G is particularly preferable.
Here, the amine value represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH.
　ブロック共重合体の重量平均分子量は１０００～３０，０００が好ましい。前記範囲内である場合には、分散安定性が良好となり、また、スリットノズル方式による塗布時に乾燥異物がより発生しにくくなる傾向がある。 The weight average molecular weight of the block copolymer is preferably 1000 to 30,000. When it is within the above range, the dispersion stability is good, and dry foreign matter tends to be less likely to be generated during coating by the slit nozzle method.
　ブロック共重合体は、公知の方法により製造することができる。例えば、上記各繰り返し単位を導入する単量体をリビング重合することにより製造することができる。
　リビング重合法としては、例えば、日本国特開平９－６２００２号公報、日本国特開２００２－３１７１３号公報や、Ｐ．Ｌｕｔｚ，Ｐ．Ｍａｓｓｏｎ ｅｔ ａｌ，Ｐｏｌｙｍ．Ｂｕｌｌ．１２，７９（１９８４），Ｂ．Ｃ．Ａｎｄｅｒｓｏｎ，Ｇ．Ｄ．Ａｎｄｒｅｗｓ ｅｔ ａｌ，Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，１４，１６０１（１９８１），Ｋ．Ｈａｔａｄａ，Ｋ．Ｕｔｅ，ｅｔ ａｌ，Ｐｏｌｙｍ．Ｊ．１７，９７７（１９８５），１８，１０３７（１９８６），右手浩一、畑田耕一、高分子加工、３６，３６６（１９８７），東村敏延、沢本光男、高分子論文集、４６，１８９（１９８９），Ｍ．Ｋｕｒｏｋｉ，Ｔ．Ａｉｄａ，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ，１０９，４７３７（１９８７）、相田卓三、井上祥平、有機合成化学、４３，３００（１９８５），Ｄ．Ｙ．Ｓｏｇｏｈ，Ｗ．Ｒ．Ｈｅｒｔｌｅｒ ｅｔ ａｌ，Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，２０，１４７３（１９８７）に記載されている公知の方法を採用することができる。 The block copolymer can be produced by a known method. For example, it can be produced by performing living polymerization of a monomer into which each of the above repeating units is introduced.
Examples of the living polymerization method include Japanese Patent Application Laid-Open No. 9-62002, Japanese Patent Application Laid-Open No. 2002-31713, and P.M. Lutz, P. et al. Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K. et al. Ute, et al, Polym. J. 17,977 (1985), 18,1037 (1986), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36,366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46,189 (1989), M. Kuroki, T.I. Aida, J.M. Am. Chem. Soc, 109,4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43,300 (1985), D.I. Y. Sogoh, W.M. R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) can be employed.
　本発明の着色樹脂組成物が分散剤を含む場合、分散剤の含有割合は特に限定されないが、着色樹脂組成物の全固形分中に、０．００１質量％以上が好ましく、０．０１質量％以上がより好ましく、０．１質量％以上がさらに好ましく、１質量％以上がよりさらに好ましく、２質量％以上が特に好ましく、また、２５質量％以下が好ましく、２０質量％以下がより好ましく、１５質量％以下がさらに好ましく、１０質量％以下が特に好ましい。前記下限値以上とすることで分散性や保存安定性が向上する傾向があり、また、前記上限値以下とすることで電気信頼性や現像性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物が分散剤を含む場合、分散剤の含有割合は、着色樹脂組成物の全固形分中に０．００１～２５質量％が好ましく、０．０１～２５質量％がより好ましく、０．１～２０質量％がさらに好ましく、１～１５質量％がよりさらに好ましく、２～１０質量％が特に好ましい。 When the colored resin composition of the present invention contains a dispersant, the content ratio of the dispersant is not particularly limited, but it is preferably 0.001% by mass or more, preferably 0.01% by mass, in the total solid content of the colored resin composition. The above is more preferable, 0.1% by mass or more is further preferable, 1% by mass or more is further preferable, 2% by mass or more is particularly preferable, 25% by mass or less is preferable, 20% by mass or less is more preferable, and 15 by mass. More preferably, it is more preferably 10% by mass or less, and particularly preferably 10% by mass or less. When it is at least the above lower limit value, dispersibility and storage stability tend to be improved, and when it is at least the above upper limit value, electric reliability and developability tend to be improved. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains a dispersant, the content ratio of the dispersant is preferably 0.001 to 25% by mass, more preferably 0.01 to 25% by mass in the total solid content of the colored resin composition. , 0.1 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass.
　本発明の着色樹脂組成物が顔料及び分散剤を含む場合、分散剤の含有割合は特に限定されるものではないが、顔料１００質量部に対して、好ましくは０．５質量部以上、より好ましくは５質量部以上、さらに好ましくは１０質量部以上、よりさらに好ましくは１５質量部以上、特に好ましくは２０質量部以上であり、また、好ましくは７０質量部以下、より好ましくは５０質量部以下、さらに好ましくは４０質量部以下、特に好ましくは３０質量部以下である。前記範囲内とすることで、分散安定性に優れ、高輝度な着色性樹脂組成物を得ることができる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物が顔料及び分散剤を含む場合、分散剤の含有割合は、顔料１００質量部に対して、０．５～７０質量部が好ましく、５～７０質量部がより好ましく、１０～５０質量部がさらに好ましく、１５～４０質量部がよりさらに好ましく、２０～３０質量部が特に好ましい。 When the colored resin composition of the present invention contains a pigment and a dispersant, the content ratio of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the pigment. Is 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass or less. It is more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. Within the above range, there is a tendency that a colorable resin composition having excellent dispersion stability and high brightness can be obtained. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains a pigment and a dispersant, the content ratio of the dispersant is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the pigment. Up to 50 parts by mass is even more preferable, 15 to 40 parts by mass is even more preferable, and 20 to 30 parts by mass is particularly preferable.
　本発明の着色樹脂組成物が顔料を含む場合、顔料の分散性の向上、分散安定性の向上のために分散助剤として、例えば、顔料誘導体を含んでいてもよい。
　顔料誘導体としては、例えば、アゾ系、フタロシアニン系、キナクリドン系、ベンツイミダゾロン系、キノフタロン系、イソインドリノン系、イソインドリン系、ジオキサジン系、アントラキノン系、インダンスレン系、ペリレン系、ペリノン系、ジケトピロロピロール系、ジオキサジン系顔料の誘導体が挙げられる。顔料誘導体の置換基としては、例えば、スルホン酸基、スルホンアミド基及びその４級塩、フタルイミドメチル基、ジアルキルアミノアルキル基、水酸基、カルボキシ基、アミド基が顔料骨格に直接またはアルキル基、アリール基、複素環基等を介して結合したものが挙げられ、好ましくはスルホンアミド基及びその４級塩、スルホン酸基が挙げられ、より好ましくはスルホン酸基である。またこれら置換基は一つの顔料骨格に複数置換していてもよいし、置換数の異なる化合物の混合物でもよい。顔料誘導体としては、例えば、アゾ顔料のスルホン酸誘導体、フタロシアニン顔料のスルホン酸誘導体、キノフタロン顔料のスルホン酸誘導体、イソインドリン顔料のスルホン酸誘導体、アントラキノン顔料のスルホン酸誘導体、キナクリドン顔料のスルホン酸誘導体、ジケトピロロピロール顔料のスルホン酸誘導体、ジオキサジン顔料のスルホン酸誘導体等が挙げられる。 When the colored resin composition of the present invention contains a pigment, for example, a pigment derivative may be contained as a dispersion aid in order to improve the dispersibility of the pigment and the dispersion stability.
Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, isoindoline-based, dioxazine-based, anthraquinone-based, indanthrone-based, perylene-based, and perinone-based. Examples thereof include derivatives of diketopyrrolopyrrole-based and dioxazine-based pigments. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, and an amide group directly on the pigment skeleton or an alkyl group or an aryl group. , A group bonded via a heterocyclic group or the like, preferably a sulfonic amide group and a quaternary salt thereof, a sulfonic acid group, and more preferably a sulfonic acid group. Further, these substituents may be substituted in a plurality of one pigment skeleton, or may be a mixture of compounds having different numbers of substitutions. Examples of the pigment derivative include a sulfonic acid derivative of an azo pigment, a sulfonic acid derivative of a phthalocyanine pigment, a sulfonic acid derivative of a quinophthalone pigment, a sulfonic acid derivative of an isoindrin pigment, a sulfonic acid derivative of an anthraquinone pigment, and a sulfonic acid derivative of a quinacridone pigment. Examples thereof include a sulfonic acid derivative of a diketopyrrolopyrrole pigment and a sulfonic acid derivative of a dioxazine pigment.
［１－６－２］界面活性剤
　界面活性剤としては、アニオン系、カチオン系、非イオン系、両性界面活性剤等、各種の界面活性剤を用いることができるが、諸特性に悪影響を及ぼす可能性が低い点で、非イオン系界面活性剤が好ましい。本発明の着色樹脂組成物が界面活性剤を含む場合、界面活性剤の含有割合は特に限定されないが、着色樹脂組成物の全固形分中に通常０．００１質量％以上、好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上、さらに好ましくは０．１質量％以上、また、通常１０質量％以下、好ましくは１質量％以下、さらに好ましくは０．５質量％以下、特に好ましくは０．３質量％以下の範囲で用いられる。上記の上限及び下限は任意に組み合わせることができる。例えば、界面活性剤の含有割合は、着色樹脂組成物の全固形分中、０．００１～１０質量％が好ましく、０．０１～１質量％がより好ましく、０．０５～０．５質量％がさらに好ましく、０．１～０．３質量％が特に好ましい。 [1-6-2] Surfactant As the surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but they adversely affect various properties. Nonionic surfactants are preferred because they are less likely. When the colored resin composition of the present invention contains a surfactant, the content ratio of the surfactant is not particularly limited, but is usually 0.001% by mass or more, preferably 0.01 in the total solid content of the colored resin composition. By mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 1% by mass or less, still more preferably 0.5% by mass or less, particularly. It is preferably used in the range of 0.3% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, and 0.05 to 0.5% by mass in the total solid content of the colored resin composition. Is more preferable, and 0.1 to 0.3% by mass is particularly preferable.
［１－６－３］密着向上剤
　本発明の着色樹脂組成物は、基板との密着性を改善するため、密着向上剤を含有していてもよい。密着向上剤としては例えば、シランカップリング剤、チタンカップリング剤が挙げられる。シランカップリング剤が好ましい。
　シランカップリング剤としては、例えば、ＫＢＭ－４０２、ＫＢＭ－４０３、ＫＢＭ－５０２、ＫＢＭ－５１０３、ＫＢＥ－９００７、Ｘ－１２－１０４８、Ｘ－１２－１０５０（信越シリコーン社製）、Ｚ－６０４０、Ｚ－６０４３、Ｚ－６０６２（東レ・ダウコーニング社製）が挙げられる。シランカップリング剤は、１種を単独で用いてもよく、２種以上を任意の組み合わせ及び比率で併用してもよい。
　シランカップリング剤以外の密着向上剤を本発明の感光性樹脂組成物に含有させてもよい。例えば、リン酸系密着向上剤、その他の密着向上剤が挙げられる。 [1-6-3] Adhesion Improver The colored resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. Examples of the adhesion improving agent include a silane coupling agent and a titanium coupling agent. Silane coupling agents are preferred.
Examples of the silane coupling agent include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shinetsu Silicone Co., Ltd.), Z-6040. , Z-6043, Z-6062 (manufactured by Toray Dow Corning). As the silane coupling agent, one type may be used alone, or two or more types may be used in combination in any combination and ratio.
An adhesion improver other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention. For example, a phosphoric acid-based adhesion improver and other adhesion improvers can be mentioned.
　リン酸系密着向上剤としては、（メタ）アクリロイルオキシ基含有ホスフェート類が好ましい。下記一般式（ｇ１）、（ｇ２）、（ｇ３）で表されるリン酸系密着向上剤が好ましい。 As the phosphoric acid-based adhesion improver, (meth) acryloyloxy group-containing phosphates are preferable. Phosphoric acid-based adhesion improvers represented by the following general formulas (g1), (g2), and (g3) are preferable.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　式（ｇ１）、（ｇ２）、（ｇ３）において、Ｒ51は各々独立に水素原子又はメチル基を表す。ｌ及びｌ’は各々独立に１～１０の整数、ｍは各々独立に１、２又は３を表す。
　その他の密着向上剤としては、例えば、ＴＥＧＯ（登録商標）Ａｄｄ　Ｂｏｎｄ　ＬＴＨ（Ｅｖｏｎｉｋ社製）が挙げられる。これらのリン酸系密着向上剤やその他の密着剤は１種類を単独で用いてもよく、２種以上を併用してもよい。 In the formulas (g1), (g2) and (g3), R 51 independently represents a hydrogen atom or a methyl group. l and l'independently represent an integer of 1 to 10, and m independently represents 1, 2 or 3, respectively.
Examples of other adhesion improvers include TEGO (registered trademark) Add Bond LTH (manufactured by Evonik). One of these phosphoric acid-based adhesion improvers and other adhesives may be used alone, or two or more thereof may be used in combination.
　本発明の着色樹脂組成物が密着向上剤を含有する場合、その含有割合は特に限定されないが、全固形分中に０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．３質量％以上がさらに好ましく、０．４質量％以上が特に好ましく、また、３質量％以下が好ましく、２質量％以下がより好ましく、１．５質量％以下がさらに好ましく、１質量％以下が特に好ましい。前記下限値以上とすることでパターニング特性が向上し、高湿条件下のパターン密着が向上する傾向があり、また、前記上限値以下とすることで残渣発生が抑制される傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、着色樹脂組成物が密着向上剤を含有する場合、その含有割合は、全固形分中に０．１～３質量％が好ましく、０．２～２質量％がより好ましく、０．３～１．５質量％がさらに好ましく、０．４～１質量％が特に好ましい。 When the colored resin composition of the present invention contains an adhesion improver, the content ratio thereof is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0 by mass in the total solid content. .3% by mass or more is further preferable, 0.4% by mass or more is particularly preferable, 3% by mass or less is preferable, 2% by mass or less is more preferable, 1.5% by mass or less is further preferable, and 1% by mass or less. Is particularly preferable. When the value is not less than the lower limit, the patterning characteristics are improved and the pattern adhesion under high humidity conditions tends to be improved, and when the value is not more than the upper limit, the generation of residues tends to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains an adhesion improver, the content ratio thereof is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and 0.3 to 3% by mass in the total solid content. 1.5% by mass is more preferable, and 0.4 to 1% by mass is particularly preferable.
［２］着色樹脂組成物の調製
　次に、本発明に係る着色樹脂組成物（以下、レジストと称することがある。）を調製する方法を説明する。 [2] Preparation of Colored Resin Composition Next, a method for preparing a colored resin composition (hereinafter, may be referred to as a resist) according to the present invention will be described.
　着色剤として顔料を含むものを調製する場合にはまず、顔料、溶剤および分散剤を各所定量秤量し、分散処理工程において、顔料を含む着色剤を分散させて顔料分散液を調製する。この分散処理工程では、ペイントコンディショナー、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザーなどを使用することができる。この分散処理を行なうことによって着色剤が微粒子化されるため、着色樹脂組成物の塗布特性が向上し、製品のカラーフィルタ基板における画素の透過率が向上する。 When preparing a colorant containing a pigment, first, the pigment, the solvent and the dispersant are weighed in predetermined amounts, and in the dispersion treatment step, the colorant containing the pigment is dispersed to prepare a pigment dispersion liquid. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer and the like can be used. By performing this dispersion treatment, the colorant is made into fine particles, so that the coating characteristics of the colored resin composition are improved and the transmittance of pixels in the color filter substrate of the product is improved.
　顔料を分散処理する際には、上述の通り、分散助剤又は分散樹脂などを適宜併用することが好ましい。
　サンドグラインダーを用いて分散処理を行なう場合は、０．１から数ｍｍ径のガラスビーズ、又は、ジルコニアビーズを用いることが好ましい。分散処理する際の温度は、通常０℃以上、好ましくは室温以上、また、通常１００℃以下、好ましくは８０℃以下の範囲に設定する。なお、分散時間は、顔料分散液の組成、及びサンドグラインダーの装置の大きさなどにより適正時間が異なるため、適宜調整すればよい。 When the pigment is dispersed, it is preferable to appropriately use a dispersion aid, a dispersion resin, or the like as described above.
When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several mm or zirconia beads. The temperature at the time of the dispersion treatment is usually set in the range of 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time varies depending on the composition of the pigment dispersion liquid, the size of the sand grinder device, and the like, and may be appropriately adjusted.
　上記分散処理によって得られた顔料分散液に、溶剤、アルカリ可溶性樹脂、光重合開始剤、必要に応じて上記以外の成分などを混合し、均一な分散溶液とする。なお、分散処理工程及び混合の各工程においては、微細なゴミが混入することがあるため、得られた顔料分散液をフィルタなどによって、ろ過処理することが好ましい。 The pigment dispersion obtained by the above dispersion treatment is mixed with a solvent, an alkali-soluble resin, a photopolymerization initiator, and if necessary, components other than the above to obtain a uniform dispersion solution. Since fine dust may be mixed in each of the dispersion treatment step and the mixing step, it is preferable to filter the obtained pigment dispersion liquid with a filter or the like.
　着色剤として顔料を含まない場合には、着色剤、溶剤、アルカリ可溶性樹脂、光重合開始剤、必要に応じて上記以外の成分などを混合し、均一な溶液として得ることができる。得られた溶液をフィルタなどによってろ過処理することが好ましい。 When the pigment is not contained as the colorant, a colorant, a solvent, an alkali-soluble resin, a photopolymerization initiator, and if necessary, components other than the above can be mixed to obtain a uniform solution. It is preferable to filter the obtained solution with a filter or the like.
［３］カラーフィルタ基板の製造
　本発明に係るカラーフィルタは、本発明の着色樹脂組成物を用いて作成した画素を有する。 [3] Manufacture of Color Filter Substrate The color filter according to the present invention has pixels prepared by using the colored resin composition of the present invention.
［３－１］透明基板（支持体）
　カラーフィルタの透明基板としては、透明で適度の強度があれば、その材質は特に限定されるものではない。材質としては、例えば、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリプロピレン、ポリエチレンなどのポリオレフィン系樹脂、ポリカーボネート、ポリメチルメタクリレート、ポリスルホンの熱可塑性樹脂製シート、エポキシ樹脂、不飽和ポリエステル樹脂、ポリ（メタ）アクリル系樹脂などの熱硬化性樹脂シート、又は各種ガラスなどが挙げられる。この中でも、耐熱性の観点からガラスまたは耐熱性樹脂が好ましい。 [3-1] Transparent substrate (support)
The material of the transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethylmethacrylate, and polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylics. Examples thereof include a thermoplastic resin sheet such as a based resin, and various types of glass. Among these, glass or a heat-resistant resin is preferable from the viewpoint of heat resistance.
　透明基板及びブラックマトリクス形成基板には、接着性などの表面物性の改良のため、必要に応じ、コロナ放電処理、オゾン処理、シランカップリング剤や、ウレタン系樹脂などの各種樹脂の薄膜形成処理などを行なってもよい。透明基板の厚さは、通常０．０５ｍｍ以上、好ましくは０．１ｍｍ以上、また、通常１０ｍｍ以下、好ましくは７ｍｍ以下の範囲とされる。また、各種樹脂の薄膜形成処理を行なう場合、その膜厚は、通常０．０１μｍ以上、好ましくは０．０５μｍ以上、また、通常１０μｍ以下、好ましくは５μｍ以下の範囲である。例えば、０．０１～１０μｍ、０．０５～５μｍである。 For the transparent substrate and the black matrix-forming substrate, in order to improve the surface physical properties such as adhesiveness, corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc. are required. May be done. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When the thin film forming treatment of various resins is performed, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less. For example, it is 0.01 to 10 μm and 0.05 to 5 μm.
［３－２］ブラックマトリクス
　透明基板上にブラックマトリクスを設け、さらに通常は赤色、緑色、青色の画素画像を形成することにより、本発明のカラーフィルタを製造することができる。本発明の着色樹脂組成物は、赤色、緑色、青色の画素のうち、緑色又は青色の画素（レジストパターン）形成用塗布液として使用することが好ましい。緑色又は青色の画素（レジストパターン）形成用塗布液を用い、透明基板上に形成された樹脂ブラックマトリクス形成面上、又は、クロム化合物その他の遮光金属材料を用いて形成した金属ブラックマトリクス形成面上に、塗布、加熱乾燥、画像露光、現像及び熱硬化の各処理を行なって画素画像を形成する。 [3-2] Black Matrix The color filter of the present invention can be manufactured by providing a black matrix on a transparent substrate and further forming red, green, and blue pixel images. The colored resin composition of the present invention is preferably used as a coating liquid for forming green or blue pixels (resist pattern) among red, green, and blue pixels. On the resin black matrix forming surface formed on the transparent substrate using the coating liquid for forming green or blue pixels (resist pattern), or on the metal black matrix forming surface formed by using a chromium compound or other light-shielding metal material. A pixel image is formed by performing each of coating, heat-drying, image exposure, development, and heat curing.
　ブラックマトリクスは、遮光金属薄膜又はブラックマトリクス用着色樹脂組成物を利用して、透明基板上に形成される。遮光金属材料としては、金属クロム、酸化クロム、窒化クロムなどのクロム化合物、ニッケルとタングステン合金などが用いられ、これらを複数層状に積層させたものであってもよい。
　これらの金属遮光膜は、一般にスパッタリング法によって形成され、ポジ型フォトレジストにより、膜状に所望のパターンを形成した後、クロムに対しては硝酸第二セリウムアンモニウムと過塩素酸及び／又は硝酸とを混合したエッチング液を用い、その他の材料に対しては、材料に応じたエッチング液を用いて蝕刻され、最後にポジ型フォトレジストを専用の剥離剤で剥離することによって、ブラックマトリクスを形成することができる。 The black matrix is formed on a transparent substrate by using a light-shielding metal thin film or a colored resin composition for a black matrix. As the light-shielding metal material, a chromium compound such as metallic chromium, chromium oxide, or chromium nitride, a nickel-tungsten alloy, or the like is used, and these may be laminated in a plurality of layers.
These metal light-shielding films are generally formed by an etching method, and after forming a desired pattern in a film shape by a positive photoresist, dicerium ammonium nitrate and perchloric acid and / or nitric acid are added to chromium. A black matrix is formed by using an etching solution mixed with the above, and for other materials, it is carved using an etching solution suitable for the material, and finally the positive photoresist is peeled off with a special release agent. be able to.
　この場合、まず、蒸着又はスパッタリング法などにより、透明基板上にこれら金属又は金属・金属酸化物の薄膜を形成する。次いで、この薄膜上に着色樹脂組成物の塗布膜を形成した後、ストライプ、モザイク、トライアングルなどの繰り返しパターンを有するフォトマスクを用いて、塗布膜を露光・現像し、レジスト画像を形成する。その後、この塗布膜にエッチング処理を施してブラックマトリクスを形成することができる。 In this case, first, a thin film of these metals or metal / metal oxides is formed on a transparent substrate by a vapor deposition method or a sputtering method. Next, after forming a coating film of the colored resin composition on this thin film, the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, and triangles to form a resist image. After that, the coating film can be etched to form a black matrix.
　ブラックマトリクス用感光性着色樹脂組成物を利用する場合は、黒色の着色剤を含有する着色樹脂組成物を使用して、ブラックマトリクスを形成する。例えば、カーボンブラック、黒鉛、鉄黒、アニリンブラック、シアニンブラック、チタンブラックなどの黒色色材単独又は複数、もしくは、無機又は有機の顔料、染料の中から適宜選択される赤色、緑色、青色などの混合による黒色色材を含有する着色樹脂組成物を使用し、下記の赤色、緑色、青色の画素画像を形成する方法と同様にして、ブラックマトリクスを形成することができる。 When using a photosensitive colored resin composition for a black matrix, a colored resin composition containing a black colorant is used to form a black matrix. For example, black color materials such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc., or red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes. A black matrix can be formed by using a colored resin composition containing a black color material by mixing in the same manner as the method for forming red, green, and blue pixel images described below.
［３－３］画素の形成
　ブラックマトリクスを設けた透明基板上に、赤色、緑色、青色のうち一色の着色樹脂組成物を塗布し、乾燥した後、塗布膜の上にフォトマスクを重ね、このフォトマスクを介して画像露光、現像、必要に応じて熱硬化又は光硬化により画素画像を形成する。この操作を、赤色、緑色、青色の三色の着色樹脂組成物について各々行なうことによって、カラーフィルタ画像を形成することができる。 [3-3] Pixel formation A colored resin composition of one of red, green, and blue is applied onto a transparent substrate provided with a black matrix, dried, and then a photomask is placed on the coating film. A pixel image is formed by image exposure, development, and optionally heat curing or photocuring via a photomask. By performing this operation for each of the three colored resin compositions of red, green, and blue, a color filter image can be formed.
　カラーフィルタ用の着色樹脂組成物の塗布は、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、スプレーコート法などによって行なうことができる。中でも、ダイコート法によれば、塗布液使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミストなどの影響が全くなく、さらには異物発生が抑制されるなど、総合的な観点から好ましい。 The colored resin composition for a color filter can be applied by a spinner method, a wire bar method, a flow coat method, a die coat method, a roll coat method, a spray coat method, or the like. Above all, according to the die coating method, the amount of coating liquid used is significantly reduced, there is no influence of mist adhering when the spin coating method is used, and the generation of foreign substances is suppressed. It is preferable from the above viewpoint.
　塗布膜の厚さは、大き過ぎるとパターン現像が困難となるとともに、液晶セル化工程でのギャップ調整が困難となることがある一方で、小さ過ぎると顔料濃度を高めることが困難となり、所望の色発現が不可能となることがある。塗布膜の厚さは、乾燥後の膜厚として、通常０．２μｍ以上、好ましくは０．５μｍ以上、より好ましくは０．８μｍ以上、また、通常２０μｍ以下、好ましくは１０μｍ以下、より好ましくは５μｍ以下の範囲である。例えば、０．２～２０μｍ、０．５～１０μｍ、０．８～５μｍである。 If the thickness of the coating film is too large, it may be difficult to develop the pattern and it may be difficult to adjust the gap in the liquid crystal cell formation process, while if it is too small, it is difficult to increase the pigment concentration, which is desired. Color development may be impossible. The thickness of the coating film after drying is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm. The range is as follows. For example, it is 0.2 to 20 μm, 0.5 to 10 μm, and 0.8 to 5 μm.
［３－４］塗布膜の乾燥
　基板に着色樹脂組成物を塗布した後の塗布膜の乾燥（プリベーク）は、ホットプレート、ＩＲオーブン、コンベクションオーブンを使用した乾燥法によるのが好ましい。通常は、予備乾燥の後、再度加熱させて乾燥させる。予備乾燥の条件は、前記溶剤成分の種類、使用する乾燥機の性能などに応じて適宜選択することができる。乾燥温度及び乾燥時間は、溶剤成分の種類、使用する乾燥機の性能などに応じて選択されるが、具体的には、乾燥温度は通常４０℃以上、好ましくは５０℃以上、また、通常８０℃以下、好ましくは７０℃以下の範囲であり、乾燥時間は通常１５秒以上、好ましくは３０秒以上、また、通常５分間以下、好ましくは３分間以下の範囲である。 [3-4] Drying of Coating Film The coating film is preferably dried (prebaked) after the colored resin composition is applied to the substrate by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after pre-drying, it is heated again to dry. The conditions for pre-drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected according to the type of solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 ° C. or higher. The temperature is in the range of ° C. or lower, preferably 70 ° C. or lower, and the drying time is usually in the range of 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.
　再加熱乾燥の温度条件は、予備乾燥温度より高い温度が好ましく、具体的には、通常５０℃以上、好ましくは７０℃以上、また、通常２００℃以下、好ましくは１６０℃以下、特に好ましくは１３０℃以下の範囲である。また、乾燥時間は、加熱温度にもよるが、通常１０秒以上、中でも１５秒以上、また、通常１０分以下、中でも５分の範囲とするのが好ましい。乾燥温度は、高いほど透明基板に対する接着性が向上するが、高過ぎるとバインダー樹脂が分解し、熱重合を誘発して現像不良を生ずる場合がある。なお、この塗布膜の乾燥工程としては、温度を高めず減圧チャンバー内で乾燥を行なう減圧乾燥法を用いてもよい。 The temperature condition for reheating and drying is preferably higher than the pre-drying temperature, specifically, usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130 ° C. or higher. It is in the range of ℃ or less. The drying time is usually 10 seconds or longer, particularly preferably 15 seconds or longer, and usually 10 minutes or shorter, preferably 5 minutes or longer, although it depends on the heating temperature. The higher the drying temperature, the better the adhesiveness to the transparent substrate, but if it is too high, the binder resin may be decomposed, inducing thermal polymerization and causing development defects. As the drying step of the coating film, a vacuum drying method may be used in which the coating film is dried in the vacuum chamber without raising the temperature.
［３－５］露光工程
　画像露光は、着色樹脂組成物の塗布膜上に、ネガのマトリクスパターンを重ね、このマスクパターンを介し、紫外線又は可視光線の光源を照射して行なう。この際、必要に応じ、酸素による光重合性層の感度の低下を防ぐため、光重合性層上にポリビニルアルコール層などの酸素遮断層を形成した後に露光を行なってもよい。上記の画像露光に使用される光源は、特に限定されるものではない。光源としては、例えば、キセノンランプ、ハロゲンランプ、タングステンランプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、中圧水銀灯、低圧水銀灯、カーボンアーク、蛍光ランプなどのランプ光源や、アルゴンイオンレーザー、ＹＡＧレーザー、エキシマレーザー、窒素レーザー、ヘリウムカドミニウムレーザー、半導体レーザーなどのレーザー光源などが挙げられる。特定の波長の光を照射して使用する場合には、光学フィルタを利用することもできる。 [3-5] Exposure Step Image exposure is performed by superimposing a negative matrix pattern on a coating film of a colored resin composition and irradiating a light source of ultraviolet rays or visible light through this mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. The light source used for the above image exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc. Examples thereof include laser light sources such as an excima laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser. An optical filter can also be used when irradiating light of a specific wavelength for use.
［３－６］現像工程
　本発明に係るカラーフィルタは、本発明に係る着色樹脂組成物を用いた塗布膜に対し、上記の光源によって画像露光を行なった後、界面活性剤とアルカリ性化合物とを含む水溶液を用いて現像を行なうことによって、基板上に画像を形成して製造することができる。
この水溶液には、さらに有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることができる。 [3-6] Development Step In the color filter according to the present invention, a coating film using the colored resin composition according to the present invention is subjected to image exposure with the above-mentioned light source, and then a surfactant and an alkaline compound are applied. By developing with the contained aqueous solution, an image can be formed on the substrate and manufactured.
The aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.
　アルカリ性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、メタケイ酸ナトリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ナトリウム、リン酸水素カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、水酸化アンモニウムなどの無機アルカリ性化合物や、モノ－・ジ－又はトリエタノールアミン、モノ－・ジ－又はトリメチルアミン、モノ－・ジ－又はトリエチルアミン、モノ－又はジイソプロピルアミン、ｎ－ブチルアミン、モノ－・ジ－又はトリイソプロパノールアミン、エチレンイミン、エチレンジイミン、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、コリンなどの有機アルカリ性化合物が挙げられる。これらのアルカリ性化合物は、１種単独で用いてもよく、２種以上を併用してもよい。 Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphorus. Inorganic alkaline compounds such as potassium acid, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di or triethanolamine, mono-di- Or trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Examples include organic alkaline compounds. These alkaline compounds may be used alone or in combination of two or more.
　界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレンアルキルエステル類、ソルビタンアルキルエステル類、モノグリセリドアルキルエステル類などのノニオン系界面活性剤、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキル硫酸塩類、アルキルスルホン酸塩類、スルホコハク酸エステル塩類などのアニオン性界面活性剤、アルキルベタイン類、アミノ酸類などの両性界面活性剤が挙げられる。 Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkyl betaines and amino acids.
　有機溶剤としては、例えば、イソプロピルアルコール、ベンジルアルコール、エチルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、プロピレングリコール、ジアセトンアルコールが挙げられる。有機溶剤は、水溶液と併用して使用できる。
　現像処理の条件には特に制限はないが、現像温度は通常１０℃以上、中でも１５℃以上、さらには２０℃以上、また、通常５０℃以下、中でも４５℃以下、さらには４０℃以下の範囲が好ましい。現像方法は、浸漬現像法、スプレー現像法、ブラシ現像法、超音波現像法などの何れかの方法によることができる。 Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol and diacetone alcohol. The organic solvent can be used in combination with an aqueous solution.
The conditions of the development process are not particularly limited, but the development temperature is usually in the range of 10 ° C. or higher, particularly 15 ° C. or higher, further 20 ° C. or higher, and usually 50 ° C. or lower, particularly 45 ° C. or lower, further 40 ° C. or lower. Is preferable. The developing method can be any one of a dipping developing method, a spray developing method, a brush developing method, an ultrasonic developing method and the like.
［３－７］熱硬化処理
　現像の後のカラーフィルタには、熱硬化処理を施す。この際の熱硬化処理条件は、温度は通常１００℃以上、好ましくは１５０℃以上、また、通常２８０℃以下、好ましくは２５０℃以下の範囲で選ばれ、時間は５分間以上、６０分間以下の範囲で選ばれる。これら一連の工程を経て、一色のパターニング画像形成は終了する。この工程を順次繰り返し、ブラック、赤色、緑色、青色をパターニングし、カラーフィルタを形成する。なお、４色のパターニングの順番は、上記した順番に限定されるものではない。 [3-7] Thermosetting treatment The color filter after development is subjected to a thermosetting treatment. The thermosetting treatment conditions at this time are selected in a temperature range of usually 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 250 ° C. or lower, and the time is 5 minutes or longer and 60 minutes or lower. Selected by range. Through these series of steps, the formation of a one-color patterning image is completed. This process is repeated in sequence to pattern black, red, green, and blue to form a color filter. The order of patterning of the four colors is not limited to the above-mentioned order.
［３－８］透明電極の形成
　本発明に係るカラーフィルタは、このままの状態で画像上にＩＴＯなどの透明電極を形成して、カラーディスプレー、液晶表示装置などの部品の一部として使用されるが、表面平滑性や耐久性を高めるため、必要に応じ、画像上にポリアミド、ポリイミドなどのトップコート層を設けることもできる。また一部、平面配向型駆動方式（ＩＰＳモード）などの用途においては、透明電極を形成しないこともある。 [3-8] Formation of Transparent Electrode The color filter according to the present invention forms a transparent electrode such as ITO on an image in this state and is used as a part of parts such as a color display and a liquid crystal display device. However, in order to improve the surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image if necessary. Further, in some applications such as a plane alignment type drive system (IPS mode), a transparent electrode may not be formed.
［４］画像表示装置（パネル）
　本発明の画像表示装置は、本発明のカラーフィルタを有する。
　以下、画像表示装置として、液晶表示装置及び有機ＥＬ表示装置について詳述する。 [4] Image display device (panel)
The image display device of the present invention has the color filter of the present invention.
Hereinafter, the liquid crystal display device and the organic EL display device will be described in detail as the image display device.
［４－１］液晶表示装置
　本発明に係る液晶表示装置の製造方法について説明する。本発明に係る液晶表示装置は、通常、本発明のカラーフィルタ上に配向膜を形成し、この配向膜上にスペーサを散布した後、対向基板と貼り合わせて液晶セルを形成し、形成した液晶セルに液晶を注入し、対向電極に結線して完成する。配向膜は、ポリイミド等の樹脂膜が好適である。配向膜の形成には、通常、グラビア印刷法及び／又はフレキソ印刷法が採用され、配向膜の厚さは数１０ｎｍとされる。熱焼成によって配向膜の硬化処理を行なった後、紫外線の照射やラビング布による処理によって表面処理し、液晶の傾きを調整しうる表面状態に加工される。 [4-1] Liquid Crystal Display Device A method for manufacturing a liquid crystal display device according to the present invention will be described. In the liquid crystal display device according to the present invention, an alignment film is usually formed on the color filter of the present invention, a spacer is sprayed on the alignment film, and then the liquid crystal display device is bonded to a facing substrate to form a liquid crystal cell. The liquid crystal is injected into the cell and connected to the counter electrode to complete the process. As the alignment film, a resin film such as polyimide is suitable. A gravure printing method and / or a flexographic printing method is usually adopted for forming the alignment film, and the thickness of the alignment film is several tens of nm. After the alignment film is hardened by heat firing, it is surface-treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface state in which the inclination of the liquid crystal can be adjusted.
　スペーサは、対向基板とのギャップ（隙間）に応じた大きさのものが用いられ、通常２～８μｍのものが好適である。カラーフィルタ基板上に、フォトリソグラフィ法によって透明樹脂膜のフォトスペーサ（ＰＳ）を形成し、これをスペーサの代わりに活用することもできる。対向基板としては、通常、アレイ基板が用いられ、特にＴＦＴ（薄膜トランジスタ）基板が好適である。 The spacer used has a size corresponding to the gap (gap) with the facing substrate, and is usually preferably 2 to 8 μm. A photospacer (PS) of a transparent resin film can be formed on a color filter substrate by a photolithography method, and this can be used instead of the spacer. As the facing substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.
　対向基板との貼り合わせのギャップは、液晶表示装置の用途によって異なるが、通常２μｍ以上、８μｍ以下の範囲で選ばれる。対向基板と貼り合わせた後、液晶注入口以外の部分は、エポキシ樹脂等のシール材によって封止する。シール材は、ＵＶ照射及び／又は加熱することによって硬化させ、液晶セル周辺がシールされる。
　周辺をシールされた液晶セルは、パネル単位に切断した後、真空チャンバー内で減圧とし、上記液晶注入口を液晶に浸漬した後、チャンバー内をリークすることによって、液晶を液晶セル内に注入する。液晶セル内の減圧度は、通常１×１０-2Ｐａ以上、好ましくは１×１０-3以上、また、通常１×１０-7Ｐａ以下、好ましくは１×１０-6Ｐａ以下の範囲である。また、減圧時に液晶セルを加温するのが好ましく、加温温度は通常３０℃以上、好ましくは５０℃以上、また、通常１００℃以下、好ましくは９０℃以下の範囲である。 The gap for bonding to the facing substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After bonding to the facing substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the inside of the chamber leaks to inject the liquid crystal into the liquid crystal cell. .. The degree of decompression in the liquid crystal cell is usually in the range of 1 × 10 −2 Pa or more, preferably 1 × 10 -3 or more, and usually 1 × 10 -7 Pa or less, preferably 1 × 10 -6 Pa or less. .. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually in the range of 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.
　減圧時の加温保持は、通常１０分間以上、６０分間以下の範囲とされ、その後、液晶中に浸漬される。液晶を注入した液晶セルは、液晶注入口を、ＵＶ硬化樹脂を硬化させて封止することによって、液晶表示装置（パネル）が完成する。
　液晶の種類には特に制限がなく、芳香族系、脂肪族系、多環状化合物等、従来から知られている液晶であって、リオトロピック液晶、サーモトロピック液晶等の何れでもよい。
サーモトロピック液晶には、ネマティック液晶、スメスティック液晶及びコレステリック液晶等が知られているが、何れであってもよい。 The heat retention at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal display. A liquid crystal display device (panel) is completed by sealing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected by curing the UV curable resin.
The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic type, an aliphatic type, or a polycyclic compound, and may be any of a lyotropic liquid crystal, a thermotropic liquid crystal, and the like.
As the thermotropic liquid crystal, a nematic liquid crystal, a smestic liquid crystal, a cholesteric liquid crystal and the like are known, but any of them may be used.
［４－２］有機ＥＬ表示装置
　本発明のカラーフィルタを有する有機ＥＬ表示装置を作成する場合、例えば図１に示すように、透明支持基板１０上に、本発明の着色樹脂組成物により画素２０が形成された青色カラーフィルタ上に有機保護層３０及び無機酸化膜４０を介して有機発光体５００を積層することによって多色の有機ＥＬ素子を作製する。 [4-2] Organic EL Display Device When creating an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, the pixels 20 are formed on the transparent support substrate 10 by the colored resin composition of the present invention. A multicolored organic EL element is manufactured by laminating an organic illuminant 500 on a blue color filter on which an organic protective layer 30 is formed and an inorganic oxide film 40.
　有機発光体５００の積層方法としては、カラーフィルタ上面へ透明陽極５０、正孔注入層５１、正孔輸送層５２、発光層５３、電子注入層５４、及び陰極５５を逐次形成していく方法や、別基板上へ形成した有機発光体５００を無機酸化膜４０上に貼り合わせる方法などが挙げられる。このようにして作製された有機ＥＬ素子１００は、パッシブ駆動方式の有機ＥＬ表示装置にもアクティブ駆動方式の有機ＥＬ表示装置にも適用可能である。 As a method of laminating the organic illuminant 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of a color filter, or Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40. The organic EL element 100 thus produced can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.
　次に、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。 Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
＜フタロシアニン化合物Ａ＞
　日本国特開平０５－３４５８６１号公報の実施例３０に基づいて合成した、以下の化学構造を有するフタロシアニン化合物Ａを使用した。 <Parthalocyanine compound A>
A phthalocyanine compound A having the following chemical structure synthesized based on Example 30 of Japanese Patent Application Laid-Open No. 05-345861 was used.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
　なお、式中のＥｔはエチルを表す。 Et in the formula represents ethyl.
＜分散剤Ａ＞
　窒素原子含有官能基を有するＡブロックと、親溶媒性基を有するＢブロックからなるメタクリル系ＡＢブロック共重合体。下記式（１ａ）で表される繰り返し単位、下記式（２ａ）で表される繰り返し単位、下記式（３ａ）で表される繰り返し単位、下記式（４ａ）で表される繰り返し単位、及び下記式（５ａ）で表される繰り返し単位を有する。アミン価は１２０ｍｇＫＯＨ／ｇであり、酸価は１ｍｇＫＯＨ／ｇ未満である。 <Dispersant A>
A methacrylic AB block copolymer composed of an A block having a nitrogen atom-containing functional group and a B block having a prosolvent group. The repeating unit represented by the following formula (1a), the repeating unit represented by the following formula (2a), the repeating unit represented by the following formula (3a), the repeating unit represented by the following formula (4a), and the following. It has a repeating unit represented by the formula (5a). The amine value is 120 mgKOH / g and the acid value is less than 1 mgKOH / g.
　全繰り返し単位中における下記式（１ａ）、（２ａ）、（３ａ）、（４ａ）、及び（５ａ）で表される繰り返し単位の含有割合はそれぞれ１モル％未満、３４．５モル％、６．９モル％、１３．８モル％、及び６．９モル％である。 The content ratios of the repeating units represented by the following formulas (1a), (2a), (3a), (4a), and (5a) in all the repeating units are less than 1 mol%, 34.5 mol%, 6 respectively. It is 9.9 mol%, 13.8 mol%, and 6.9 mol%.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
＜アルカリ可溶性樹脂Ａ＞
　プロピレングリコールモノメチルエーテルアセテート１４５質量部を窒素置換しながら攪拌し１２０℃に昇温した。ここにスチレン１０質量部、グリシジルメタクリレート９０質量部及びトリシクロデカン骨格を有するモノメタクリレート（日立化成社製ＦＡ－５１３Ｍ）１０質量部を滴下し、さらに１２０℃で２時間攪拌し続けた。次に反応容器内を空気置換に変え、アクリル酸５０質量部にトリスジメチルアミノメチルフェノール０．７質量部及びハイドロキノン０．１２質量部を投入し、１２０℃で６時間反応を続けた。その後、テトラヒドロ無水フタル酸（ＴＨＰＡ）１３質量部、トリエチルアミン０．７質量部を加え、１２０℃３．５時間反応させた。こうして得られたアルカリ可溶性樹脂ＡのＧＰＣにより測定したポリスチレン換算の重量平均分子量Ｍｗは約９０００、酸価は２５ｍｇＫＯＨ／ｇ、二重結合当量は２６０ｇ／ｍｏｌであった。 <Alkali-soluble resin A>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. To this, 10 parts by mass of styrene, 90 parts by mass of glycidyl methacrylate and 10 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise, and stirring was continued at 120 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 50 parts by mass of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Then, 13 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 120 ° C. for 3.5 hours. The polystyrene-equivalent weight average molecular weight Mw measured by GPC of the alkali-soluble resin A thus obtained was about 9000, the acid value was 25 mgKOH / g, and the double bond equivalent was 260 g / mol.
＜アルカリ可溶性樹脂Ｂ＞
　反応槽として冷却管を付けたセパラブルフラスコを準備し、プロピレングリコールモノメチルエーテルアセテート４００質量部を仕込み、窒素置換した後、攪拌しながらオイルバスで加熱して反応槽の温度を９０℃まで昇温した。 <Alkali-soluble resin B>
A separable flask equipped with a cooling tube was prepared as a reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate was charged, and after nitrogen substitution, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. did.
　一方、モノマー槽中にジメチル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート３０質量部、メタクリル酸６０質量部、メタクリル酸シクロヘキシル１１０質量部、ｔ－ブチルパーオキシ－２－エチルヘキサノエート５．２質量部、プロピレングリコールモノメチルエーテルアセテート４０質量部を仕込み、連鎖移動剤槽にｎ－ドデシルメルカプタン５．２質量部、プロピレングリコールモノメチルエーテルアセテート２７質量部を仕込み、反応槽の温度が９０℃に安定してからモノマー槽及び連鎖移動剤槽から滴下を開始し、重合を開始させた。温度を９０℃に保ちながら滴下をそれぞれ１３５分かけて行い、滴下が終了して６０分後に昇温を開始して反応槽を１１０℃にした。 On the other hand, in the monomer tank, 30 parts by mass of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, and t-butylperoxy-2-ethyl. 5.2 parts by mass of hexanoate and 40 parts by mass of propylene glycol monomethyl ether acetate were charged, and 5.2 parts by mass of n-dodecylmercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged in the chain transfer agent tank, and the temperature of the reaction tank was charged. Was stabilized at 90 ° C., and then dropping was started from the monomer tank and the chain transfer agent tank to start the polymerization. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C., and 60 minutes after the dropping was completed, the temperature was raised to 110 ° C.
　３時間、１１０℃を維持した後、セパラブルフラスコにガス導入管を付け、酸素／窒素＝５／９５（ｖ／ｖ）混合ガスのバブリングを開始した。次いで、反応槽に、メタクリル酸グリシジル３９．６質量部、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）０．４質量部、トリエチルアミン０．８質量部を仕込み、そのまま１１０℃で９時間反応させた。
　室温まで冷却し、ＧＰＣにより測定したポリスチレン換算の重量平均分子量Ｍｗが９０００、酸価が１０１ｍｇＫＯＨ／ｇ、二重結合当量が５５０ｇ／ｍｏｌのアルカリ可溶性樹脂Ｂを得た。 After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were charged in the reaction vessel, and the temperature was 110 ° C. as it was. Was reacted for 9 hours.
After cooling to room temperature, an alkali-soluble resin B having a polystyrene-equivalent weight average molecular weight Mw measured by GPC of 9000, an acid value of 101 mgKOH / g, and a double bond equivalent of 550 g / mol was obtained.
＜緑色染料分散液Ａの調製＞
　表１に記載のとおり、フタロシアニン化合物Ａを９．９質量部、分散剤Ａを固形分換算で０．１質量部、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７２．０質量部（分散剤Ａ由来の溶剤を含む）、プロピレングリコールモノメチルエーテルを１８．０質量部、直径０．５ｍｍのジルコニアビーズ２２５質量部をステンレス容器に充填し、ペイントシェーカーにて６時間分散処理を行った。分散終了後、フィルタによりビーズと分散液を分離して、緑色染料分散液Ａを調製した。 <Preparation of green dye dispersion A>
As shown in Table 1, 9.9 parts by mass of phthalocyanine compound A, 0.1 parts by mass of dispersant A in terms of solid content, and 72.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (derived from dispersant A). A stainless steel container was filled with 18.0 parts by mass of propylene glycol monomethyl ether (including a solvent) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm, and dispersed with a paint shaker for 6 hours. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a green dye dispersion A.
＜緑色顔料分散液Ａの調製＞
　表１に記載のとおり、Ｃ．Ｉ．ピグメントグリーン５８を１３．９質量部、分散剤Ａを固形分換算で１．９質量部、アルカリ可溶性樹脂Ｂを固形分換算で４．２質量部、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８０．０質量部（分散剤Ａ由来の溶剤及びアルカリ可溶性樹脂Ｂ由来の溶剤も含む）、直径０．５ｍｍのジルコニアビーズ２２５質量部をステンレス容器に充填し、ペイントシェーカーにて６時間分散処理を行った。分散終了後、フィルタによりビーズと分散液を分離して、緑色顔料分散液Ａを調製した。 <Preparation of green pigment dispersion liquid A>
As shown in Table 1, C.I. I. Pigment Green 58 is 13.9 parts by mass, dispersant A is 1.9 parts by mass in terms of solid content, alkali-soluble resin B is 4.2 parts by mass in terms of solid content, and propylene glycol monomethyl ether acetate is 80.0 parts by mass as a solvent. A stainless steel container was filled with a mass portion (including a solvent derived from the dispersant A and a solvent derived from the alkali-soluble resin B) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm, and the dispersion treatment was performed with a paint shaker for 6 hours. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a green pigment dispersion A.
＜黄色顔料分散液Ａの調製＞
　表１に記載のとおり、Ｃ．Ｉ．ピグメントイエロー１３８を１１．４質量部、分散剤Ａを固形分換算で２．９質量部、アルカリ可溶性樹脂Ｂを固形分換算で５．７質量部、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７６．０質量部（分散剤Ａ由来の溶剤及びアルカリ可溶性樹脂Ｂ由来の溶剤も含む）、プロピレングリコールモノメチルエーテルを４．０質量部、直径０．５ｍｍのジルコニアビーズ２２５質量部をステンレス容器に充填し、ペイントシェーカーにて６時間分散処理を行った。分散終了後、フィルタによりビーズと分散液を分離して、黄色顔料分散液Ａを調製した。 <Preparation of yellow pigment dispersion liquid A>
As shown in Table 1, C.I. I. Pigment Yellow 138 by mass 11.4 parts by mass, dispersant A by 2.9 parts by mass in terms of solid content, alkali-soluble resin B by 5.7 parts by mass in terms of solid content, and propylene glycol monomethyl ether acetate as a solvent 76.0 parts by mass. Fill a stainless steel container with 4.0 parts by mass (including solvent derived from dispersant A and solvent derived from alkali-soluble resin B), 4.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads having a diameter of 0.5 mm, and paint. Dispersion processing was performed for 6 hours with a shaker. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a yellow pigment dispersion A.
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
＜光重合性モノマーＡ＞
　ポリエトキシ化テトラメチロールメタンテトラアクリレート（ＮＫエステル　ＡＴＭ－４Ｅ、新中村化学工業社製）、エトキシ化ペンタエリスリトールテトラアクリレートであって、１モル当たり平均４モルのエチレンオキサイドを付加させたもの。光重合性モノマー（ｅ１）に該当する。 <Photopolymerizable Monomer A>
Polyethoxylated tetramethylolmethane tetraacrylate (NK ester ATM-4E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethoxylated pentaerythritol tetraacrylate, to which an average of 4 mol of ethylene oxide is added per mol. It corresponds to the photopolymerizable monomer (e1).
＜光重合性モノマーＢ＞
　ジペンタエリスリトールヘキサアクリレート及びジペンタエリスリトールペンタアクリレートの混合物（Ａ－９５５０、新中村化学工業社製）。光重合性モノマー（ｅ１）に該当しない。 <Photopolymerizable Monomer B>
A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). It does not correspond to the photopolymerizable monomer (e1).
＜光重合性モノマーＣ＞
　エチレンオキサイド変性（１２）ジペンタエリスリトールヘキサアクリレート（ＫＡＹＡＲＡＤ　ＤＰＥＡ－１２、日本化薬社製）。光重合性モノマー（ｅ１）に該当する。 <Photopolymerizable Monomer C>
Ethylene oxide denaturation (12) Dipentaerythritol hexaacrylate (KAYARAD DPEA-12, manufactured by Nippon Kayaku Co., Ltd.). It corresponds to the photopolymerizable monomer (e1).
＜光重合開始剤Ａ＞
　以下の化学構造を有するオキシムエステル系化合物
（４－アセトキシイミノ－５－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－５－オキソペンタン酸メチル） <Photopolymerization Initiator A>
Oxime ester compound having the following chemical structure (4-acetoxyimino-5- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -5-oxopentanoate methyl)
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　なお、式中のＭｅはメチルを表す。 Me in the formula represents methyl.
＜連鎖移動剤Ａ＞
　ペンタエリスリトールテトラ（３－メルカプトプロピオナート）（淀化学社製） <Chain transfer agent A>
Pentaerythritol Tetra (3-Mercaptopropionate) (manufactured by Yodo Kagaku Co., Ltd.)
＜界面活性剤Ａ＞
　メガファックＦ－５５４（ＤＩＣ社製） <Surfactant A>
Mega Fuck F-554 (manufactured by DIC Corporation)
＜密着性向上剤Ａ＞
　以下の化学構造を有する化合物。 <Adhesion improver A>
A compound having the following chemical structure.
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　なお、式中、Ｃ２Ｈ４はジメチレンを、Ｃ３Ｈ６はトリメチレンを表す。 In the formula, C 2 H 4 represents dimethylene and C 3 H 6 represents trimethylene.
＜着色樹脂組成物の調製＞
　表２に記載の各成分を、記載の固形分比率で混合し着色樹脂組成物を調製した。なお、着色樹脂組成物の全固形分の含有割合が１７．３質量％になるように、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）及びプロピレングリコールモノメチルエーテル（ＰＧＭＥ）を使用した。得られた着色樹脂組成物中におけるＰＧＭＥＡ／ＰＧＭＥの混合比（質量比）は９０／１０であった。 <Preparation of colored resin composition>
Each component shown in Table 2 was mixed at the stated solid content ratio to prepare a colored resin composition. Propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were used so that the content ratio of the total solid content of the colored resin composition was 17.3% by mass. The mixing ratio (mass ratio) of PGMEA / PGME in the obtained colored resin composition was 90/10.
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000051
＜色特性の測定＞
　５０ｍｍ角、厚さ０．７ｍｍのガラス基板（ＡＧＣ社製、ＡＮ１００）上に、得られた着色樹脂組成物をスピンコート法で塗布し、減圧乾燥させた後、ホットプレート上にて９０℃で９０秒間プリベークした。次いで、２ｋＷ高圧水銀灯により、４０ｍＪ／ｃｍ2の露光量、照度３０ｍＷ／ｃｍ２で全面露光処理を行った。その後、０．０４質量％水酸化カリウム水溶液を使用し、現像液温度２３℃で６０秒間現像処理を行った。次いで、１ｋｇ／ｃｍ2の水圧で１０秒間スプレー水洗処理を行った。その後、クリーンオーブンにて２３０℃で２０分間の熱硬化処理を行い、着色基板を作成した。 <Measurement of color characteristics>
The obtained colored resin composition was applied onto a 50 mm square, 0.7 mm thick glass substrate (AN100 manufactured by AGC) by a spin coating method, dried under reduced pressure, and then placed on a hot plate at 90 ° C. Prebaked for 90 seconds. Next, the entire surface was exposed with a 2 kW high-pressure mercury lamp at an exposure amount of 40 mJ / cm 2 and an illuminance of 30 mW / cm 2 . Then, using a 0.04 mass% potassium hydroxide aqueous solution, development treatment was carried out at a developer temperature of 23 ° C. for 60 seconds. Then, a spray water washing treatment was performed for 10 seconds at a water pressure of 1 kg / cm 2 . Then, it was heat-cured at 230 ° C. for 20 minutes in a clean oven to prepare a colored substrate.
　得られた着色基板について、日立製作所社製分光光度計Ｕ－３３１０により透過スペクトルを測定し、Ｃ光源にてｓｙ＝０．５７６の色度となった際の輝度を算出した。その結果を表２に示す。 The transmission spectrum of the obtained colored substrate was measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd., and the brightness was calculated when the chromaticity was sy = 0.576 with a C light source. The results are shown in Table 2.
＜パターン形成性の評価＞
　５０ｍｍ角、厚さ０．７ｍｍのガラス基板（ＡＧＣ社製、ＡＮ１００）上に、熱硬化処理後の色度がＣ光源にてｓｙ＝０．５７６の色度となる様に、得られた着色樹脂組成物をスピンコート法で塗布し、８０℃でそれぞれ９０秒間プリベークした。次いで、２ｋＷ高圧水銀灯により、４０ｍＪ／ｃｍ2の露光量、照度３０ｍＷ／ｃｍ２で、直径３０μｍの円形被覆部を有する露光マスクを介して露光処理を行った。その後、０．０４質量％水酸化カリウム水溶液を使用し、現像液温度２３℃で６０秒間現像処理を行った。次いで、１ｋｇ／ｃｍ2の水圧で１０秒間スプレー水洗処理を行った。その後、２３０℃で２０分間の熱硬化処理を行い、パターン基板を作成した。得られたパターン基板Ａについて、光学顕微鏡を用いて、パターンのホール部の直径（μｍ）を測定した（ホール径Ａ）。 <Evaluation of pattern formation>
Coloring obtained on a 50 mm square, 0.7 mm thick glass substrate (AGC, AN100) so that the chromaticity after heat curing treatment is sy = 0.576 with a C light source. The resin composition was applied by a spin coat method and prebaked at 80 ° C. for 90 seconds each. Next, an exposure process was performed using a 2 kW high-pressure mercury lamp with an exposure amount of 40 mJ / cm 2 and an illuminance of 30 mW / cm 2 via an exposure mask having a circular coating portion having a diameter of 30 μm. Then, using a 0.04 mass% potassium hydroxide aqueous solution, development treatment was carried out at a developer temperature of 23 ° C. for 60 seconds. Then, a spray water washing treatment was performed for 10 seconds at a water pressure of 1 kg / cm 2 . Then, the thermosetting treatment was performed at 230 ° C. for 20 minutes to prepare a pattern substrate. With respect to the obtained pattern substrate A, the diameter (μm) of the hole portion of the pattern was measured using an optical microscope (hole diameter A).
　次に、パターン基板Ａの上記工程において、プリベークの温度を８０℃から１００℃に変更した以外は同一の条件にてパターン基板Ｂを作成した。得られたパターン基板Ｂについて、光学顕微鏡を用いて、パターンのホール部の直径（μｍ）を測定した（ホール径Ｂ）。 Next, in the above step of the pattern substrate A, the pattern substrate B was prepared under the same conditions except that the prebake temperature was changed from 80 ° C. to 100 ° C. With respect to the obtained pattern substrate B, the diameter (μm) of the hole portion of the pattern was measured using an optical microscope (hole diameter B).
　ホール径Ａとホール径Ｂから、プリベーク温度のホール直径への影響を計算し、温度依存性の指標とした。温度依存性（＝│（ホール径Ａ－ホール径Ｂ）［μｍ］／（１００－８０）［℃］│）の結果を表２に示す。 The effect of prebake temperature on the hole diameter was calculated from the hole diameter A and hole diameter B, and used as an index of temperature dependence. Table 2 shows the results of temperature dependence (= │ (hole diameter A-hole diameter B) [μm] / (100-80) [° C] │).
　表２から明らかなように、比較例２のＣ．Ｉ．ピグメントグリーン５８を含む着色樹脂組成物と比べ、比較例１のようにフタロシアニン化合物Ａを用いた場合には輝度が高くなっている。ただしフタロシアニン化合物Ａを用いることでホール径のプリベーク温度依存性は大幅に悪化している。 As is clear from Table 2, C.I. I. Compared with the colored resin composition containing Pigment Green 58, the brightness is higher when the phthalocyanine compound A is used as in Comparative Example 1. However, by using the phthalocyanine compound A, the prebake temperature dependence of the hole diameter is significantly deteriorated.
　一般的に、顔料と異なり染料は系中に単分子で存在する事によって高輝度、高着色力を得ることができるが、分子が孤立状態であるが故に耐熱性が劣り、パターンを得るための熱硬化処理によって昇華や酸化するため、熱硬化処理後のパターンにおいてはその輝度が低くなる傾向がある。
　これに対してフタロシアニン化合物（１）は、フタロシアニン骨格を構成する水素原子の１つ以上が原子半径の小さいフッ素原子で置換されており、フタロシアニン化合物（１）同士の会合を阻害しにくい構造であることから、加熱等で分子間距離が縮まった際に会合体を形成する事によって、加熱による輝度低下を抑制していると考えられる。また会合後においても、Ｃ．Ｉ．ピグメントグリーン５８と比較して、その粒子径は小さくなっていると考えられ、総合的に熱硬化処理後のパターンにおいて輝度が高くなっていると考えられる。 In general, unlike pigments, dyes can obtain high brightness and high coloring power by being present in a single molecule in the system, but heat resistance is inferior because the molecules are isolated, and a pattern can be obtained. Since it is sublimated and oxidized by the thermosetting treatment, its brightness tends to be low in the pattern after the thermosetting treatment.
On the other hand, the phthalocyanine compound (1) has a structure in which one or more of the hydrogen atoms constituting the phthalocyanine skeleton are replaced with fluorine atoms having a small atomic radius, and the association between the phthalocyanine compounds (1) is not easily inhibited. Therefore, it is considered that the decrease in brightness due to heating is suppressed by forming an aggregate when the intermolecular distance is shortened by heating or the like. Also after the meeting, C.I. I. It is considered that the particle size is smaller than that of Pigment Green 58, and the brightness is generally higher in the pattern after the thermosetting treatment.
　その一方で、比較例１と比較例２との比較から、フタロシアニン化合物（１）を用いることで、ホール径のプリベーク温度依存性が悪化している。
　比較例１ではフタロシアニン化合物（１）が粒子径の小さい会合体となって塗膜内に密に存在していると考えられ、現像液の塗膜への浸透と溶解が抑制されやすい状態になっていると考えられる。プリベーク温度が８０℃の場合には塗膜中に残留溶媒が一定量存在することで、現像液の塗膜への浸透を促進する事ができていると考えられる。その一方で、プリベーク温度が１００℃のような高温領域では残留溶媒が少なく、現像液の塗膜内部への浸透が十分には起こらず、未露光部においても塗膜の現像液への溶解性が不足し、パターニング形成不良に陥ってしまい、ホール径が小さくなる事で、ホール径のプリベーク温度依存性が悪化していると考えられる。 On the other hand, from the comparison between Comparative Example 1 and Comparative Example 2, the use of the phthalocyanine compound (1) worsens the prebake temperature dependence of the hole diameter.
In Comparative Example 1, it is considered that the phthalocyanine compound (1) forms an aggregate having a small particle size and is densely present in the coating film, so that the permeation and dissolution of the developer into the coating film are easily suppressed. It is thought that it is. When the prebake temperature is 80 ° C., it is considered that the presence of a certain amount of residual solvent in the coating film can promote the penetration of the developer into the coating film. On the other hand, in the high temperature region where the prebake temperature is 100 ° C., the residual solvent is small, the developer does not sufficiently penetrate into the coating film, and the coating film is soluble in the developer even in the unexposed area. It is considered that the prebake temperature dependence of the hole diameter is deteriorated due to the shortage of the holes, the poor patterning formation, and the small hole diameter.
　これに対し、フタロシアニン化合物（１）を含む実施例１、２及び３では、高輝度を維持しつつ、ホール径のプリベーク温度依存性が良好である。実施例１、２及び３は、比較例１の光重合性モノマーＢの一部又は全部を光重合性モノマー（ｅ１）に替えたものであるが、光重合性モノマー（ｅ１）はアルキレンオキサイド鎖を有するものであることにより、１００℃のような残留溶媒の少ない塗膜状態であったとしても現像液浸透性を良好に保つ事で、８０℃のような残留溶媒の多い塗膜状態と同程度の径のホールを形成することができ、ホール径のプリベーク温度依存性の悪化が抑制されたものと考えられる。 On the other hand, in Examples 1, 2 and 3 containing the phthalocyanine compound (1), the prebake temperature dependence of the hole diameter is good while maintaining high brightness. In Examples 1, 2 and 3, a part or all of the photopolymerizable monomer B of Comparative Example 1 is replaced with the photopolymerizable monomer (e1), but the photopolymerizable monomer (e1) is an alkylene oxide chain. By maintaining good developer permeability even in a coating state with a small residual solvent such as 100 ° C, it is the same as a coating state with a large residual solvent such as 80 ° C. It is considered that a hole having a diameter of about the same size could be formed, and the deterioration of the prebake temperature dependence of the hole diameter was suppressed.
　なお、比較例２のＣ．Ｉ．ピグメントグリーン５８を含む着色樹脂組成物に関しては、Ｃ．Ｉ．ピグメントグリーン５８の粒径が実施例１、実施例２、実施例３及び比較例１のフタロシアニン化合物（１）の会合体のそれと比べて大きく、塗膜に現像液が浸透するための十分な隙間が確保されている状態の為、残留溶媒量に関わらず、つまりプリベーク温度に依らず十分な現像液浸透性があり、ホール径のプリベーク温度依存性は良好であったと考えられる。 Note that C.I. I. For colored resin compositions containing Pigment Green 58, see C.I. I. The particle size of Pigment Green 58 is larger than that of the aggregate of the phthalocyanine compound (1) of Example 1, Example 2, Example 3 and Comparative Example 1, and there is a sufficient gap for the developer to penetrate into the coating film. It is probable that there was sufficient developer permeability regardless of the amount of residual solvent, that is, regardless of the prebake temperature, and the hole diameter was well dependent on the prebake temperature.
　本発明を特定の態様を用いて詳細に説明したが、本発明の意図と範囲を離れることなく様々な変更および変形が可能であることは、当業者にとって明らかである。 Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible without departing from the intent and scope of the invention.
　１０　透明支持基板
　２０　画素
　３０　有機保護層
　４０　無機酸化膜
　５０　透明陽極
　５１　正孔注入層
　５２　正孔輸送層
　５３　発光層
　５４　電子注入層
　５５　陰極
　１００　有機ＥＬ素子
　５００　有機発光体 10 Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims (6)

  1. 　（Ａ）着色剤、（Ｂ）溶剤、（Ｃ）アルカリ可溶性樹脂、（Ｄ）光重合開始剤、及び（Ｅ）光重合性モノマーを含有する着色樹脂組成物であって、
    　前記（Ａ）着色剤が、下記一般式（１）で表される化学構造を有するフタロシアニン化合物を含み、
    　前記（Ｅ）光重合性モノマーが、下記一般式（Ｉ）で表される部分構造を有する光重合性モノマー（ｅ１）を含むことを特徴とする着色樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式（１）中、Ａ1～Ａ16は各々独立に、水素原子、ハロゲン原子、又は下記一般式（２）で表される基を表す。ただし、Ａ1～Ａ16のうち１つ以上はフッ素原子を表し、かつ、Ａ1～Ａ16のうち１つ以上は下記一般式（２）で表される基を表す。）
    Figure JPOXMLDOC01-appb-C000002
     （式（２）中、Ｘは２価の連結基を表す。式（２）中のベンゼン環は任意の置換基を有していてもよい。＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000003
     （式（Ｉ）中、Ｒ1は炭素数２以上のアルキレン基を表す。
    　Ｒ2は、水素原子又はメチル基を表す。
    　ｎは１以上の整数を表す。
    　＊は結合手を表す。）     A colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer.
    The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1).
    A colored resin composition, wherein the photopolymerizable monomer (E) contains a photopolymerizable monomer (e1) having a partial structure represented by the following general formula (I).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (1), A 1 to A 16 each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), but one or more of A 1 to A 16 . Represents a fluorine atom, and one or more of A 1 to A 16 represents a group represented by the following general formula (2).)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula (2), X represents a divalent linking group. The benzene ring in the formula (2) may have an arbitrary substituent. * Represents a bond.)
    Figure JPOXMLDOC01-appb-C000003
     (In the formula (I), R 1 represents an alkylene group having 2 or more carbon atoms.
    R 2 represents a hydrogen atom or a methyl group.
    n represents an integer of 1 or more.
    * Represents a bond. )
  2. 　前記光重合性モノマー（ｅ１）が、下記一般式（ＩＩ）で表される化合物である、請求項１に記載の着色樹脂組成物。
    Figure JPOXMLDOC01-appb-C000004
     （式（ＩＩ）中、Ｒ1、Ｒ2及びｎは、前記式（Ｉ）と同義である。
    　Ｚは、直接結合、酸素原子、硫黄原子、２～４価の脂肪族炭化水素基、４価の炭素原子、２～４価の非芳香族複素環基、２～４価の芳香族環基、又は下記一般式（ＩＩＩ）で表される部分構造を表す。
    　ｐは、２～６の整数を表す。
    　なお、一分子中に含まれる複数の下記一般式（ＩＩ’）で表される構造は、同じでもよく、また異なっていてもよい。）
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
     （式（ＩＩＩ）中、＊は結合手を表す。）     The colored resin composition according to claim 1, wherein the photopolymerizable monomer (e1) is a compound represented by the following general formula (II).
    Figure JPOXMLDOC01-appb-C000004
     (In the formula (II), R 1 , R 2 and n are synonymous with the above formula (I).
    Z is a direct bond, an oxygen atom, a sulfur atom, a 2- to 4-valent aliphatic hydrocarbon group, a 4-valent carbon atom, a 2- to 4-valent non-aromatic heterocyclic group, and a 2- to 4-valent aromatic ring group. , Or a partial structure represented by the following general formula (III).
    p represents an integer of 2 to 6.
    The structures represented by the following general formula (II') contained in one molecule may be the same or different. )
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
     (In formula (III), * represents a bond.)
  3. 　前記（Ａ）着色剤の含有割合が、全固形分中に１０質量％以上である、請求項１又は２に記載の着色樹脂組成物。 The colored resin composition according to claim 1 or 2, wherein the content ratio of the colorant (A) is 10% by mass or more in the total solid content.
  4. 　前記光重合性モノマー（ｅ１）の含有割合が、全固形分中に１質量％以上である、請求項１～３のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 3, wherein the content ratio of the photopolymerizable monomer (e1) is 1% by mass or more in the total solid content.
  5. 　請求項１～４のいずれか１項に記載の着色樹脂組成物を用いて作成した画素を有する、カラーフィルタ。 A color filter having pixels created by using the colored resin composition according to any one of claims 1 to 4.
  6. 　請求項５に記載のカラーフィルタを有する、画像表示装置。 An image display device having the color filter according to claim 5.
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WO2023176888A1 (en) * 2022-03-16 2023-09-21 三菱ケミカル株式会社 Color filter manufacturing method and image display device manufacturing method
JP7464184B1 (en) 2023-02-01 2024-04-09 ａｒｔｉｅｎｃｅ株式会社 Photosensitive coloring composition, film using the same, color filter, solid-state imaging device, and image display device

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JP2014043555A (en) * 2012-07-30 2014-03-13 Fujifilm Corp Coloring curable composition and color filter
JP2019144543A (en) * 2018-02-16 2019-08-29 三菱ケミカル株式会社 Coloring resin composition, color filter, and image display device
JP2020042263A (en) * 2018-09-10 2020-03-19 三菱ケミカル株式会社 Coloring resin composition, color filter, and image display device

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JP7003637B2 (en) 2017-12-25 2022-01-20 三菱ケミカル株式会社 Colored resin composition, color filter, and image display device

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JP2014043555A (en) * 2012-07-30 2014-03-13 Fujifilm Corp Coloring curable composition and color filter
JP2019144543A (en) * 2018-02-16 2019-08-29 三菱ケミカル株式会社 Coloring resin composition, color filter, and image display device
JP2020042263A (en) * 2018-09-10 2020-03-19 三菱ケミカル株式会社 Coloring resin composition, color filter, and image display device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023176888A1 (en) * 2022-03-16 2023-09-21 三菱ケミカル株式会社 Color filter manufacturing method and image display device manufacturing method
JP7464184B1 (en) 2023-02-01 2024-04-09 ａｒｔｉｅｎｃｅ株式会社 Photosensitive coloring composition, film using the same, color filter, solid-state imaging device, and image display device

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