WO2020162009A1 - Colored curable resin composition - Google Patents

Colored curable resin composition Download PDF

Info

Publication number
WO2020162009A1
WO2020162009A1 PCT/JP2019/047175 JP2019047175W WO2020162009A1 WO 2020162009 A1 WO2020162009 A1 WO 2020162009A1 JP 2019047175 W JP2019047175 W JP 2019047175W WO 2020162009 A1 WO2020162009 A1 WO 2020162009A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
parts
formula
meth
resin
Prior art date
Application number
PCT/JP2019/047175
Other languages
French (fr)
Japanese (ja)
Inventor
崇夫 土谷
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN201980088648.XA priority Critical patent/CN113286828B/en
Priority to KR1020217027733A priority patent/KR20210124315A/en
Publication of WO2020162009A1 publication Critical patent/WO2020162009A1/en

Links

Classifications

    • 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
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of amides or imides
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F22/00—Homopolymers and 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
    • C08F22/36—Amides or imides
    • C08F22/40—Imides, e.g. cyclic imides
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Definitions

  • the present invention relates to a colored curable resin composition.
  • Color filters used for display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are manufactured from a colored resin composition.
  • a squarylium dye is known as a colorant used in such a colored resin composition (Patent Documents 1 and 2).
  • the conventionally known color filter formed from the above colored curable resin composition using a squarylium dye as a colorant may not be able to sufficiently satisfy the absorbance retention rate. Therefore, it is an object of the present invention to provide a colored curable resin composition capable of forming a color filter having excellent absorbance retention.
  • the gist of the present invention is as follows.
  • [1] contains a colorant, a resin, a polymerizable compound, and a polymerization initiator,
  • the colorant is a colorant containing a squarylium dye of formula (I)
  • a colored curable resin composition wherein the resin is a resin containing a structural unit derived from an N-substituted maleimide.
  • R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
  • R 5 to R 8 each independently represent a hydrogen atom or a hydroxy group.
  • Ar 1 and Ar 2 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, or a group represented by the formula (i).
  • R 12 is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent.
  • m represents an integer of 0 to 5.
  • An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
  • a plurality of R 12's may be the same or different.
  • R 9 and R 10 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i). An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
  • the colored curable resin composition of the present invention it is possible to provide a color filter having excellent absorbance retention.
  • the colored curable resin composition of the present invention includes a colorant (hereinafter sometimes referred to as a colorant (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, a polymerizable compound). (C) and a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)).
  • the colorant includes a squarylium dye represented by formula (I) (hereinafter sometimes referred to as compound (I)).
  • the resin comprises structural units derived from N-substituted maleimides.
  • the colored curable resin composition of the present invention preferably further contains a solvent (hereinafter sometimes referred to as solvent (E)).
  • the colored curable resin composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as a leveling agent (F)).
  • a leveling agent hereinafter sometimes referred to as a leveling agent (F)
  • the compounds exemplified as the respective components can be used alone or in combination of two or more kinds unless otherwise specified.
  • the colorant (A) includes the compound (I).
  • the present invention will be described in detail using the formula (I).
  • the resonance structure of the formula (I) and each group in the formula (I) are rotated around a single bond bond axis.
  • the compound obtained by the above is also included.
  • R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
  • R 5 to R 8 each independently represent a hydrogen atom or a hydroxy group.
  • Ar 1 and Ar 2 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i), and preferably a group represented by the formula ( represents a group represented by i).
  • R 12 is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent.
  • m represents an integer of 0 to 5.
  • An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
  • R 9 and R 10 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i).
  • An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
  • examples of the halogen atom for R 1 to R 4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1 to R 4 , R 9 , R 10 , R 12 , Ar 1 and Ar 2 include a methyl group, an ethyl group, a propyl group and a butyl group.
  • Substituents for these saturated hydrocarbon groups include halogen atoms such as fluorine atom, chlorine atom and iodine; hydroxy group; carboxy group; -NR a R b (R a and R b are each independently a hydrogen atom or An alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group;
  • Examples of the monovalent saturated hydrocarbon group of 20 include groups represented by the following formula. In the following formula, * represents a bond.
  • Examples of groups in which an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting these saturated hydrocarbon groups include groups represented by the following formula.
  • * represents a bond.
  • Examples of the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms in R 12 include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group and decenyl group.
  • a halogen atom such as a fluorine atom, a chlorine atom and iodine; a hydroxy group; a carboxy group; —NR c R d (R c and R d are each independently a hydrogen atom or A C1-C20 alkyl group); a nitro group; a C1-C10 alkoxy group such as a methoxy group and an ethoxy group; a C1-C10 alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; Etc.
  • R 1 to R 4 a hydrogen atom, a hydroxy group and an alkyl group having 1 to 4 carbon atoms are preferable, a hydrogen atom, a hydroxy group and a methyl group are more preferable, and a hydrogen atom is still more preferable.
  • At least one of R 5 to R 8 is preferably a hydroxy group. More preferably, at least one of R 5 and R 6 is a hydroxy group, and at least one of R 7 and R 8 is a hydroxy group.
  • an alkyl group having 3 to 14 carbon atoms which may have a substituent and a group represented by the formula (i) are preferable, and an alkyl group having 3 carbon atoms which may have a substituent.
  • an alkyl group having 3 carbon atoms which may have a substituent eg, octyl group, nonyl group, decyl group, dodecyl group, 2 -Ethylhexyl group, etc.
  • a linear alkyl group having a hydroxy group at a terminal and having 3 to 5 carbon atoms, and a group having a carboxy group at a terminal and having 3 to 5 carbon atoms A linear alkyl group and a 2-ethylhexyl group are more preferable.
  • the saturated hydrocarbon group for R 12 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group.
  • the unsaturated hydrocarbon group for R 12 is preferably an alkenyl group having 2 to 4 carbon atoms, more preferably a vinyl group or an allyl group.
  • m is 2 or more
  • at least one R 12 is preferably a saturated hydrocarbon group.
  • m is 2 or more, an embodiment in which all R 12 are saturated hydrocarbon groups or an embodiment in which some R 12 are saturated hydrocarbon groups and some R 12 are unsaturated hydrocarbon groups is more preferable. preferable.
  • n is preferably 1 to 5, more preferably 1 to 3.
  • Examples of the group represented by the formula (i) include the following groups. * Represents a bond with the nitrogen atom.
  • examples of the group represented by X 1 and X 2 include groups represented by formulas (A2-1) to (A2-9). * Represents a bond with a carbon atom.
  • Examples of the compound (I) include the compounds (AII-1) to (AII-27) shown in Table 1.
  • Compound (AII-10) to compound (AII-18) are more preferable.
  • the compound represented by formula (I) can be produced by reacting the compound represented by formula (pt1) with the compound represented by formula (pt2) and the compound represented by formula (pt3). ..
  • the amount of the compound represented by the formula (pt3) used is preferably 0.05 with respect to 1 mol in total of the compound represented by the formula (pt1) and the compound represented by the formula (pt2).
  • the amount is not less than 0.8 and not more than 0.8, and more preferably not less than 0.1 and not more than 0.6.
  • R 1 to R 10 , Ar 1 and Ar 2 have the same meanings as described above.
  • the reaction temperature is preferably 30°C to 180°C, more preferably 80°C to 140°C.
  • the reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.
  • Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl.
  • hydrocarbon solvents such as toluene and xylene
  • halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform
  • alcohol solvents such as methanol, ethanol, isopropanol and butanol
  • nitro hydrocarbon solvents such as nitrobenzene
  • methyl isobutyl examples thereof include ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone; and the like, and these may be mixed and used.
  • a mixed solvent of butanol and toluene is preferable.
  • the amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 1 part by mass of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). Is 30 parts by mass or more and 150 parts by mass or less.
  • the method for taking out the target compound (I) from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method may be mentioned in which the reaction mixture is cooled after completion of the reaction and the precipitated crystals are collected by filtration. The crystals collected by filtration are preferably washed with water or the like and then dried. If necessary, it may be further purified by a known method such as recrystallization.
  • R 1 , R 2 , R 5 , R 6 , R 9 and Ar 1 each have the same meaning as described above.
  • a compound represented by the formula (pt2) can be produced by using the same method as described above.
  • the colorant (A) may contain a colorant different from the compound (I) in addition to the compound (I), and the colorant different from the compound (I) is a dye (hereinafter, referred to as a dye (A1)). Or a pigment (hereinafter sometimes referred to as a pigment (A2)), and the colorant different from the compound (I) is one of the dye (A1) and the pigment (A2). Alternatively, both may be included.
  • the dye (A1) is not particularly limited as long as it does not include the compound (I), and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes and mordant dyes.
  • Examples of the dyes include compounds that are classified as having a hue other than pigment in the color index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Note (Shikisosha).
  • azo dye cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, acridine dye, styryl dye, coumarin dye, quinoline dye.
  • examples thereof include dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.
  • C.I. I. Solvent Yellow 4 (hereinafter, CI Solvent Yellow is omitted and only the numbers are shown), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99. 117, 162, 163, 167, 189;
  • Acid Green 1 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, C. 104, 105, 106, 109, etc.
  • Acid dyes C. 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, 136, 138, 141; C. I.
  • I. C. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like.
  • I. Direct dye C. I. Disperse Yellow 51, 54, 76; C. I. Disperse Violet 26, 27; C. I. C. such as Disperse Blue 1, 14, 56, 60 and the like.
  • I. Disperse dye C. I. Basic Red 1, 10; C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; C. I. Basic Violet 2; C. I.
  • Basic Red 9; C. I. C. such as Basic Green 1 I. Basic dye, C. I. Reactive Yellow 2,76,116; C. I. Reactive Orange 16; C. I. C. such as Reactive Red 36 I. Reactive dye, C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C. I. Mordan tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C. I.
  • Modant dye such as Modern Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53.
  • Modant dye C.I. I. C. such as Bat Green 1 I.
  • examples include vat dyes and the like. These dyes may be appropriately selected according to the desired spectrum of the color filter.
  • the pigment (A2) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments by Color Index (published by The Society of Dyers and Colorists).
  • Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C. I.
  • the pigment may be rosin treated, surface treated with a pigment derivative having an acidic group or a basic group introduced therein, grafted on the surface of the pigment with a polymer compound, or atomized by a sulfuric acid atomization method, etc.
  • a treatment, a cleaning treatment with an organic solvent or water for removing impurities, a treatment for removing ionic impurities by an ion exchange method, or the like may be performed.
  • the pigment preferably has a uniform particle size.
  • pigment dispersant examples include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more kinds.
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Floren manufactured by Kyoeisha Chemical Co., Ltd.
  • Sols Perth manufactured by Zeneca Co., Ltd.
  • EFKA manufactured by CIBA
  • Azisper Alignomoto Fine Co., Ltd.
  • Techno Co., Ltd. Disperbyk (manufactured by Big Chemie), and the like.
  • the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A2).
  • the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniform dispersed state tends to be obtained.
  • the content of the colorant (A) in the colored curable resin composition is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 60% by mass, based on the total amount of solids. It is not more than mass%, more preferably not less than 1 mass% and not more than 50 mass%.
  • the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, the pattern having sufficient mechanical strength can be formed.
  • total amount of solids in the present specification means the amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition.
  • the total amount of solid content and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.
  • the content of the compound (I) in the total amount of the colorant (A) is preferably 1% by mass or more, more preferably 3% by mass or more, and may be 100% by mass, or 90% by mass. It may be the following, 60% by mass or less, or 40% by mass or less.
  • the resin contains a resin containing structural units derived from N-substituted maleimides.
  • the absorbance retention of the color filter is improved.
  • the structural unit derived from the N-substituted maleimide is preferably a structural unit represented by the following formula (Bm).
  • R 13 is a monovalent saturated hydrocarbon group having 1 to 15 carbon atoms, which may have a substituent, and 1 having 6 to 20 carbon atoms, which may have a substituent. It represents a valent aromatic hydrocarbon group or a monovalent heterocyclic group having 3 to 20 carbon atoms, which may have a substituent.
  • Examples of the monovalent saturated hydrocarbon group having 1 to 15 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group.
  • Linear alkyl groups having 1 to 15 carbon atoms such as hexadecyl group and icosyl group; carbon numbers such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group 3-15 branched chain alkyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecyl group, adamantyl group, and other alicyclic saturated hydrocarbon groups having 3-15 carbon atoms Are listed.
  • substituent of the saturated hydrocarbon group examples include a halogen atom such as a fluorine atom, a chlorine atom and iodine; a hydroxy group; a carboxy group; —NR h R i (R h and R i are each independently a hydrogen atom or a carbon atom).
  • a C1-C10 alkoxy group such as a methoxy group or an ethoxy group; a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group or the like having a carbon number of 6 to Examples thereof include an aromatic hydrocarbon group of 15; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; and a group represented by the following formula (m-1).
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group and terphenyl group.
  • a hydroxy group As the substituent of the aromatic hydrocarbon group, a hydroxy group; a carboxy group; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; Sulfamoyl group; alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group; alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group; group represented by formula (m-1), etc. Can be mentioned.
  • R 13 is a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms having a substituent, the saturated hydrocarbon group is an alkyl group, and the substituent is an aromatic hydrocarbon group having 6 to 15 carbon atoms.
  • R 13 represents a monovalent aralkyl group having 7 to 21 carbon atoms. Examples of the monovalent aralkyl group having 7 to 21 carbon atoms include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and naphthylethyl group.
  • Examples of the monovalent heterocyclic group having 3 to 20 carbon atoms include thienyl group, benzo[b]thienyl group, naphtho[2,3-b]thienyl group, thianthrenyl group, furyl group, pyranyl group and isobenzofuranyl group.
  • Examples of the substituent of the heterocyclic group include the same groups as those described as the substituent of the aromatic hydrocarbon group.
  • R 13 is preferably an alicyclic saturated hydrocarbon group having 3 to 8 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a monovalent aralkyl group having 7 to 11 carbon atoms. ..
  • Structural units derived from N-substituted maleimides include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl- Structural units derived from 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N-(9-acridinyl)maleimide and the like are exemplified, among which N-phenylmaleimide, N-cyclohexylmaleimide, N- Structural units derived from benzylmaleimide are preferred.
  • the resin (B) is preferably an alkali-soluble resin.
  • alkali-soluble resin (B) include the following resins [K1] to [K6].
  • Resin [K1] a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides
  • Resin [K2] a structural unit derived from (a), a structural unit derived from (b), a structural unit derived from (m), and a monomer (c) (copolymerizable with (a) ( However, it is different from (a), (b) and (m).)
  • the structural unit derived from (a) above it is preferable that the carboxy group or carboxylic acid anhydride contained in (a) remains unreacted. Further, in the resins [K1] and [K2], it is preferable that the structural unit derived from (b) has a cyclic ether structure having 2 to 4 carbon atoms, which is contained in (b), remaining unreacted.
  • (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethy
  • (B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond.
  • (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
  • (meth)acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid.
  • the notations such as “(meth)acryloyl” and “(meth)acrylate” have the same meaning.
  • Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), a monomer having an oxetanyl group and an ethylenically unsaturated bond.
  • Examples include a monomer (b2) (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”).
  • Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)” And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).
  • Examples of (b1-1) include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, ⁇ -ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p.
  • Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation, 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by the formula (BI) and a formula (BII) And the like.
  • vinylcyclohexene monooxide for example, 1,2-epoxy-4-vinylcyclohexane
  • 3,4-epoxycyclohexylmethyl (meth)acrylate for example, Cyclomer A400; manufactured by Daicel Corporation, 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation
  • R e and R f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
  • X e and X f is a single bond, * - R g -, * - R g -O -, * - represents the R g -S- or * -R g -NH-.
  • R g represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O.
  • alkyl group having 1 to 4 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
  • alkyl group having a hydrogen atom substituted with hydroxy examples include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group and a 1-hydroxy group.
  • Examples thereof include a 1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.
  • R e and R f a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.
  • alkanediyl group examples include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group and the like can be mentioned.
  • Examples of X e and X f include a single bond, a methylene group, an ethylene group, *—CH 2 —O— and *—CH 2 CH 2 —O—, and a more preferred single bond, *—CH 2 CH 2 —O— can be mentioned (* represents a bond with O).
  • Examples of the compound represented by the formula (BI) include compounds represented by any of the formulas (BI-1) to (BI-15). Among them, formula (BI-1), formula (BI-3), formula (BII-5), formula (BI-7), formula (BI-9) or formula (BI-11) to formula (BI-15) The compound represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15) is more preferred.
  • Examples of the compound represented by the formula (BII) include compounds represented by any of the formulas (BII-1) to (BII-15). Among them, formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) to formula (BII-15)
  • the compound represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) or the formula (BII-15) is more preferable.
  • the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination of two or more kinds.
  • the content ratio thereof [the compound represented by the formula (BI): the compound represented by the formula (BII)] is The molar ratio is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.
  • (b2) a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable.
  • Examples of (b2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane.
  • (b3) a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable.
  • Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.
  • (b1) is preferable because the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. Further, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.
  • Examples of (c) include methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, sec-butyl(meth)acrylate, tert-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, Dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2, 6 ] Decane-8-yl(meth)acrylate (in the art, it is commonly called “dicyclopentanyl(meth)acrylate”.
  • tricyclodecyl(meth)acrylate It may also be called “tricyclodecyl(meth)acrylate”. .), tricyclo[5.2.1.0 2,6 ]decen-8-yl(meth)acrylate (known in the art as a trivial name "dicyclopentenyl (meth)acrylate"), Dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth) ) (Meth)acrylic acid esters such as acrylates; Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethy
  • the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K1], Structural unit derived from (a); 2-55 mol% Structural unit derived from (b); 2-85 mol% Structural unit derived from (m); 1 to 65 mol% Is preferred, Structural unit derived from (a); 5 to 50 mol% Structural unit derived from (b); 5-70 mol% Structural unit derived from (m); 5 to 60 mol% Is more preferable.
  • the ratio of the structural unit of the resin [K1] is within the above range, the absorption retention of the color filter obtained from the colored curable resin composition can be further improved.
  • the resin [K1] is, for example, the method described in “Experimental Method for Polymer Synthesis” (written by Takayuki Otsu, published by Kagaku Doujin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the literature. It can be manufactured by referring to the cited document described in.
  • a predetermined amount of (a), (b) and (m), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and oxygen is replaced by, for example, nitrogen to create a deoxygenated atmosphere, Examples of the method include heating and keeping heat while stirring.
  • the polymerization initiator, solvent and the like used here are not particularly limited, and those usually used in the relevant field can be used.
  • the solvent may be any solvent that can dissolve each monomer, and examples thereof include the solvent described below as the solvent (E) of the colored curable resin composition of the present invention.
  • the obtained copolymer may be used as the solution after the reaction as it is, or may be used as a concentrated or diluted solution, or taken out as a solid (powder) by a method such as reprecipitation. You may use the thing.
  • the solvent contained in the colored curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.
  • the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K2], Structural unit derived from (a); 2-55 mol% Structural unit derived from (b); 2-85 mol% Structural unit derived from (m); 1 to 65 mol% Structural unit derived from (c); 1 to 50 mol% Is preferred, Structural unit derived from (a); 5 to 50 mol% Structural unit derived from (b); 5-70 mol% Structural unit derived from (m); 5 to 60 mol% Structural unit derived from (c); 2 to 40 mol% Is more preferable.
  • the ratio of the structural unit of the resin [K2] is within the above range, the absorption retention of the color filter obtained from the colored curable resin composition can be further improved.
  • the resin [K2] can be manufactured, for example, in the same manner as the method described as the method for manufacturing the resin [K1].
  • the ratio of the structural units derived from each is as follows: Structural unit derived from (a); 2 to 60 mol% Structural unit derived from (m); 40 to 98 mol% Is preferred, Structural unit derived from (a); 10 to 55 mol% Structural unit derived from (m); 45 to 90 mol% Is more preferable.
  • the resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].
  • the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K1], Structural unit derived from (a); 2-55 mol% Structural unit derived from (m); 1 to 65 mol% Structural unit derived from (c); 1 to 50 mol% Is preferred, Structural unit derived from (a); 5 to 50 mol% Structural unit derived from (m); 5 to 60 mol% Structural unit derived from (c); 2 to 40 mol% Is more preferable.
  • the resin [K4] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].
  • a copolymer of (b) and (m) is obtained in the same manner as in the method for producing the resin [K1].
  • the obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
  • the ratios of the structural units derived from (b) and (m) are, respectively, with respect to the total number of moles of all the structural units constituting the copolymer.
  • the inside of the flask is made into an air atmosphere, and the reaction catalyst of the copolymer of (b) and (m), (a), carboxylic acid or carboxylic acid anhydride and cyclic ether (eg tris(dimethylaminomethyl)).
  • (Phenol, etc.) and a polymerization inhibitor eg, hydroquinone, etc.
  • the resin [K5] can be obtained by reacting the cyclic ether derived from b) with the carboxylic acid or carboxylic acid anhydride contained in (a).
  • the amount of (a) used to react with the above copolymer is preferably 5 to 80 mol per 100 mol of (b).
  • (B1) is preferable as (b) used in the resin [K5] because the reactivity of the cyclic ether is high and the unreacted (b) hardly remains.
  • the amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (m).
  • the amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (m).
  • Reaction conditions such as a charging method, reaction temperature and time can be appropriately adjusted in consideration of production equipment, the amount of heat generated by polymerization and the like.
  • the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization.
  • the resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride.
  • the carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction between the cyclic ether and the carboxylic acid or the carboxylic acid anhydride.
  • carboxylic acid anhydrides examples include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and 1 2,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like.
  • the amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mol per 1 mol of the amount used of (a).
  • the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid/N-phenylmaleimide copolymer and 3,4-epoxycyclohexylmethyl (meth)acrylate/( (Meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid/N-benzylmaleimide copolymer, 3,4-epoxytricyclo[5.2] .1.0 2,6 ]decyl acrylate/(meth)acrylic acid/N-phenylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate/(meth) Resins such as acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decy
  • the resin [K6] such as a resin obtained by further reacting the resin with tetrahydrophthalic anhydride may be mentioned.
  • resin (B) resins [K1] to resin [K4] are preferable, and resins [K1] and resin [K2] are more preferable.
  • the polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. .. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed area in the developing solution is good, and the resolution of the colored pattern tends to be improved.
  • the dispersity [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
  • the acid value of the resin (B) is, in terms of solid content, preferably 70 mg-KOH/g or more, more preferably 90 mg-KOH/g or more, further preferably 110 mg-KOH/g or more, preferably 220 mg-KOH. /G or less, more preferably 210 mg-KOH/g or less, still more preferably 200 mg-KOH/g or less.
  • the acid value is a value measured as an amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by, for example, titration using an aqueous potassium hydroxide solution. ..
  • the content of the resin (B) is preferably 7 to 80% by mass, more preferably 13 to 75% by mass, and further preferably 17 to 65% by mass, based on the total solid content.
  • the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to be improved.
  • the content of the resin (B) is preferably 10 parts by mass or more and 95 parts by mass or less, more preferably 20 parts by mass or more with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).
  • the amount is 90 parts by mass or less, and more preferably 30 parts by mass or more and 85 parts by mass or less.
  • the content of the resin (B) is within the above range, the absorbance retention of the obtained color filter is further improved.
  • the content of the resin (B) is 55 parts by mass or more and 95 parts by mass or less, preferably 60 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Is also preferable.
  • the content of the resin (B) is 10 parts by mass or more and 60 parts by mass or less, preferably 20 parts by mass or more and 55 parts by mass or less based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). In some cases, the absorbance retention and brightness of the resulting color filter are improved.
  • the polymerizable compound (C) is a compound that can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenic unsaturated bond, and preferably It is a (meth)acrylic acid ester compound.
  • the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds.
  • a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( (Meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl ) Isocyanurate, ethylene glycol
  • the content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, further preferably 10 to 55% by mass, based on the total amount of the solid content. is there.
  • the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.
  • the polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
  • Examples of polymerization initiators that generate active radicals include O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.
  • O-acyl oxime compound examples include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane.
  • the O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3- Cyclohexylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6- ⁇ 2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) Benzoyl ⁇ -9H-carbazol-3-yl]ethane-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime At least one selected from the group is preferable. With these O-acyl oxime compounds, a color filter with high brightness tends to be obtained.
  • alkylphenone compound examples include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane.
  • triazine compound examples include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-(4- Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy Styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4 -Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-Methylpheny
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • a commercially available product such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.
  • biimidazole compound examples include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3-dichlorophenyl)- 4,4′,5,5′-Tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis(2-chlorophenyl)-4 ,4',5,5'-Tetraphenylbiimidazole,2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole,2,2'-bis (2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trime
  • Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate and 4-acetoxy.
  • Onium salts such as phenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate and nitrobenzyl Examples thereof include tosylates and benzoin tosylates.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.
  • the polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds.
  • a polymerization initiator containing a vinyl compound is more preferable.
  • the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Parts by mass.
  • the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.
  • the solvent (E) is not particularly limited, and a solvent commonly used in this field can be used.
  • a solvent commonly used in this field can be used.
  • ester solvents solvents containing -COO- and not -O- in the molecule
  • ether solvents solvents containing -O- and not -COO-
  • ether ester solvents intramolecular
  • a solvent containing -COO- and -O- solvent containing -CO- in the molecule but not -COO-
  • an alcohol solvent containing OH in the molecule, -O-,- CO- and -COO--free solvents
  • aromatic hydrocarbon solvents aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.
  • Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and ⁇ -butyrolactone.
  • ether solvent ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl
  • ether diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methylanisole.
  • ether ester solvent examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and 3-ethoxy.
  • Ethyl propionate methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.
  • Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. And so on.
  • alcohol solvents examples include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.
  • aromatic hydrocarbon solvents examples include benzene, toluene, xylene, mesitylene and the like.
  • amide solvent examples include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
  • organic solvents having a boiling point of 120° C. or more and 180° C. or less at 1 atm are preferable from the viewpoints of coating properties and drying properties.
  • the solvent propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone And N,N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.
  • the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention.
  • the total solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass.
  • Leveling agent (F) examples include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
  • silicone-based surfactant examples include surfactants having a siloxane bond in the molecule.
  • Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 manufactured by Toray Dow Corning Co., Ltd.
  • KP321, KP322, KP323, KP324, KP326, Examples include KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 manufactured by Momentive Performance Materials Japan LLC.
  • fluorine-based surfactant examples include surfactants having a fluorocarbon chain in the molecule.
  • Florard (registered trademark) FC430, FC431 manufactured by Sumitomo 3M Limited
  • Megafac registered trademark
  • F142D F171, F172, F173, F177, F183, F554, and F543.
  • R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).
  • silicone-based surfactant having a fluorine atom examples include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megafac (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).
  • the content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.02% by mass or less with respect to the total amount of the colored curable resin composition. It is 2% by mass or less, and more preferably 0.005% by mass or more and 0.2% by mass or less.
  • the content of the dispersant is not included in this content.
  • the colored curable resin composition of the present invention if necessary, a polymerization initiation auxiliary agent, a filler, another polymer compound, an adhesion promoter, a light stabilizer, a chain transfer agent, etc., which are known additives in the technical field.
  • An agent may be included.
  • Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiene.
  • the colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary, It can be prepared by mixing the leveling agent (F) and other components.
  • Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, a printing method and the like. Among them, the photolithographic method is preferable.
  • the photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed.
  • a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and/or not developing.
  • the colored pattern or colored coating film thus formed is the color filter of the present invention.
  • the film thickness of the color filter to be produced is not particularly limited and may be appropriately adjusted depending on the purpose and application. For example, it is 0.1 to 30 ⁇ m, preferably 0.1 to 20 ⁇ m, and more preferably 0.5. ⁇ 6 ⁇ m.
  • each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions.
  • it can be manufactured as follows.
  • the colored curable resin composition is applied onto a substrate, and dried by heating (prebaking) and/or vacuum drying to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.
  • the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.
  • the temperature for heat drying is preferably 30 to 120°C, more preferably 50 to 110°C.
  • the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
  • the thickness of the coloring composition layer is not particularly limited and may be appropriately selected according to the intended thickness of the color filter.
  • the colored composition layer is exposed through a photomask for forming an intended colored pattern.
  • the pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
  • the light source used for exposure is preferably a light source that emits light having a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You may Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.
  • Use an exposure device such as a mask aligner or stepper because it can irradiate parallel rays uniformly on the entire exposed surface and can perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed. Is preferred.
  • a colored pattern is formed on the substrate by bringing the colored composition layer after exposure into contact with a developing solution for development.
  • a developing solution for development By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developing solution.
  • the developing solution for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable.
  • the concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.
  • the developer may contain a surfactant.
  • the developing method may be a paddle method, a dipping method, a spray method or the like.
  • the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
  • the post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C.
  • the post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.
  • a mixed solution prepared by dissolving 6 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 150 parts of 3-methoxybutylacetate was placed in a flask for 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 130 mPas and a solid content of 30.9% (resin (B-1 )) was obtained.
  • the produced copolymer had a weight average molecular weight (Mw) of 8,800, an acid value in terms of solid content of 137 mg-KOH/g, and a dispersity of 1.76.
  • the resin (B-1) has the following structural unit.
  • the polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
  • the polystyrene equivalent weight average molecular weight and number average molecular weight ratio (Mw/Mn) obtained above was taken as the dispersity.
  • a mixed solution prepared by dissolving 8 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 183 parts of propylene glycol monomethyl ether acetate was placed in the flask for 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 22 mPas and a solid content of 26.1% (resin (B-2 )) was obtained.
  • the produced copolymer had a weight average molecular weight (Mw) of 8900, an acid value in terms of solid content of 143 mg-KOH/g, and a dispersity of 1.92.
  • the resin (B-2) has the same structural unit as the resin (B-1).
  • a mixed solution prepared by dissolving 20 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 145 parts of propylene glycol monomethyl ether acetate was placed in the flask for 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 18 mPas and a solid content of 25.7% (resin (B-3 )) was obtained.
  • the resulting copolymer had a weight average molecular weight (Mw) of 8,000, an acid value in terms of solid content of 119 mg-KOH/g, and a dispersity of 2.09.
  • the resin (B-3) has the same structural unit as the resin (B-1).
  • a mixed solution prepared by dissolving 7 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 145 parts of propylene glycol monomethyl ether acetate was placed in the flask for 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 75 mPas and a solid content of 34.7% (resin (B-4 )) was obtained.
  • the produced copolymer had a weight average molecular weight (Mw) of 8,800, an acid value in terms of solid content of 181 mg-KOH/g, and a dispersity of 2.20.
  • the resin (B-4) has the same structural unit as the resin (B-1).
  • the weight average molecular weight (Mw) of the produced copolymer was 9000, the acid value in terms of solid content was 183 mg-KOH/g, and the dispersity was 2.06.
  • the resin (B-5) has the same structural unit as the resin (B-1).
  • a solution of 171 parts of a mixture of 1.0 2,6 ]decane-9-yl acrylate (mixing ratio is 1:1) in 40 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours by using a dropping pump. ..
  • a solution prepared by dissolving 26 parts of the polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was put into the flask for about 5 hours using another dropping pump. Dropped.
  • the temperature was maintained at the same temperature for about 3 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (B-6)) having a solid content of 43.5%. ..
  • the obtained resin (B-2) had a weight average molecular weight of 8,000, a dispersity of 1.98 and an acid value in terms of solid content of 53 mg-KOH/g.
  • the resin (B-6) has the following structural unit.
  • each component represents the following compound.
  • a colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by a spin coating method so that the film thickness after post-baking would be 2.0 ⁇ m, and then 3 at 100° C. It was prebaked for a minute to form a colored composition layer. After allowing to cool, the colored composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon Corp.) in an air atmosphere at an exposure dose of 100 mJ/cm 2 (365 nm standard). Then, post-baking was performed in an oven at 230° C. for 30 minutes to obtain a colored coating film.
  • TAE-150RSK an exposure machine
  • a color filter having excellent absorbance retention can be formed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Theoretical Computer Science (AREA)
  • Engineering & Computer Science (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention addresses the problem of providing a colored curable resin composition with which it is possible to form a color filter that exhibits superior light-absorbency retention rate.　The present invention relates to a colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant includes a squarylium dye represented by formula (I), and the resin includes a structural unit derived from an N-substituted maleimide.

Description

着色硬化性樹脂組成物Colored curable resin composition
　本発明は、着色硬化性樹脂組成物に関する。 The present invention relates to a colored curable resin composition.
　液晶表示装置、エレクトロルミネッセンス表示装置及びプラズマディスプレイ等の表示装置やＣＣＤやＣＭＯＳセンサなどの固体撮像素子に使用されるカラーフィルタは、着色樹脂組成物から製造される。このような着色樹脂組成物に用いられる着色剤として、スクアリリウム染料が知られている（特許文献１、２など）。 Color filters used for display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are manufactured from a colored resin composition. A squarylium dye is known as a colorant used in such a colored resin composition (Patent Documents 1 and 2).
特開２０１５－８６３７９号公報JP, 2005-86379, A 特開２０１５－８６３８０号公報JP, 2005-86380, A
　しかし従来から知られる、着色剤としてスクアリリウム染料を用いた上記の着色硬化性樹脂組成物から形成されるカラーフィルタは、吸光度保持率を十分に満足できない場合があった。そこで、本発明は吸光度保持率に優れたカラーフィルタを形成できる着色硬化性樹脂組成物を提供することを課題とする。 However, the conventionally known color filter formed from the above colored curable resin composition using a squarylium dye as a colorant may not be able to sufficiently satisfy the absorbance retention rate. Therefore, it is an object of the present invention to provide a colored curable resin composition capable of forming a color filter having excellent absorbance retention.
　本発明の要旨は以下の通りである。
［１］　着色剤、樹脂、重合性化合物、及び重合開始剤を含み、
　前記着色剤が、式（Ｉ）で表されるスクアリリウム染料を含む着色剤であり、
　前記樹脂が、Ｎ－置換マレイミドに由来する構造単位を含む樹脂である着色硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000003
 ［式（Ｉ）中、
　Ｒ1～Ｒ4は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基又は置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。
　Ｒ5～Ｒ8は、それぞれ独立に、水素原子又はヒドロキシ基を表す。
　Ａｒ1及びＡｒ2は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は式（ｉ）で表される基を表す。
Figure JPOXMLDOC01-appb-C000004
 ［式（ｉ）中、
　Ｒ12は、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は置換基を有していてもよい炭素数２～２０の１価の不飽和炭化水素基を表し、ｍは０～５の整数を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。ｍが２以上のとき、複数のＲ12は、それぞれ同一であっても異なっていてもよい。＊は、窒素原子との結合手を表す。］
　Ｒ9及びＲ10は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は式（ｉ）で表される基を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。］
［２］　［１］に記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［３］　［２］に記載のカラーフィルタを含む表示装置。 The gist of the present invention is as follows.
[1] contains a colorant, a resin, a polymerizable compound, and a polymerization initiator,
The colorant is a colorant containing a squarylium dye of formula (I),
A colored curable resin composition, wherein the resin is a resin containing a structural unit derived from an N-substituted maleimide.
Figure JPOXMLDOC01-appb-C000003
 [In the formula (I),
R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
R 5 to R 8 each independently represent a hydrogen atom or a hydroxy group.
Ar 1 and Ar 2 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, or a group represented by the formula (i).
Figure JPOXMLDOC01-appb-C000004
 [In formula (i),
R 12 is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent. And m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. When m is 2 or more, a plurality of R 12's may be the same or different. * Represents a bond with the nitrogen atom. ]
R 9 and R 10 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i). An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. ]
[2] A color filter formed from the colored curable resin composition according to [1].
[3] A display device including the color filter according to [2].
　本発明の着色硬化性樹脂組成物によれば吸光度保持率に優れたカラーフィルタを提供できる。 According to the colored curable resin composition of the present invention, it is possible to provide a color filter having excellent absorbance retention.
　本発明の着色硬化性樹脂組成物は、着色剤（以下、着色剤（Ａ）という場合がある）、樹脂（以下、樹脂（Ｂ）という場合がある）、重合性化合物（以下、重合性化合物（Ｃ）という場合がある）、及び重合開始剤（以下、重合開始剤（Ｄ）という場合がある）を含む。
　着色剤は、式（Ｉ）で表されるスクアリリウム染料（以下、化合物（Ｉ）という場合がある）を含む。
　樹脂は、Ｎ－置換マレイミドに由来する構造単位を含む。
　本発明の着色硬化性樹脂組成物は、さらに溶剤（以下、溶剤（Ｅ）という場合がある）を含むことが好ましい。
　本発明の着色硬化性樹脂組成物は、レベリング剤（以下、レベリング剤（Ｆ）という場合がある）を含んでもよい。
　本明細書において、各成分として例示する化合物は、特に断りのない限り、単独で又は複数種を組合せて使用することができる。 The colored curable resin composition of the present invention includes a colorant (hereinafter sometimes referred to as a colorant (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, a polymerizable compound). (C) and a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)).
The colorant includes a squarylium dye represented by formula (I) (hereinafter sometimes referred to as compound (I)).
The resin comprises structural units derived from N-substituted maleimides.
The colored curable resin composition of the present invention preferably further contains a solvent (hereinafter sometimes referred to as solvent (E)).
The colored curable resin composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as a leveling agent (F)).
In the present specification, the compounds exemplified as the respective components can be used alone or in combination of two or more kinds unless otherwise specified.
＜着色剤（Ａ）＞
　着色剤（Ａ）は、化合物（Ｉ）を含む。以下、式（Ｉ）を用いて本発明について詳述するが、化合物（Ｉ）には、式（Ｉ）の共鳴構造や、式（Ｉ）中の各基を単結合の結合軸周りに回転させて得られる化合物も含まれることとする。 <Colorant (A)>
The colorant (A) includes the compound (I). Hereinafter, the present invention will be described in detail using the formula (I). In the compound (I), the resonance structure of the formula (I) and each group in the formula (I) are rotated around a single bond bond axis. The compound obtained by the above is also included.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
［式（Ｉ）中、
　Ｒ1～Ｒ4は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基又は置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。
　Ｒ5～Ｒ8は、それぞれ独立に、水素原子又はヒドロキシ基を表す。
　Ａｒ1及びＡｒ2は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は式（ｉ）で表される基を表し、好ましくは式（ｉ）で表される基を表す。
Figure JPOXMLDOC01-appb-C000006
 ［式（ｉ）中、
　Ｒ12は、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は置換基を有していてもよい炭素数２～２０の１価の不飽和炭化水素基を表し、ｍは０～５の整数を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。ｍが２以上のとき、複数のＲ12は、それぞれ同一であっても異なっていてもよい。＊は、窒素原子との結合手を表す。］
　Ｒ9及びＲ10は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は式（ｉ）で表される基を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。］ [In the formula (I),
R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
R 5 to R 8 each independently represent a hydrogen atom or a hydroxy group.
Ar 1 and Ar 2 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i), and preferably a group represented by the formula ( represents a group represented by i).
Figure JPOXMLDOC01-appb-C000006
 [In formula (i),
R 12 is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent. And m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. When m is 2 or more, a plurality of R 12's may be the same or different. * Represents a bond with the nitrogen atom. ]
R 9 and R 10 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i). An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. ]
　式（Ｉ）中、Ｒ1～Ｒ4におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子又はヨウ素原子が挙げられる。 In formula (I), examples of the halogen atom for R 1 to R 4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
　Ｒ1～Ｒ4、Ｒ9、Ｒ10、Ｒ12、Ａｒ1及びＡｒ2における炭素数１～２０の１価の飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、ヘキサデシル基及びイコシル基等の炭素数１～２０の直鎖状アルキル基；イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソペンチル基、ネオペンチル基及び２－エチルヘキシル基等の炭素数３～２０の分岐鎖状アルキル基；シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、トリシクロデシル基及びアダマンチル基等の炭素数３～２０の脂環式飽和炭化水素基が挙げられる。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1 to R 4 , R 9 , R 10 , R 12 , Ar 1 and Ar 2 include a methyl group, an ethyl group, a propyl group and a butyl group. , Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group, and other linear alkyl groups having 1 to 20 carbon atoms; isopropyl group, isobutyl group, sec-butyl group Group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, and other branched-chain alkyl groups having 3 to 20 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, trioctyl group Examples thereof include alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclodecyl group and adamantyl group.
　これらの飽和炭化水素基の置換基としては、フッ素原子、塩素原子、ヨウ素等のハロゲン原子；ヒドロキシ基；カルボキシ基；－ＮＲaＲb(Ｒa及びＲbは、それぞれ独立に、水素原子又は炭素数１～２０のアルキル基である)；ニトロ基；メトキシカルボニル基、エトキシカルボニル基等の炭素数１～１０のアルコキシカルボニル基；等が挙げられ、置換基を有している炭素数１～２０の１価の飽和炭化水素基としては、例えば、下記式で表される基が挙げられる。下記式中、＊は結合手を表す。 Substituents for these saturated hydrocarbon groups include halogen atoms such as fluorine atom, chlorine atom and iodine; hydroxy group; carboxy group; -NR a R b (R a and R b are each independently a hydrogen atom or An alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; Examples of the monovalent saturated hydrocarbon group of 20 include groups represented by the following formula. In the following formula, * represents a bond.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　これらの飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されている基としては、例えば、下記式で表される基が挙げられる。下記式中、＊は結合手を表す。 Examples of groups in which an oxygen atom or a sulfur atom is inserted between the carbon atoms constituting these saturated hydrocarbon groups include groups represented by the following formula. In the following formula, * represents a bond.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　Ｒ12における炭素数２～２０の１価の不飽和炭化水素基としては、例えば、ビニル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基が挙げられる。 Examples of the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms in R 12 include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group and decenyl group. To be
　該不飽和炭化水素基の置換基としては、フッ素原子、塩素原子、ヨウ素等のハロゲン原子；ヒドロキシ基；カルボキシ基；－ＮＲcＲd(Ｒc及びＲdは、それぞれ独立に、水素原子又は炭素数１～２０のアルキル基である)；ニトロ基；メトキシ基、エトキシ基等の炭素数１～１０のアルコキシ基；メトキシカルボニル基、エトキシカルボニル基等の炭素数１～１０のアルコキシカルボニル基；等が挙げられる。 As the substituent of the unsaturated hydrocarbon group, a halogen atom such as a fluorine atom, a chlorine atom and iodine; a hydroxy group; a carboxy group; —NR c R d (R c and R d are each independently a hydrogen atom or A C1-C20 alkyl group); a nitro group; a C1-C10 alkoxy group such as a methoxy group and an ethoxy group; a C1-C10 alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; Etc.
　Ｒ1～Ｒ4としては、水素原子、ヒドロキシ基及び炭素数１～４のアルキル基が好ましく、水素原子、ヒドロキシ基及びメチル基がより好ましく、水素原子がさらに好ましい。 As R 1 to R 4 , a hydrogen atom, a hydroxy group and an alkyl group having 1 to 4 carbon atoms are preferable, a hydrogen atom, a hydroxy group and a methyl group are more preferable, and a hydrogen atom is still more preferable.
　Ｒ5～Ｒ8は、少なくとも１つがヒドロキシ基であることが好ましい。Ｒ5及びＲ6の少なくとも一方がヒドロキシ基であり、Ｒ7及びＲ8の少なくとも一方がヒドロキシ基であることがより好ましい。 At least one of R 5 to R 8 is preferably a hydroxy group. More preferably, at least one of R 5 and R 6 is a hydroxy group, and at least one of R 7 and R 8 is a hydroxy group.
　Ｒ9及びＲ10としては、置換基を有していてもよい炭素数３～１４のアルキル基及び式（ｉ）で表される基が好ましく、置換基を有していてもよい炭素数３～６の直鎖状アルキル基、置換基を有していてもよい炭素数７～１４の直鎖状又は分岐鎖状のアルキル基（例えば、オクチル基、ノニル基、デシル基、ドデシル基、２－エチルヘキシル基など）、及び式（ｉ）で表される基がより好ましく、末端にヒドロキシ基を有する炭素数３～５の直鎖状アルキル基、末端にカルボキシ基を有する炭素数３～５の直鎖状アルキル基、及び２－エチルヘキシル基がさらに好ましい。 As R 9 and R 10 , an alkyl group having 3 to 14 carbon atoms which may have a substituent and a group represented by the formula (i) are preferable, and an alkyl group having 3 carbon atoms which may have a substituent. To 6 straight-chain alkyl groups, and C 7-14 straight-chain or branched alkyl groups which may have a substituent (eg, octyl group, nonyl group, decyl group, dodecyl group, 2 -Ethylhexyl group, etc.) and a group represented by the formula (i) are more preferable, and a linear alkyl group having a hydroxy group at a terminal and having 3 to 5 carbon atoms, and a group having a carboxy group at a terminal and having 3 to 5 carbon atoms A linear alkyl group and a 2-ethylhexyl group are more preferable.
　Ｒ12の飽和炭化水素基としては、炭素数１～４のアルキル基が好ましく、メチル基、エチル基、イソプロピル基がより好ましい。
　Ｒ12の不飽和炭化水素基としては、炭素数２～４のアルケニル基が好ましく、ビニル基、アリル基がより好ましい。
　ｍが２以上の場合、少なくとも１つのＲ12が飽和炭化水素基であることが好ましい。ｍが２以上の場合、全てのＲ12が飽和炭化水素基である態様、又は一部のＲ12が飽和炭化水素基であって一部のＲ12が不飽和炭化水素基である態様がより好ましい。 The saturated hydrocarbon group for R 12 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group.
The unsaturated hydrocarbon group for R 12 is preferably an alkenyl group having 2 to 4 carbon atoms, more preferably a vinyl group or an allyl group.
When m is 2 or more, at least one R 12 is preferably a saturated hydrocarbon group. When m is 2 or more, an embodiment in which all R 12 are saturated hydrocarbon groups or an embodiment in which some R 12 are saturated hydrocarbon groups and some R 12 are unsaturated hydrocarbon groups is more preferable. preferable.
　ｍは、好ましくは１～５であり、より好ましくは１～３である。
　式（ｉ）で表される基としては、例えば、次のような基が挙げられる。＊は、窒素原子との結合手を表す。 m is preferably 1 to 5, more preferably 1 to 3.
Examples of the group represented by the formula (i) include the following groups. * Represents a bond with the nitrogen atom.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（Ｉ）中、 In formula (I),
Figure JPOXMLDOC01-appb-C000010
 で表される基をＸ1、
Figure JPOXMLDOC01-appb-C000010
 A group represented by X 1 ,
Figure JPOXMLDOC01-appb-C000011
 で表される基をＸ2としたとき、Ｘ1及びＸ2で表される基としては、例えば、式（Ａ２－１）～（Ａ２－９）で表される基が挙げられる。＊は、炭素原子との結合手を表す。
Figure JPOXMLDOC01-appb-C000011
 When the group represented by is represented by X 2 , examples of the group represented by X 1 and X 2 include groups represented by formulas (A2-1) to (A2-9). * Represents a bond with a carbon atom.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　化合物（Ｉ）として、例えば、表１に示す化合物（ＡＩＩ－１）～化合物（ＡＩＩ－２７）が挙げられる。 Examples of the compound (I) include the compounds (AII-1) to (AII-27) shown in Table 1.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　化合物（ＡＩＩ－１０）～化合物（ＡＩＩ－１８）がより好ましい。 Compound (AII-10) to compound (AII-18) are more preferable.
　式（Ｉ）で表される化合物は、式（ｐｔ１）で表される化合物と、式（ｐｔ２）で表される化合物と、式（ｐｔ３）で表される化合物を、反応させることにより製造できる。本反応において、式（ｐｔ３）で表される化合物の使用量は、式（ｐｔ１）で表される化合物及び式（ｐｔ２）で表される化合物の合計１モルに対して、好ましくは０．０５モル以上０．８モル以下であり、より好ましくは０．１モル以上０．６モル以下である。 The compound represented by formula (I) can be produced by reacting the compound represented by formula (pt1) with the compound represented by formula (pt2) and the compound represented by formula (pt3). .. In this reaction, the amount of the compound represented by the formula (pt3) used is preferably 0.05 with respect to 1 mol in total of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). The amount is not less than 0.8 and not more than 0.8, and more preferably not less than 0.1 and not more than 0.6.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式中、Ｒ1～Ｒ10、Ａｒ1及びＡｒ2は、それぞれ上記と同じ意味を表す。 In the formula, R 1 to R 10 , Ar 1 and Ar 2 have the same meanings as described above.
　反応温度は、３０℃～１８０℃が好ましく、８０℃～１４０℃がより好ましい。反応時間は、１時間～１２時間が好ましく、３時間～８時間がより好ましい。 The reaction temperature is preferably 30°C to 180°C, more preferably 80°C to 140°C. The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.
　反応は、収率の点から、有機溶剤中で行うことが好ましい。有機溶剤としては、トルエン、キシレン等の炭化水素溶剤；クロロベンゼン、ジクロロベンゼン、クロロホルム等のハロゲン化炭化水素溶剤；メタノール、エタノール、イソプロパノール、ブタノール等のアルコール溶剤；ニトロベンゼン等のニトロ炭化水素溶剤；メチルイソブチルケトン等のケトン溶剤；１－メチル－２－ピロリドン等のアミド溶剤；等が挙げられ、これらを混合して使用してもよい。中でもブタノール及びトルエンの混合溶剤が好ましい。有機溶剤の使用量は、式（ｐｔ１）で表される化合物及び式（ｐｔ２）で表される化合物の合計１質量部に対して、好ましくは１０質量部以上２００質量部以下であり、より好ましくは３０質量部以上１５０質量部以下である。 From the viewpoint of yield, it is preferable to carry out the reaction in an organic solvent. Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl. Examples thereof include ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone; and the like, and these may be mixed and used. Of these, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 1 part by mass of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). Is 30 parts by mass or more and 150 parts by mass or less.
　反応混合物から目的化合物である化合物（Ｉ）を取り出す方法は特に限定されず、公知の種々の方法が使用できる。例えば反応終了後に冷却し、析出した結晶を濾取する方法が挙げられる。濾取した結晶は、水などで洗浄し、次いで乾燥することが好ましい。また必要に応じて、再結晶などの公知の方法によってさらに精製してもよい。 The method for taking out the target compound (I) from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method may be mentioned in which the reaction mixture is cooled after completion of the reaction and the precipitated crystals are collected by filtration. The crystals collected by filtration are preferably washed with water or the like and then dried. If necessary, it may be further purified by a known method such as recrystallization.
　式（ＩＶ－２）で表される化合物と式（ＩＶ－３）で表される化合物とを反応させて、式（ＩＶ－４）で表される化合物を製造した後、式（ＩＶ－４）で表される化合物と式（ＩＶ－５）で表される化合物とを反応させることにより、式（ｐｔ１）で表される化合物を製造することができる。 After reacting the compound represented by formula (IV-2) with the compound represented by formula (IV-3) to produce the compound represented by formula (IV-4), the compound represented by formula (IV-4) By reacting the compound represented by the formula () with the compound represented by the formula (IV-5), the compound represented by the formula (pt1) can be produced.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（ＩＶ－２）～式（ＩＶ－５）中、Ｒ1、Ｒ2、Ｒ5、Ｒ6、Ｒ9及びＡｒ1は、それぞれ上記と同じ意味を表す。 In formulas (IV-2) to (IV-5), R 1 , R 2 , R 5 , R 6 , R 9 and Ar 1 each have the same meaning as described above.
　式（ＩＶ－２）で表される化合物と式（ＩＶ－３）で表される化合物とから、式（ＩＶ－４）で表される化合物を製造する方法としては、公知の種々の方法、例えば、Eur. J. Org. Chem. 2012, 3105-3111．に記載されている方法が挙げられる。 As a method for producing the compound represented by the formula (IV-4) from the compound represented by the formula (IV-2) and the compound represented by the formula (IV-3), various known methods can be used. For example, Eur.J. Org. Chem.2012,3105-3111. The method described in 1.
　式（ＩＶ－４）で表される化合物と式（ＩＶ－５）で表される化合物とから、式（ｐｔ１）で表される化合物を製造する方法としては、公知の種々の方法、例えばJ.Polymer Sciene Science Part A:Polymer Chemistry 2012, 50, 3788-3796に記載されている方法が挙げられる。 As a method for producing the compound represented by the formula (pt1) from the compound represented by the formula (IV-4) and the compound represented by the formula (IV-5), various known methods such as J PolymerScieneSciencePart A: Polymer Chemistry 2012, 50, 3788-3796.
　上記と同様の方法を用いて、式（ｐｔ２）で表される化合物を製造することができる。 A compound represented by the formula (pt2) can be produced by using the same method as described above.
　着色剤（Ａ）は、化合物（Ｉ）以外に、化合物（Ｉ）とは異なる着色剤を含んでいてもよく、該化合物（Ｉ）とは異なる着色剤は、染料（以下、染料（Ａ１）という場合がある。）、及び顔料（以下、顔料（Ａ２）という場合がある。）のいずれでもよく、化合物（Ｉ）とは異なる着色剤は、これら染料（Ａ１）及び顔料（Ａ２）の一方又は両方を含んでいてもよい。 The colorant (A) may contain a colorant different from the compound (I) in addition to the compound (I), and the colorant different from the compound (I) is a dye (hereinafter, referred to as a dye (A1)). Or a pigment (hereinafter sometimes referred to as a pigment (A2)), and the colorant different from the compound (I) is one of the dye (A1) and the pigment (A2). Alternatively, both may be included.
　染料（Ａ１）は、化合物（Ｉ）を包含しない限り、特に限定されず公知の染料を使用することができ、溶剤染料、酸性染料、直接染料、媒染染料等が挙げられる。染料としては、例えば、カラーインデックス（The Society of Dyers and Colourists出版）でピグメント以外で色相を有するものに分類されている化合物や、染色ノート（色染社）に記載されている公知の染料が挙げられる。また、化学構造によれば、アゾ染料、シアニン染料、トリフェニルメタン染料、キサンテン染料、フタロシアニン染料、アントラキノン染料、ナフトキノン染料、キノンイミン染料、メチン染料、アゾメチン染料、アクリジン染料、スチリル染料、クマリン染料、キノリン染料及びニトロ染料等が挙げられる。これらのうち、有機溶剤可溶性染料が好ましい。 The dye (A1) is not particularly limited as long as it does not include the compound (I), and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes and mordant dyes. Examples of the dyes include compounds that are classified as having a hue other than pigment in the color index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Note (Shikisosha). To be Further, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, acridine dye, styryl dye, coumarin dye, quinoline dye. Examples thereof include dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.
　具体的には、Ｃ．Ｉ．ソルベントイエロー４（以下、Ｃ．Ｉ．ソルベントイエローの記載を省略し、番号のみの記載とする。）、１４、１５、２３、２４、３８、６２、６３、６８、８２、９４、９８、９９、１１７、１６２、１６３、１６７、１８９；
　Ｃ．Ｉ．ソルベントレッド４５、４９、１１１、１２５、１３０、１４３、１４５、１４６、１５０、１５１、１５５、１６８、１６９、１７２、１７５、１８１、２０７、２１８、２２２、２２７、２３０、２４５、２４７；
　Ｃ．Ｉ．ソルベントオレンジ２、７、１１、１５、２６、５６、７７、８６；
　Ｃ．Ｉ．ソルベントバイオレット１１、１３、１４、２６、３１、３６、３７、３８、４５、４７、４８、５１、５９、６０；
　Ｃ．Ｉ．ソルベントブルー４、５、１４、１８、３５、３６、３７、４５、５８、５９、５９：１、６３、６７、６８、６９、７０、７８、７９、８３、９０、９４、９７、９８、１００、１０１、１０２、１０４、１０５、１１１、１１２、１２２、１２８、１３２、１３６、１３９；
　Ｃ．Ｉ．ソルベントグリーン１、３、４、５、７、２８、２９、３２、３３、３４、３５等のＣ．Ｉ．ソルベント染料、
　Ｃ．Ｉ．アシッドイエロー１、３、７、９、１１、１７、２３、２５、２９、３４、３６、３８、４０、４２、５４、６５、７２、７３、７６、７９、９８、９９、１１１、１１２、１１３、１１４、１１６、１１９、１２３、１２８、１３４、１３５、１３８、１３９、１４０、１４４、１５０、１５５、１５７、１６０、１６１、１６３、１６８、１６９、１７２、１７７、１７８、１７９、１８４、１９０、１９３、１９６、１９７、１９９、２０２、２０３、２０４、２０５、２０７、２１２、２１４、２２０、２２１、２２８、２３０、２３２、２３５、２３８、２４０、２４２、２４３、２５１；
　Ｃ．Ｉ．アシッドレッド１、４、８、１４、１７、１８、２６、２７、２９、３１、３３、３４、３５、３７、４０、４２、４４、５０、５１、５２、５７、６６、７３、７６、８０、８７、８８、９１、９２、９４、９５、９７、９８、１０３、１０６、１１１、１１４、１２９、１３３、１３４、１３８、１４３、１４５、１５０、１５１、１５５、１５８、１６０、１７２、１７６、１８２、１８３、１９５、１９８、２０６、２１１、２１５、２１６、２１７、２２７、２２８、２４９、２５２、２５７、２５８、２６０、２６１、２６６、２６８、２７０、２７４、２７７、２８０、２８１、２８９、３０８、３１２、３１５、３１６、３３９、３４１、３４５、３４６、３４９、３８２、３８３、３８８、３９４、４０１、４１２、４１７、４１８、４２２、４２６；
　Ｃ．Ｉ．アシッドオレンジ６、７、８、１０、１２、２６、５０、５１、５２、５６、６２、６３、６４、７４、７５、９４、９５、１０７、１０８、１６９、１７３；
　Ｃ．Ｉ．アシッドバイオレット６Ｂ、７、９、１５、１６、１７、１９、２１、２３、２４、２５、３０、３４、３８、４９、７２、１０２；
　Ｃ．Ｉ．アシッドブルー１、３、５、７、９、１１、１３、１５、１７、１８、２２、２３、２４、２５、２６、２７、２９、３４、３８、４０、４１、４２、４３、４５、４８、５１、５４、５９、６０、６２、７０、７２、７４、７５、７８、８０、８２、８３、８６、８７、８８、９０、９０：１、９１、９２、９３、９３：１、９６、９９、１００、１０２、１０３、１０４、１０８、１０９、１１０、１１２、１１３、１１７、１１９、１２０、１２３、１２６、１２７、１２９、１３０、１３１、１３８、１４０、１４２、１４３、１４７、１５０、１５１、１５４、１５８、１６１、１６６、１６７、１６８、１７０、１７１、１７５、１８２、１８３、１８４、１８７、１９２、１９９、２０３、２０４、２０５、２１０、２１３、２２９、２３４、２３６、２４２、２４３、２５６、２５９、２６７、２６９、２７８、２８０、２８５、２９０、２９６、３１５、３２４：１、３３５、３４０；
　Ｃ．Ｉ．アシッドグリーン１、３、５、６、７、８、９、１１、１３、１４、１５、１６、２２、２５、２７、２８、４１、５０、５０：１、５８、６３、６５、８０、１０４、１０５、１０６、１０９等のＣ．Ｉ．アシッド染料、
　Ｃ．Ｉ．ダイレクトイエロー２、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；
　Ｃ．Ｉ．ダイレクトレッド７９、８２、８３、８４、９１、９２、９６、９７、９８、９９、１０５、１０６、１０７、１７２、１７３、１７６、１７７、１７９、１８１、１８２、１８４、２０４、２０７、２１１、２１３、２１８、２２０、２２１、２２２、２３２、２３３、２３４、２４１、２４３、２４６、２５０；
　Ｃ．Ｉ．ダイレクトオレンジ２６、３４、３９、４１、４６、５０、５２、５６、５７、６１、６４、６５、６８、７０、９６、９７、１０６、１０７；
　Ｃ．Ｉ．ダイレクトバイオレット４７、５２、５４、５９、６０、６５、６６、７９、８０、８１、８２、８４、８９、９０、９３、９５、９６、１０３、１０４；
　Ｃ．Ｉ．ダイレクトブルー１、２、３、６、８、１５、２２、２５、２８、２９、４０、４１、４２、４７、５２、５５、５７、７１、７６、７７、７８、８０、８１、８４、８５、８６、９０、９３、９４、９５、９７、９８、９９、１００、１０１、１０６、１０７、１０８、１０９、１１３、１１４、１１５、１１７、１１９、１２０、１３７、１４９、１５０、１５３、１５５、１５６、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１７０、１７１、１７２、１７３、１８８、１８９、１９０、１９２、１９３、１９４、１９５、１９６、１９８、１９９、２００、２０１、２０２、２０３、２０７、２０９、２１０、２１２、２１３、２１４、２２２、２２５、２２６、２２８、２２９、２３６、２３７、２３８、２４２、２４３、２４４、２４５、２４６、２４７、２４８、２４９、２５０、２５１、２５２、２５６、２５７、２５９、２６０、２６８、２７４、２７５、２９３；
　Ｃ．Ｉ．ダイレクトグリーン２５、２７、３１、３２、３４、３７、６３、６５、６６、６７、６８、６９、７２、７７、７９、８２等のＣ．Ｉ．ダイレクト染料、
　Ｃ．Ｉ．ディスパースイエロー５１、５４，７６；
　Ｃ．Ｉ．ディスパースバイオレット２６、２７；
　Ｃ．Ｉ．ディスパースブルー１、１４、５６、６０等のＣ．Ｉ．ディスパース染料、
　Ｃ．Ｉ．ベーシックレッド１、１０；
　Ｃ．Ｉ．ベーシックブルー１、３、５、７、９、１９、２１、２２、２４、２５、２６、２８、２９、４０、４１、４５、４７、５４、５８、５９、６０、６４、６５、６６、６７、６８、８１、８３、８８、８９；
　Ｃ．Ｉ．ベーシックバイオレット２；
　Ｃ．Ｉ．ベーシックレッド９；
　Ｃ．Ｉ．ベーシックグリーン１等のＣ．Ｉ．ベーシック染料、
　Ｃ．Ｉ．リアクティブイエロー２，７６，１１６；
　Ｃ．Ｉ．リアクティブオレンジ１６；
　Ｃ．Ｉ．リアクティブレッド３６等のＣ．Ｉ．リアクティブ染料、
　Ｃ．Ｉ．モーダントイエロー５、８、１０、１６、２０、２６、３０、３１、３３、４２、４３、４５、５６、６１、６２、６５；
　Ｃ．Ｉ．モーダントレッド１、２、３、４、９、１１、１２、１４、１７、１８、１９、２２、２３、２４、２５、２６、２７、２９、３０、３２、３３、３６、３７、３８、３９、４１、４２、４３、４５、４６、４８、５２、５３、５６、６２、６３、７１、７４、７６、７８、８５、８６、８８、９０、９４、９５；
　Ｃ．Ｉ．モーダントオレンジ３、４、５、８、１２、１３、１４、２０、２１、２３、２４、２８、２９、３２、３４、３５、３６、３７、４２、４３、４７、４８；
　Ｃ．Ｉ．モーダントバイオレット１、１：１、２、３、４、５、６、７、８、１０、１１、１４、１５、１６、１７、１８、１９、２１、２２、２３、２４、２７、２８、３０、３１、３２、３３、３６、３７、３９、４０、４１、４４、４５、４７、４８、４９、５３、５８；
　Ｃ．Ｉ．モーダントブルー１、２、３、７、８、９、１２、１３、１５、１６、１９、２０、２１、２２、２３、２４、２６、３０、３１、３２、３９、４０、４１、４３、４４、４８、４９、５３、６１、７４、７７、８３、８４；
　Ｃ．Ｉ．モーダントグリーン１、３、４、５、１０、１３、１５、１９、２１、２３、２６、２９、３１、３３、３４、３５、４１、４３、５３等のＣ．Ｉ．モーダント染料、　Ｃ．Ｉ．バットグリーン１等のＣ．Ｉ．バット染料等が挙げられる。
　これらの染料は、所望するカラーフィルタの分光スペクトルに合わせて適宜選択すればよい。 Specifically, C.I. I. Solvent Yellow 4 (hereinafter, CI Solvent Yellow is omitted and only the numbers are shown), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99. 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like C.I. I. Solvent dye,
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, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;
C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, C. 104, 105, 106, 109, etc. I. Acid dyes,
C. 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, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. C. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. Direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. C. such as Disperse Blue 1, 14, 56, 60 and the like. I. Disperse dye,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. Basic Violet 2;
C. I. Basic Red 9;
C. I. C. such as Basic Green 1 I. Basic dye,
C. I. Reactive Yellow 2,76,116;
C. I. Reactive Orange 16;
C. I. C. such as Reactive Red 36 I. Reactive dye,
C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Mordan tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C. I. MODANT BLUE 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. C. such as Modern Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53. I. Modant dye, C.I. I. C. such as Bat Green 1 I. Examples include vat dyes and the like.
These dyes may be appropriately selected according to the desired spectrum of the color filter.
　顔料（Ａ２）としては、特に限定されず公知の顔料を使用することができ、例えば、カラーインデックス（The Society of Dyers and Colourists出版）でピグメントに分類されている顔料が挙げられる。
　顔料としては、例えば、Ｃ．Ｉ．ピグメントイエロー１、３、１２、１３、１４、１５、１６、１７、２０、２４、３１、５３、８３、８６、９３、９４、１０９、１１０、１１７、１２５、１２８、１３７、１３８、１３９、１４７、１４８、１５０、１５３、１５４、１６６、１７３、１９４、２１４などの黄色顔料；
Ｃ．Ｉ．ピグメントオレンジ１３、３１、３６、３８、４０、４２、４３、５１、５５、５９、６１、６４、６５、７１、７３などのオレンジ色の顔料；
Ｃ．Ｉ．ピグメントレッド９、９７、１０５、１２２、１２３、１４４、１４９、１６６、１６８、１７６、１７７、１８０、１９２、２０９、２１５、２１６、２２４、２４２、２５４、２５５、２６４、２６５などの赤色顔料；
Ｃ．Ｉ．ピグメントブルー１５：６、６０などの青色顔料；
Ｃ．Ｉ．ピグメントバイオレット１、１９、２３、２９、３２、３６、３８などのバイオレット色顔料；
Ｃ．Ｉ．ピグメントグリーン７、３６、５８などの緑色顔料；
Ｃ．Ｉ．ピグメントブラウン２３、２５などのブラウン色顔料；
Ｃ．Ｉ．ピグメントブラック１、７などの黒色顔料等が挙げられる。 The pigment (A2) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and the like;
C. I. Pigment Blue 15:6, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment Brown 23, 25 and other brown pigments;
C. I. Pigment Black 1 and 7 and the like black pigments and the like.
　顔料は、必要に応じて、ロジン処理、酸性基又は塩基性基が導入された顔料誘導体等を用いた表面処理、高分子化合物等による顔料表面へのグラフト処理、硫酸微粒化法等による微粒化処理、又は不純物を除去するための有機溶剤や水等による洗浄処理、イオン性不純物のイオン交換法等による除去処理等が施されていてもよい。
　顔料は、粒径が均一であることが好ましい。顔料分散剤を含有させて分散処理を行うことで、顔料が溶液中で均一に分散した状態の顔料分散液を得ることができる。 The pigment may be rosin treated, surface treated with a pigment derivative having an acidic group or a basic group introduced therein, grafted on the surface of the pigment with a polymer compound, or atomized by a sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a treatment for removing ionic impurities by an ion exchange method, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out the dispersion treatment by incorporating the pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.
　前記の顔料分散剤としては、例えば、カチオン系、アニオン系、ノニオン系、両性、ポリエステル系、ポリアミン系、アクリル系等の界面活性剤が挙げられる。これらの顔料分散剤は、単独でも２種以上を組み合わせて用いてもよい。顔料分散剤としては、商品名でＫＰ（信越化学工業（株）製）、フローレン（共栄社化学（株）製）、ソルスパース（ゼネカ（株）製）、ＥＦＫＡ（ＣＩＢＡ社製）、アジスパー（味の素ファインテクノ（株）製）、Ｄｉｓｐｅｒｂｙｋ（ビックケミー社製）などが挙げられる。
　顔料分散剤を用いる場合、その使用量は、顔料（Ａ２）の総量に対して、好ましくは１質量％以上１００質量％以下であり、より好ましくは５質量％以上５０質量％以下である。顔料分散剤の使用量が前記の範囲にあると、均一な分散状態の顔料分散液が得られる傾向がある。 Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more kinds. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Sols Perth (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Azisper (Ajinomoto Fine Co., Ltd.) Techno Co., Ltd., Disperbyk (manufactured by Big Chemie), and the like.
When a pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A2). When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniform dispersed state tends to be obtained.
　着色硬化性樹脂組成物における着色剤（Ａ）の含有率は、固形分の総量に対して、好ましくは０．１質量％以上７０質量％以下であり、より好ましくは０．５質量％以上６０質量％以下であり、さらに好ましくは１質量％以上５０質量％以下である。着色剤（Ａ）の含有率が前記の範囲内であると、カラーフィルタとしたときの色濃度が十分であり、かつ組成物中に樹脂（Ｂ）や重合性化合物（Ｃ）を必要量含有させることができるので、機械的強度が十分なパターンを形成することができる。 The content of the colorant (A) in the colored curable resin composition is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 60% by mass, based on the total amount of solids. It is not more than mass%, more preferably not less than 1 mass% and not more than 50 mass%. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, the pattern having sufficient mechanical strength can be formed.
　ここで、本明細書における「固形分の総量」とは、着色硬化性樹脂組成物の総量から溶剤の含有量を除いた量のことをいう。固形分の総量及びこれに対する各成分の含有量は、例えば、液体クロマトグラフィー又はガスクロマトグラフィーなどの公知の分析手段で測定することができる。 Here, the “total amount of solids” in the present specification means the amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.
　化合物（Ｉ）の含有率は、着色剤（Ａ）の総量中、１質量％以上であることが好ましく、より好ましくは３質量％以上であり、１００質量％であってもよく、９０質量％以下であってもよく、６０質量％以下であってもよく、４０質量％以下であってもよい。 The content of the compound (I) in the total amount of the colorant (A) is preferably 1% by mass or more, more preferably 3% by mass or more, and may be 100% by mass, or 90% by mass. It may be the following, 60% by mass or less, or 40% by mass or less.
＜樹脂（Ｂ）＞
　樹脂は、Ｎ－置換マレイミドに由来する構造単位を含む樹脂を含有する。 <Resin (B)>
The resin contains a resin containing structural units derived from N-substituted maleimides.
　本発明の着色硬化性樹脂組成物が前記樹脂を含有することにより、カラーフィルタの吸光度保持率が向上する。 By containing the resin in the colored curable resin composition of the present invention, the absorbance retention of the color filter is improved.
　Ｎ－置換マレイミドに由来する構造単位は、下記式（Ｂｍ）で表される構造単位であることが好ましい。 The structural unit derived from the N-substituted maleimide is preferably a structural unit represented by the following formula (Bm).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
［式（Ｂｍ）中、Ｒ13は、置換基を有していてもよい炭素数１～１５の１価の飽和炭化水素基、置換基を有していてもよい炭素数６～２０の１価の芳香族炭化水素基、又は置換基を有していてもよい炭素数３～２０の１価の複素環基を表す。］ [In the formula (Bm), R 13 is a monovalent saturated hydrocarbon group having 1 to 15 carbon atoms, which may have a substituent, and 1 having 6 to 20 carbon atoms, which may have a substituent. It represents a valent aromatic hydrocarbon group or a monovalent heterocyclic group having 3 to 20 carbon atoms, which may have a substituent. ]
　炭素数１～１５の１価の飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、ヘキサデシル基及びイコシル基等の炭素数１～１５の直鎖状アルキル基；イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソペンチル基、ネオペンチル基及び２－エチルヘキシル基等の炭素数３～１５の分岐鎖状アルキル基；シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、トリシクロデシル基及びアダマンチル基等の炭素数３～１５の脂環式飽和炭化水素基が挙げられる。 Examples of the monovalent saturated hydrocarbon group having 1 to 15 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group. , Linear alkyl groups having 1 to 15 carbon atoms such as hexadecyl group and icosyl group; carbon numbers such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group 3-15 branched chain alkyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecyl group, adamantyl group, and other alicyclic saturated hydrocarbon groups having 3-15 carbon atoms Are listed.
　該飽和炭化水素基の置換基としては、フッ素原子、塩素原子、ヨウ素等のハロゲン原子；ヒドロキシ基；カルボキシ基；－ＮＲhＲi(Ｒh及びＲiは、それぞれ独立に、水素原子又は炭素数１～２０のアルキル基である)；ニトロ基；メトキシ基、エトキシ基等の炭素数１～１０のアルコキシ基；フェニル基、ナフチル基、アントリル基、フェナントリル基、ビフェニル基等の炭素数６～１５の芳香族炭化水素基；メトキシカルボニル基、エトキシカルボニル基等の炭素数１～１０のアルコキシカルボニル基；下記式（ｍ－１）で表される基等が挙げられる。 Examples of the substituent of the saturated hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom and iodine; a hydroxy group; a carboxy group; —NR h R i (R h and R i are each independently a hydrogen atom or a carbon atom). A C1-C10 alkoxy group such as a methoxy group or an ethoxy group; a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group or the like having a carbon number of 6 to Examples thereof include an aromatic hydrocarbon group of 15; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; and a group represented by the following formula (m-1).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
［式（ｍ－１）中、＊は結合手を表す。］ [In the formula (m-1), * represents a bond. ]
　炭素数６～２０の１価の芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、フェナントリル基、ビフェニル基、ターフェニル基等が挙げられる。 Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group and terphenyl group.
　該芳香族炭化水素基の置換基としては、ヒドロキシ基；カルボキシ基；フッ素原子、塩素原子、ヨウ素原子、臭素原子等のハロゲン原子；メトキシ基、エトキシ基等の炭素数１～６のアルコキシ基；スルファモイル基；メチルスルホニル基等の炭素数１～６のアルキルスルホニル基；メトキシカルボニル基、エトキシカルボニル基等の炭素数１～６のアルコキシカルボニル基；式（ｍ－１）で表される基等が挙げられる。 As the substituent of the aromatic hydrocarbon group, a hydroxy group; a carboxy group; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; Sulfamoyl group; alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group; alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group; group represented by formula (m-1), etc. Can be mentioned.
　Ｒ13が、置換基を有する炭素数１～６の１価の飽和炭化水素基であり、該飽和炭化水素基がアルキル基であり、置換基が炭素数６～１５の芳香族炭化水素基である場合、Ｒ13は炭素数７～２１の１価のアラルキル基を表す。
　炭素数７～２１の１価のアラルキル基としては、ベンジル基、フェネチル基、フェニルプロピル基、ナフチルメチル基及びナフチルエチル基等が挙げられる。 R 13 is a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms having a substituent, the saturated hydrocarbon group is an alkyl group, and the substituent is an aromatic hydrocarbon group having 6 to 15 carbon atoms. In some cases, R 13 represents a monovalent aralkyl group having 7 to 21 carbon atoms.
Examples of the monovalent aralkyl group having 7 to 21 carbon atoms include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and naphthylethyl group.
　該アラルキル基の置換基としては、芳香族炭化水素基の置換基として説明した基と同様のものが挙げられる。 As the substituent of the aralkyl group, the same groups as those described as the substituent of the aromatic hydrocarbon group can be mentioned.
　炭素数３～２０の１価の複素環基としては、チエニル基、ベンゾ［ｂ］チエニル基、ナフト［２，３－ｂ］チエニル基、チアントレニル基、フリル基、ピラニル基、イソベンゾフラニル基、クロメニル基、キサンテニル基、フェノキサチイニル基、２Ｈ－ピロリル基、ピロリル基、イミダゾリル基、ピラゾリル基、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、インドリジニル基、イソインドリル基、３Ｈ－インドリル基、インドリル基、１Ｈ－インダゾリル基、プリニル基、４Ｈ－キノリジニル基、イソキノリル基、キノリル基、フタラジニル基、ナフチリジニル基、キノキサニリル基、キナゾリニル基、シンノリニル基、プテリジニル基、４ａＨ－カルバゾリル基、カルバゾリル基、β－カルボリニル基、フェナントリジニル基、アクリジニル基、ペリミジニル基、フェナントロリニル基、フェナジニル基、フェナルサジニル基、イソチアゾリル基、フェノチアジニル基、イソキサゾリル基、フラザニル基、フェノキサジニル基、イソクロマニル基、クロマニル基、ピロリジニル基、ピロリニル基、イミダゾリジニル基、イミダゾリニル基、ピラゾリジニル基、ピラゾリニル基、ピペリジル基、ピペラジニル基、インドリニル基、イソインドリニル基、キヌクリジニル基、モルホリニル基、チオキサントリル基等が挙げられる。 Examples of the monovalent heterocyclic group having 3 to 20 carbon atoms include thienyl group, benzo[b]thienyl group, naphtho[2,3-b]thienyl group, thianthrenyl group, furyl group, pyranyl group and isobenzofuranyl group. , Chromenyl group, xanthenyl group, phenoxathiynyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, Indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β- Carborinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, flazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group Group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.
　該複素環基の置換基としては、芳香族炭化水素基の置換基として説明した基と同様のものが挙げられる。 Examples of the substituent of the heterocyclic group include the same groups as those described as the substituent of the aromatic hydrocarbon group.
　Ｒ13としては、炭素数３～８の脂環式飽和炭化水素基、炭素数６～１０の１価の芳香族炭化水素基又は炭素数７～１１の１価のアラルキル基であることが好ましい。 R 13 is preferably an alicyclic saturated hydrocarbon group having 3 to 8 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a monovalent aralkyl group having 7 to 11 carbon atoms. ..
　Ｎ－置換マレイミドに由来する構造単位としては、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド、Ｎ－スクシンイミジル－３－マレイミドベンゾエート、Ｎ－スクシンイミジル－４－マレイミドブチレート、Ｎ－スクシンイミジル－６－マレイミドカプロエート、Ｎ－スクシンイミジル－３－マレイミドプロピオネート、Ｎ－（９－アクリジニル）マレイミド等に由来する構造単位が例示され、中でも、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミドに由来する構造単位が好ましい。 Structural units derived from N-substituted maleimides include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl- Structural units derived from 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N-(9-acridinyl)maleimide and the like are exemplified, among which N-phenylmaleimide, N-cyclohexylmaleimide, N- Structural units derived from benzylmaleimide are preferred.
　樹脂（Ｂ）は、アルカリ可溶性樹脂であることが好ましい。アルカリ可溶性を示す樹脂（Ｂ）としては、以下の樹脂［Ｋ１］～［Ｋ６］等が挙げられる。 The resin (B) is preferably an alkali-soluble resin. Examples of the alkali-soluble resin (B) include the following resins [K1] to [K6].
　樹脂［Ｋ１］；不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種の単量体（ａ）（以下「（ａ）」という場合がある）に由来する構造単位と、炭素数２～４の環状エーテル構造とエチレン性不飽和結合とを有する単量体（ｂ）（以下「（ｂ）」という場合がある）に由来する構造単位と、Ｎ－置換マレイミド（ｍ）（以下「（ｍ）」という場合がある）に由来する構造単位からなる共重合体；
　樹脂［Ｋ２］；（ａ）に由来する構造単位と、（ｂ）に由来する構造単位と、（ｍ）に由来する構造単位と、（ａ）と共重合可能な単量体（ｃ）（ただし、（ａ）、（ｂ）及び（ｍ）とは異なる。）（以下「（ｃ）」という場合がある）に由来する構造単位からなる共重合体；
　樹脂［Ｋ３］；（ａ）に由来する構造単位と、（ｍ）に由来する構造単位からなる共重合体；
　樹脂［Ｋ４］；（ａ）に由来する構造単位と、（ｍ）に由来する構造単位と、（ｃ）に由来する構造単位からなる共重合体；
　樹脂［Ｋ５］；（ｂ）に由来する構造単位に（ａ）を付加させた構造単位と、（ｍ）に由来する構造単位とを含む共重合体；
　樹脂［Ｋ６］；（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位と、（ｍ）に由来する構造単位とを含む共重合体。 Resin [K1]; a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides A structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”), and an N-substituted maleimide (m ) (Hereinafter sometimes referred to as “(m)”), a copolymer composed of structural units;
Resin [K2]; a structural unit derived from (a), a structural unit derived from (b), a structural unit derived from (m), and a monomer (c) (copolymerizable with (a) ( However, it is different from (a), (b) and (m).) A copolymer composed of a structural unit derived from (hereinafter sometimes referred to as “(c)”);
Resin [K3]; a copolymer comprising a structural unit derived from (a) and a structural unit derived from (m);
Resin [K4]; a copolymer comprising a structural unit derived from (a), a structural unit derived from (m), and a structural unit derived from (c);
A resin [K5]; a copolymer containing a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (m);
Resin [K6]; A copolymer containing a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride, and a structural unit derived from (m).
　前記（ａ）に由来する構造単位は、（ａ）が有するカルボキシ基又はカルボン酸無水物が未反応のまま残っていることが好ましい。また樹脂［Ｋ１］、［Ｋ２］では、前記（ｂ）に由来する構造単位は、（ｂ）が有する炭素数２～４の環状エーテル構造が未反応のまま残っていることが好ましい。 In the structural unit derived from (a) above, it is preferable that the carboxy group or carboxylic acid anhydride contained in (a) remains unreacted. Further, in the resins [K1] and [K2], it is preferable that the structural unit derived from (b) has a cyclic ether structure having 2 to 4 carbon atoms, which is contained in (b), remaining unreacted.
　（ａ）としては、具体的には、例えば、アクリル酸、メタクリル酸、クロトン酸、ｏ－、ｍ－、ｐ－ビニル安息香酸等の不飽和モノカルボン酸類；
　マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、３－ビニルフタル酸、４－ビニルフタル酸、３，４，５，６－テトラヒドロフタル酸、１，２，３，６－テトラヒドロフタル酸、ジメチルテトラヒドロフタル酸、１，４－シクロヘキセンジカルボン酸等の不飽和ジカルボン酸類；
　メチル－５－ノルボルネン－２，３－ジカルボン酸、５－カルボキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－６－メチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－６－エチルビシクロ［２．２．１］ヘプト－２－エン等のカルボキシ基を含有するビシクロ不飽和化合物類；
　無水マレイン酸、シトラコン酸無水物、イタコン酸無水物、３－ビニルフタル酸無水物、４－ビニルフタル酸無水物、３，４，５，６－テトラヒドロフタル酸無水物、１，２，３，６－テトラヒドロフタル酸無水物、ジメチルテトラヒドロフタル酸無水物、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン無水物等の不飽和ジカルボン酸類無水物；
　こはく酸モノ〔２－（メタ）アクリロイルオキシエチル〕、フタル酸モノ〔２－（メタ）アクリロイルオキシエチル〕等の２価以上の多価カルボン酸の不飽和モノ〔（メタ）アクリロイルオキシアルキル〕エステル類；
　α－（ヒドロキシメチル）アクリル酸のような、同一分子中にヒドロキシ基及びカルボキシ基を含有する不飽和アクリレート類等が挙げられる。
　これらのうち、共重合反応性の点や得られる樹脂のアルカリ水溶液への溶解性の点から、アクリル酸、メタクリル酸、無水マレイン酸等が好ましい。 Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;
Unsaturated mono[(meth)acryloyloxyalkyl]esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution.
　（ｂ）は、例えば、炭素数２～４の環状エーテル構造（例えば、オキシラン環、オキセタン環及びテトラヒドロフラン環からなる群から選ばれる少なくとも１種）とエチレン性不飽和結合とを有する重合性化合物をいう。（ｂ）は、炭素数２～４の環状エーテルと（メタ）アクリロイルオキシ基とを有する単量体が好ましい。
　尚、本明細書において、「（メタ）アクリル酸」とは、アクリル酸及びメタクリル酸よりなる群から選ばれる少なくとも１種を表す。「（メタ）アクリロイル」及び「（メタ）アクリレート」等の表記も、同様の意味を有する。 (B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
In addition, in this specification, "(meth)acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid. The notations such as “(meth)acryloyl” and “(meth)acrylate” have the same meaning.
　（ｂ）としては、例えば、オキシラニル基とエチレン性不飽和結合とを有する単量体（ｂ１）（以下「（ｂ１）」という場合がある）、オキセタニル基とエチレン性不飽和結合とを有する単量体（ｂ２）（以下「（ｂ２）」という場合がある）、テトラヒドロフリル基とエチレン性不飽和結合とを有する単量体（ｂ３）（以下「（ｂ３）」という場合がある）が挙げられる。 Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), a monomer having an oxetanyl group and an ethylenically unsaturated bond. Examples include a monomer (b2) (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”). To be
　（ｂ１）としては、例えば、直鎖状又は分枝鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－１）（以下「（ｂ１－１）」という場合がある）、脂環式不飽和炭化水素がエポキシ化された構造を有する単量体（ｂ１－２）（以下「（ｂ１－２）」という場合がある）が挙げられる。 Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)” And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).
　（ｂ１－１）としては、グリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート、β－エチルグリシジル（メタ）アクリレート、グリシジルビニルエーテル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、α－メチル－ｏ－ビニルベンジルグリシジルエーテル、α－メチル－ｍ－ビニルベンジルグリシジルエーテル、α－メチル－ｐ－ビニルベンジルグリシジルエーテル、２，３－ビス（グリシジルオキシメチル）スチレン、２，４－ビス（グリシジルオキシメチル）スチレン、２，５－ビス（グリシジルオキシメチル）スチレン、２，６－ビス（グリシジルオキシメチル）スチレン、２，３，４－トリス（グリシジルオキシメチル）スチレン、２，３，５－トリス（グリシジルオキシメチル）スチレン、２，３，６－トリス（グリシジルオキシメチル）スチレン、３，４，５－トリス（グリシジルオキシメチル）スチレン、２，４，６－トリス（グリシジルオキシメチル）スチレン等が挙げられる。 Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p. -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene 2,2-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris (Glycidyloxymethyl)styrene and the like can be mentioned.
　（ｂ１－２）としては、ビニルシクロヘキセンモノオキサイド、１，２－エポキシ－４－ビニルシクロヘキサン（例えば、セロキサイド２０００；（株）ダイセル製）、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート（例えば、サイクロマーＡ４００；（株）ダイセル製）、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート（例えば、サイクロマーＭ１００；（株）ダイセル製）、式（ＢＩ）で表される化合物及び式（ＢＩＩ）で表される化合物等が挙げられる。 Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation, 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by the formula (BI) and a formula (BII) And the like.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
［式（ＢＩ）及び式（ＢＩＩ）中、Ｒe及びＲfは、水素原子、又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
　Ｘe及びＸfは、単結合、＊－Ｒg－、＊－Ｒg－Ｏ－、＊－Ｒg－Ｓ－又は＊－Ｒg－ＮＨ－を表す。
　Ｒgは、炭素数１～６のアルカンジイル基を表す。
　＊は、Ｏとの結合手を表す。］ [In the formulas (BI) and (BII), R e and R f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X e and X f is a single bond, * - R g -, * - R g -O -, * - represents the R g -S- or * -R g -NH-.
R g represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]
　炭素数１～４のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等が挙げられる。
　水素原子がヒドロキシで置換されたアルキル基としては、ヒドロキシメチル基、１－ヒドロキシエチル基、２－ヒドロキシエチル基、１－ヒドロキシプロピル基、２－ヒドロキシプロピル基、３－ヒドロキシプロピル基、１－ヒドロキシ－１－メチルエチル基、２－ヒドロキシ－１－メチルエチル基、１－ヒドロキシブチル基、２－ヒドロキシブチル基、３－ヒドロキシブチル基、４－ヒドロキシブチル基等が挙げられる。
　Ｒe及びＲfとしては、好ましくは水素原子、メチル基、ヒドロキシメチル基、１－ヒドロキシエチル基、２－ヒドロキシエチル基が挙げられ、より好ましくは水素原子、メチル基が挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
Examples of the alkyl group having a hydrogen atom substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group and a 1-hydroxy group. Examples thereof include a 1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.
As R e and R f , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.
　アルカンジイル基としては、メチレン基、エチレン基、プロパン－１，２－ジイル基、プロパン－１，３－ジイル基、ブタン－１，４－ジイル基、ペンタン－１，５－ジイル基、ヘキサン－１，６－ジイル基等が挙げられる。
　Ｘe及びＸfとしては、好ましくは単結合、メチレン基、エチレン基、＊－ＣＨ2－Ｏ－及び＊－ＣＨ2ＣＨ2－Ｏ－が挙げられ、より好ましくは単結合、＊－ＣＨ2ＣＨ2－Ｏ－が挙げられる（＊はＯとの結合手を表す）。 Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group and the like can be mentioned.
Examples of X e and X f include a single bond, a methylene group, an ethylene group, *—CH 2 —O— and *—CH 2 CH 2 —O—, and a more preferred single bond, *—CH 2 CH 2 —O— can be mentioned (* represents a bond with O).
　式（ＢＩ）で表される化合物としては、式（ＢＩ－１）～式（ＢＩ－１５）のいずれかで表される化合物等が挙げられる。中でも、式（ＢＩ－１）、式（ＢＩ－３）、式（ＢＩＩ－５）、式（ＢＩ－７）、式（ＢＩ－９）又は式（ＢＩ－１１）～式（ＢＩ－１５）で表される化合物が好ましく、式（ＢＩ－１）、式（ＢＩ－７）、式（ＢＩ－９）又は式（ＢＩ－１５）で表される化合物がより好ましい。 Examples of the compound represented by the formula (BI) include compounds represented by any of the formulas (BI-1) to (BI-15). Among them, formula (BI-1), formula (BI-3), formula (BII-5), formula (BI-7), formula (BI-9) or formula (BI-11) to formula (BI-15) The compound represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15) is more preferred.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　式（ＢＩＩ）で表される化合物としては、式（ＢＩＩ－１）～式（ＢＩＩ－１５）のいずれかで表される化合物等が挙げられる。中でも、式（ＢＩＩ－１）、式（ＢＩＩ－３）、式（ＢＩＩ－５）、式（ＢＩＩ－７）、式（ＢＩＩ－９）又は式（ＢＩＩ－１１）～式（ＢＩＩ－１５）で表される化合物が好ましく、式（ＢＩＩ－１）、式（ＢＩＩ－７）、式（ＢＩＩ－９）又は式（ＢＩＩ－１５）で表される化合物がより好ましい。 Examples of the compound represented by the formula (BII) include compounds represented by any of the formulas (BII-1) to (BII-15). Among them, formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) to formula (BII-15) The compound represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) or the formula (BII-15) is more preferable.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　式（ＢＩ）で表される化合物及び式（ＢＩＩ）で表される化合物は、それぞれ単独で用いても、２種以上を併用してもよい。式（ＢＩ）で表される化合物及び式（ＢＩＩ）で表される化合物を併用する場合、これらの含有比率〔式（ＢＩ）で表される化合物：式（ＢＩＩ）で表される化合物〕はモル基準で、好ましくは５：９５～９５：５、より好ましくは２０：８０～８０：２０である。 The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination of two or more kinds. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination, the content ratio thereof [the compound represented by the formula (BI): the compound represented by the formula (BII)] is The molar ratio is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.
　（ｂ２）としては、オキセタニル基と（メタ）アクリロイルオキシ基とを有する単量体がより好ましい。（ｂ２）としては、３－メチル－３－メタクリルロイルオキシメチルオキセタン、３－メチル－３－アクリロイルオキシメチルオキセタン、３－エチル－３－メタクリロイルオキシメチルオキセタン、３－エチル－３－アクリロイルオキシメチルオキセタン、３－メチル－３－メタクリロイルオキシエチルオキセタン、３－メチル－３－アクリロイルオキシエチルオキセタン、３－エチル－３－メタクリロイルオキシエチルオキセタン、３－エチル－３－アクリロイルオキシエチルオキセタン等が挙げられる。 As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane. , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and the like.
　（ｂ３）としては、テトラヒドロフリル基と（メタ）アクリロイルオキシ基とを有する単量体がより好ましい。（ｂ３）としては、具体的には、テトラヒドロフルフリルアクリレート（例えば、ビスコートＶ＃１５０、大阪有機化学工業（株）製）、テトラヒドロフルフリルメタクリレート等が挙げられる。 As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.
　（ｂ）としては、得られるカラーフィルタの耐熱性、耐薬品性等の信頼性をより高くすることができる点で、（ｂ１）であることが好ましい。さらに、着色硬化性樹脂組成物の保存安定性が優れるという点で、（ｂ１－２）がより好ましい。 As (b), (b1) is preferable because the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. Further, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.
　（ｃ）としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２－メチルシクロヘキシル（メタ）アクリレート、トリシクロ［５．２．１．０2,6］デカン－８－イル（メタ）アクリレート（当該技術分野では、慣用名として「ジシクロペンタニル（メタ）アクリレート」といわれている。また、「トリシクロデシル（メタ）アクリレート」という場合がある。）、トリシクロ［５．２．１．０2,6］デセン－８－イル（メタ）アクリレート（当該技術分野では、慣用名として「ジシクロペンテニル（メタ）アクリレート」といわれている。）、ジシクロペンタニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、アリル（メタ）アクリレート、プロパルギル（メタ）アクリレート、フェニル（メタ）アクリレート、ナフチル（メタ）アクリレート、ベンジル（メタ）アクリレート等の（メタ）アクリル酸エステル類；
　２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシ基含有（メタ）アクリル酸エステル類；
　マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル等のジカルボン酸ジエステル；
　ビシクロ［２．２．１］ヘプト－２－エン、５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシメチルビシクロ［２．２．１］ヘプト－２－エン、５－（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５－メトキシビシクロ［２．２．１］ヘプト－２－エン、５－エトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジヒドロキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジ（ヒドロキシメチル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ジ（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ジメトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジエトキシビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシ－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシ－５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシメチル－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－ｔｅｒｔ－ブトキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－シクロヘキシルオキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－フェノキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５，６－ビス（ｔｅｒｔ－ブトキシカルボニル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ビス（シクロヘキシルオキシカルボニル）ビシクロ［２．２．１］ヘプト－２－エン等のビシクロ不飽和化合物類；
　スチレン、α－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ビニルトルエン、ｐ－メトキシスチレン、アクリロニトリル、メタクリロニトリル、塩化ビニル、塩化ビニリデン、アクリルアミド、メタクリルアミド、酢酸ビニル、１，３－ブタジエン、イソプレン、２，３－ジメチル－１，３－ブタジエン等が挙げられる。 Examples of (c) include methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, sec-butyl(meth)acrylate, tert-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, Dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2, 6 ] Decane-8-yl(meth)acrylate (in the art, it is commonly called “dicyclopentanyl(meth)acrylate”. It may also be called “tricyclodecyl(meth)acrylate”. .), tricyclo[5.2.1.0 2,6 ]decen-8-yl(meth)acrylate (known in the art as a trivial name "dicyclopentenyl (meth)acrylate"), Dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth) ) (Meth)acrylic acid esters such as acrylates;
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and itaconic acid diethyl;
Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2] .1]Hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy -5-Methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2 1.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyl) Bicyclo unsaturated compounds such as oxycarbonyl)bicyclo[2.2.1]hept-2-ene;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
　樹脂［Ｋ１］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ１］を構成する全構造単位中、
（ａ）に由来する構造単位；２～５５モル％
（ｂ）に由来する構造単位；２～８５モル％
（ｍ）に由来する構造単位；１～６５モル％
であることが好ましく、
（ａ）に由来する構造単位；５～５０モル％
（ｂ）に由来する構造単位；５～７０モル％
（ｍ）に由来する構造単位；５～６０モル％
であることがより好ましい。
　樹脂［Ｋ１］の構造単位の比率が、上記の範囲にあると、着色硬化性樹脂組成物から得られるカラーフィルタの吸光保持率をより一層向上できる。 In the resin [K1], the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K1],
Structural unit derived from (a); 2-55 mol%
Structural unit derived from (b); 2-85 mol%
Structural unit derived from (m); 1 to 65 mol%
Is preferred,
Structural unit derived from (a); 5 to 50 mol%
Structural unit derived from (b); 5-70 mol%
Structural unit derived from (m); 5 to 60 mol%
Is more preferable.
When the ratio of the structural unit of the resin [K1] is within the above range, the absorption retention of the color filter obtained from the colored curable resin composition can be further improved.
　樹脂［Ｋ１］は、例えば、文献「高分子合成の実験法」（大津隆行著　発行所（株）化学同人　第１版第１刷　１９７２年３月１日発行）に記載された方法及び当該文献に記載された引用文献を参考にして製造することができる。 The resin [K1] is, for example, the method described in “Experimental Method for Polymer Synthesis” (written by Takayuki Otsu, published by Kagaku Doujin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the literature. It can be manufactured by referring to the cited document described in.
　具体的には、（ａ）、（ｂ）及び（ｍ）の所定量、重合開始剤及び溶剤等を反応容器中に入れて、例えば、窒素により酸素を置換することにより、脱酸素雰囲気にし、撹拌しながら、加熱及び保温する方法が挙げられる。なお、ここで用いられる重合開始剤及び溶剤等は、特に限定されず、当該分野で通常使用されているものを使用することができる。例えば、重合開始剤としては、アゾ化合物（２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）等）や有機過酸化物（ベンゾイルペルオキシド等）が挙げられ、溶剤としては、各モノマーを溶解するものであればよく、本発明の着色硬化性樹脂組成物の溶剤（Ｅ）として後述する溶剤等が挙げられる。 Specifically, a predetermined amount of (a), (b) and (m), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and oxygen is replaced by, for example, nitrogen to create a deoxygenated atmosphere, Examples of the method include heating and keeping heat while stirring. The polymerization initiator, solvent and the like used here are not particularly limited, and those usually used in the relevant field can be used. For example, as a polymerization initiator, an azo compound (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) The solvent may be any solvent that can dissolve each monomer, and examples thereof include the solvent described below as the solvent (E) of the colored curable resin composition of the present invention.
　なお、得られた共重合体は、反応後の溶液をそのまま使用してもよいし、濃縮あるいは希釈した溶液を使用してもよいし、再沈殿等の方法で固体（粉体）として取り出したものを使用してもよい。特に、この重合の際に溶剤として、本発明の着色硬化性樹脂組成物に含まれる溶剤を使用することにより、反応後の溶液をそのまま本発明の着色硬化性樹脂組成物の調製に使用することができるため、本発明の着色硬化性樹脂組成物の製造工程を簡略化することができる。 The obtained copolymer may be used as the solution after the reaction as it is, or may be used as a concentrated or diluted solution, or taken out as a solid (powder) by a method such as reprecipitation. You may use the thing. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.
　樹脂［Ｋ２］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ２］を構成する全構造単位中、
（ａ）に由来する構造単位；２～５５モル％
（ｂ）に由来する構造単位；２～８５モル％
（ｍ）に由来する構造単位；１～６５モル％
（ｃ）に由来する構造単位；１～５０モル％
であることが好ましく、
（ａ）に由来する構造単位；５～５０モル％
（ｂ）に由来する構造単位；５～７０モル％
（ｍ）に由来する構造単位；５～６０モル％
（ｃ）に由来する構造単位；２～４０モル％
であることがより好ましい。
　樹脂［Ｋ２］の構造単位の比率が、上記の範囲にあると、着色硬化性樹脂組成物から得られるカラーフィルタの吸光保持率をより一層向上できる。 In the resin [K2], the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K2],
Structural unit derived from (a); 2-55 mol%
Structural unit derived from (b); 2-85 mol%
Structural unit derived from (m); 1 to 65 mol%
Structural unit derived from (c); 1 to 50 mol%
Is preferred,
Structural unit derived from (a); 5 to 50 mol%
Structural unit derived from (b); 5-70 mol%
Structural unit derived from (m); 5 to 60 mol%
Structural unit derived from (c); 2 to 40 mol%
Is more preferable.
When the ratio of the structural unit of the resin [K2] is within the above range, the absorption retention of the color filter obtained from the colored curable resin composition can be further improved.
　樹脂［Ｋ２］は、例えば、樹脂［Ｋ１］の製造方法として記載した方法と同様に製造することができる。 The resin [K2] can be manufactured, for example, in the same manner as the method described as the method for manufacturing the resin [K1].
　樹脂［Ｋ３］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ３］を構成する全構造単位中、
（ａ）に由来する構造単位；２～６０モル％
（ｍ）に由来する構造単位；４０～９８モル％
であることが好ましく、
（ａ）に由来する構造単位；１０～５５モル％
（ｍ）に由来する構造単位；４５～９０モル％
であることがより好ましい。
　樹脂［Ｋ３］は、例えば、樹脂［Ｋ１］の製造方法として記載した方法と同様に製造することができる。 In the resin [K3], the ratio of the structural units derived from each is as follows:
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (m); 40 to 98 mol%
Is preferred,
Structural unit derived from (a); 10 to 55 mol%
Structural unit derived from (m); 45 to 90 mol%
Is more preferable.
The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].
　樹脂［Ｋ４］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ１］を構成する全構造単位中、
（ａ）に由来する構造単位；２～５５モル％
（ｍ）に由来する構造単位；１～６５モル％
（ｃ）に由来する構造単位；１～５０モル％
であることが好ましく、
（ａ）に由来する構造単位；５～５０モル％
（ｍ）に由来する構造単位；５～６０モル％
（ｃ）に由来する構造単位；２～４０モル％
であることがより好ましい。
　樹脂［Ｋ４］は、例えば、樹脂［Ｋ１］の製造方法として記載した方法と同様に製造することができる。 In the resin [K4], the ratio of the structural units derived from each is such that in all the structural units constituting the resin [K1],
Structural unit derived from (a); 2-55 mol%
Structural unit derived from (m); 1 to 65 mol%
Structural unit derived from (c); 1 to 50 mol%
Is preferred,
Structural unit derived from (a); 5 to 50 mol%
Structural unit derived from (m); 5 to 60 mol%
Structural unit derived from (c); 2 to 40 mol%
Is more preferable.
The resin [K4] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].
　樹脂［Ｋ５］は、第一段階として、上述した樹脂［Ｋ１］の製造方法と同様にして、（ｂ）と（ｍ）との共重合体を得る。上記と同様に、得られた共重合体は、反応後の溶液をそのまま使用してもよいし、濃縮あるいは希釈した溶液を使用してもよいし、再沈殿等の方法で固体（粉体）として取り出したものを使用してもよい。
　（ｂ）及び（ｍ）に由来する構造単位の比率は、前記の共重合体を構成する全構造単位の合計モル数に対して、それぞれ、
（ｂ）に由来する構造単位；５～９５モル％
（ｍ）に由来する構造単位；５～９５モル％
であることが好ましく、
（ｂ）に由来する構造単位；１０～９０モル％
（ｍ）に由来する構造単位；１０～９０モル％
であることがより好ましい。 As the resin [K5], in the first step, a copolymer of (b) and (m) is obtained in the same manner as in the method for producing the resin [K1]. In the same manner as above, the obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratios of the structural units derived from (b) and (m) are, respectively, with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol%
Structural unit derived from (m); 5-95 mol%
Is preferred,
Structural unit derived from (b); 10 to 90 mol%
Structural unit derived from (m); 10 to 90 mol%
Is more preferable.
　次に、フラスコ内を空気雰囲気にして、（ｂ）と（ｍ）との共重合体、（ａ）、カルボン酸又はカルボン酸無水物と環状エーテルとの反応触媒（例えばトリス（ジメチルアミノメチル）フェノール等）及び重合禁止剤（例えばハイドロキノン等）等をフラスコ内に入れて、例えば、６０～１３０℃で、１～１０時間反応させ、（ｂ）と（ｍ）との共重合体が有する（ｂ）に由来する環状エーテルに、（ａ）が有するカルボン酸又はカルボン酸無水物を反応させることにより、樹脂［Ｋ５］を得ることができる。
　前記の共重合体に反応させる（ａ）の使用量は、（ｂ）１００モルに対して、５～８０モルが好ましい。環状エーテルの反応性が高く、未反応の（ｂ）が残存しにくいことから、樹脂［Ｋ５］に用いる（ｂ）としては（ｂ１）が好ましい。
前記反応触媒の使用量は、（ａ）、（ｂ）及び（ｍ）の合計量１００質量部に対して０．００１～５質量部が好ましい。前記重合禁止剤の使用量は、（ａ）、（ｂ）及び（ｍ）の合計量１００質量部に対して０．００１～５質量部が好ましい。
　仕込方法、反応温度及び時間等の反応条件は、製造設備や重合による発熱量等を考慮して適宜調整することができる。なお、重合条件と同様に、製造設備や重合による発熱量等を考慮し、仕込方法や反応温度を適宜調整することができる。 Next, the inside of the flask is made into an air atmosphere, and the reaction catalyst of the copolymer of (b) and (m), (a), carboxylic acid or carboxylic acid anhydride and cyclic ether (eg tris(dimethylaminomethyl)). (Phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are put in a flask and reacted at, for example, 60 to 130° C. for 1 to 10 hours to obtain a copolymer of (b) and (m) ( The resin [K5] can be obtained by reacting the cyclic ether derived from b) with the carboxylic acid or carboxylic acid anhydride contained in (a).
The amount of (a) used to react with the above copolymer is preferably 5 to 80 mol per 100 mol of (b). (B1) is preferable as (b) used in the resin [K5] because the reactivity of the cyclic ether is high and the unreacted (b) hardly remains.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (m). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (m).
Reaction conditions such as a charging method, reaction temperature and time can be appropriately adjusted in consideration of production equipment, the amount of heat generated by polymerization and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization.
　樹脂［Ｋ６］は、樹脂［Ｋ５］に、さらにカルボン酸無水物を反応させた樹脂である。
環状エーテルとカルボン酸又はカルボン酸無水物との反応により発生するヒドロキシ基に、カルボン酸無水物を反応させる。
　カルボン酸無水物としては、無水マレイン酸、シトラコン酸無水物、イタコン酸無水物、３－ビニルフタル酸無水物、４－ビニルフタル酸無水物、３，４，５，６－テトラヒドロフタル酸無水物、１，２，３，６－テトラヒドロフタル酸無水物、ジメチルテトラヒドロフタル酸無水物、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン無水物等が挙げられる。カルボン酸無水物の使用量は、（ａ）の使用量１モルに対して、０．５～１モルが好ましい。 The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride.
The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction between the cyclic ether and the carboxylic acid or the carboxylic acid anhydride.
Examples of carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and 1 2,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mol per 1 mol of the amount used of (a).
　樹脂（Ｂ）としては、具体的に、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－フェニルマレイミド共重合体、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド共重合体、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－ベンジルマレイミド共重合体、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸／Ｎ－フェニルマレイミド共重合体、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド共重合体、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸／Ｎ－ベンジルマレイミド共重合体等の樹脂［Ｋ１］；
グリシジル（メタ）アクリレート／ベンジル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－フェニルマレイミド共重合体、グリシジル（メタ）アクリレート／ベンジル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド共重合体、グリシジル（メタ）アクリレート／ベンジル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－ベンジルマレイミド共重合、グリシジル（メタ）アクリレート／スチレン／（メタ）アクリル酸／Ｎ－フェニルマレイミド共重合体、グリシジル（メタ）アクリレート／スチレン／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド共重合体、グリシジル（メタ）アクリレート／スチレン／（メタ）アクリル酸／Ｎ－ベンジルマレイミド共重合、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸／Ｎ－フェニルマレイミド／２－ヒドロキシエチル（メタ）アクリレート共重合体、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド／２－ヒドロキシエチル（メタ）アクリレート共重合体、３，４－エポキシトリシクロ［５．２．１．０2,6］デシルアクリレート／（メタ）アクリル酸／Ｎ－ベンジルマレイミド／２－ヒドロキシエチル（メタ）アクリレート共重合体、３－メチル－３－（メタ）アクリルロイルオキシメチルオキセタン／（メタ）アクリル酸／スチレン／Ｎ－フェニルマレイミド共重合体、３－メチル－３－（メタ）アクリルロイルオキシメチルオキセタン／（メタ）アクリル酸／スチレン／Ｎ－シクロヘキシルマレイミド共重合体、３－メチル－３－（メタ）アクリルロイルオキシメチルオキセタン／（メタ）アクリル酸／スチレン／Ｎ－ベンジルマレイミド共重合体等の樹脂［Ｋ２］；
Ｎ－フェニルマレイミド／（メタ）アクリル酸共重合体、Ｎ－シクロヘキシルマレイミド／（メタ）アクリル酸共重合体、Ｎ－ベンジルマレイミド／（メタ）アクリル酸共重合体等の樹脂［Ｋ３］；
ベンジル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－フェニルマレイミド共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－ベンジルマレイミド共重合、スチレン／（メタ）アクリル酸／Ｎ－フェニルマレイミド共重合体、スチレン／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド共重合体、スチレン／（メタ）アクリル酸／Ｎ－ベンジルマレイミド共重合、（メタ）アクリル酸／Ｎ－フェニルマレイミド／２－ヒドロキシエチル（メタ）アクリレート共重合体、（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド／２－ヒドロキシエチル（メタ）アクリレート共重合体、（メタ）アクリル酸／Ｎ－ベンジルマレイミド／２－ヒドロキシエチル（メタ）アクリレート共重合体等の樹脂［Ｋ４］；
Ｎ－フェニルマレイミド／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂、Ｎ－シクロヘキシルマレイミド／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂、Ｎ－ベンジルマレイミド／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂等の樹脂［Ｋ５］；
Ｎ－フェニルマレイミド／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂にさらにテトラヒドロフタル酸無水物を反応させた樹脂、Ｎ－シクロヘキシルマレイミド／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂にさらにテトラヒドロフタル酸無水物を反応させた樹脂、Ｎ－ベンジルマレイミド／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂にさらにテトラヒドロフタル酸無水物を反応させた樹脂等の樹脂［Ｋ６］等が挙げられる。
　中でも、樹脂（Ｂ）としては、樹脂［Ｋ１］～樹脂［Ｋ４］が好ましく、樹脂［Ｋ１］及び樹脂［Ｋ２］がより好ましい。 Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid/N-phenylmaleimide copolymer and 3,4-epoxycyclohexylmethyl (meth)acrylate/( (Meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid/N-benzylmaleimide copolymer, 3,4-epoxytricyclo[5.2] .1.0 2,6 ]decyl acrylate/(meth)acrylic acid/N-phenylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate/(meth) Resins such as acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate/(meth)acrylic acid/N-benzylmaleimide copolymer K1];
Glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid/N-phenylmaleimide copolymer, glycidyl(meth)acrylate/benzyl(meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer Coalescence, glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid/N-benzylmaleimide copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid/N-phenylmaleimide copolymer, glycidyl (Meth)acrylate/styrene/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid/N-benzylmaleimide copolymer, 3,4-epoxytricyclo[ 5.2.1.0 2,6 ]decyl acrylate/(meth)acrylic acid/N-phenyl maleimide/2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1] .0 2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexyl maleimide/2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate/(meth)acrylic acid/N-benzyl maleimide/2-hydroxyethyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyl oxetane/(meth)acrylic acid/styrene/ N-phenylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyl Resin [K2] such as oxymethyloxetane/(meth)acrylic acid/styrene/N-benzylmaleimide copolymer;
Resins such as N-phenylmaleimide/(meth)acrylic acid copolymer, N-cyclohexylmaleimide/(meth)acrylic acid copolymer, N-benzylmaleimide/(meth)acrylic acid copolymer [K3];
Benzyl (meth)acrylate/(meth)acrylic acid/N-phenylmaleimide copolymer, benzyl(meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, benzyl(meth)acrylate/(meth)acrylic Acid/N-benzylmaleimide copolymer, styrene/(meth)acrylic acid/N-phenylmaleimide copolymer, styrene/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, styrene/(meth)acrylic acid/N -Benzylmaleimide copolymerization, (meth)acrylic acid/N-phenylmaleimide/2-hydroxyethyl(meth)acrylate copolymer, (meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl(meth)acrylate copolymer A resin [K4] such as a combination, a (meth)acrylic acid/N-benzylmaleimide/2-hydroxyethyl(meth)acrylate copolymer;
N-phenylmaleimide/glycidyl(meth)acrylate copolymer reacted with (meth)acrylic acid, N-cyclohexylmaleimide/glycidyl(meth)acrylate copolymer reacted with (meth)acrylic acid Resin [K5] such as a resin, a resin obtained by reacting a (meth)acrylic acid with a copolymer of N-benzylmaleimide/glycidyl (meth)acrylate;
Resin of N-phenylmaleimide/glycidyl (meth)acrylate copolymer reacted with (meth)acrylic acid and tetrahydrophthalic anhydride is further reacted, N-cyclohexylmaleimide/glycidyl (meth)acrylate copolymer A resin obtained by reacting a polymer with (meth)acrylic acid was further reacted with a tetrahydrophthalic anhydride, and a copolymer of N-benzylmaleimide/glycidyl (meth)acrylate was reacted with (meth)acrylic acid. The resin [K6] such as a resin obtained by further reacting the resin with tetrahydrophthalic anhydride may be mentioned.
Among them, as the resin (B), resins [K1] to resin [K4] are preferable, and resins [K1] and resin [K2] are more preferable.
　樹脂（Ｂ）のポリスチレン換算の重量平均分子量は、好ましくは３，０００～１００，０００であり、より好ましくは５，０００～５０，０００であり、さらに好ましくは５，０００～３０，０００である。分子量が前記の範囲内にあると、カラーフィルタの硬度が向上し、残膜率が高く、未露光部の現像液に対する溶解性が良好で、着色パターンの解像度が向上する傾向がある。 The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. .. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed area in the developing solution is good, and the resolution of the colored pattern tends to be improved.
　樹脂（Ｂ）の分散度［重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）］は、好ましくは１．１～６であり、より好ましくは１．２～４である。 The dispersity [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
　樹脂（Ｂ）の酸価は、固形分換算で、好ましくは７０ｍｇ－ＫＯＨ／ｇ以上、より好ましくは９０ｍｇ－ＫＯＨ／ｇ以上、さらに好ましくは１１０ｍｇ－ＫＯＨ／ｇ以上であり、好ましくは２２０ｍｇ－ＫＯＨ／ｇ以下、より好ましくは２１０ｍｇ－ＫＯＨ／ｇ以下、さらに好ましくは２００ｍｇ－ＫＯＨ／ｇ以下である。ここで酸価は樹脂（Ｂ）１ｇを中和するために必要な水酸化カリウムの量（ｍｇ）として測定される値であり、例えば水酸化カリウム水溶液を用いて滴定することにより求めることができる。 The acid value of the resin (B) is, in terms of solid content, preferably 70 mg-KOH/g or more, more preferably 90 mg-KOH/g or more, further preferably 110 mg-KOH/g or more, preferably 220 mg-KOH. /G or less, more preferably 210 mg-KOH/g or less, still more preferably 200 mg-KOH/g or less. Here, the acid value is a value measured as an amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by, for example, titration using an aqueous potassium hydroxide solution. ..
　樹脂（Ｂ）の含有率は、固形分の総量に対して、好ましくは７～８０質量％であり、より好ましくは１３～７５質量％であり、さらに好ましくは１７～６５質量％である。樹脂（Ｂ）の含有率が、前記の範囲内にあると、着色パターンが形成でき、また着色パターンの解像度及び残膜率が向上する傾向がある。 The content of the resin (B) is preferably 7 to 80% by mass, more preferably 13 to 75% by mass, and further preferably 17 to 65% by mass, based on the total solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to be improved.
　樹脂（Ｂ）の含有量は、樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、好ましくは１０質量部以上９５質量部以下であり、より好ましくは２０質量部以上９０質量部以下であり、さらに好ましくは３０質量部以上８５質量部以下である。樹脂（Ｂ）の含有量が上記範囲内にあると、得られるカラーフィルタの吸光度保持率がさらに向上する。
　また樹脂（Ｂ）の含有量が、樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、５５質量部以上９５質量部以下、好ましくは６０質量部以上９０質量部以下であることも好ましい。樹脂（Ｂ）の含有量が前記範囲にあると、得られるカラーフィルタの吸光度保持率が顕著に向上する。
　樹脂（Ｂ）の含有量が、樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、１０質量部以上６０質量部以下、好ましくは２０質量部以上５５質量部以下である場合、得られるカラーフィルタの吸光度保持率と明度が向上する。 The content of the resin (B) is preferably 10 parts by mass or more and 95 parts by mass or less, more preferably 20 parts by mass or more with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). The amount is 90 parts by mass or less, and more preferably 30 parts by mass or more and 85 parts by mass or less. When the content of the resin (B) is within the above range, the absorbance retention of the obtained color filter is further improved.
Further, the content of the resin (B) is 55 parts by mass or more and 95 parts by mass or less, preferably 60 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Is also preferable. When the content of the resin (B) is within the above range, the absorbance retention of the obtained color filter is remarkably improved.
The content of the resin (B) is 10 parts by mass or more and 60 parts by mass or less, preferably 20 parts by mass or more and 55 parts by mass or less based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). In some cases, the absorbance retention and brightness of the resulting color filter are improved.
＜重合性化合物（Ｃ）＞
　重合性化合物（Ｃ）は、重合開始剤（Ｄ）から発生した活性ラジカル及び／又は酸によって重合しうる化合物であり、例えば、重合性のエチレン性不飽和結合を有する化合物が挙げられ、好ましくは（メタ）アクリル酸エステル化合物である。 <Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenic unsaturated bond, and preferably It is a (meth)acrylic acid ester compound.
　中でも、重合性化合物（Ｃ）は、エチレン性不飽和結合を３つ以上有する重合性化合物であることが好ましい。このような重合性化合物としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールオクタ（メタ）アクリレート、トリペンタエリスリトールヘプタ（メタ）アクリレート、テトラペンタエリスリトールデカ（メタ）アクリレート、テトラペンタエリスリトールノナ（メタ）アクリレート、トリス（２－（メタ）アクリロイルオキシエチル）イソシアヌレート、エチレングリコール変性ペンタエリスリトールテトラ（メタ）アクリレート、エチレングリコール変性ジペンタエリスリトールヘキサ（メタ）アクリレート、プロピレングリコール変性ペンタエリスリトールテトラ（メタ）アクリレート、プロピレングリコール変性ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールテトラ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレートが挙げられる。
　中でも、ジペンタエリスリトールペンタ（メタ）アクリレート及びジペンタエリスリトールヘキサ（メタ）アクリレートが好ましい。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( (Meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl ) Isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, Examples thereof include caprolactone-modified pentaerythritol tetra(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate.
Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.
　重合性化合物（Ｃ）の含有率は、固形分の総量に対して、１～６５質量％であることが好ましく、より好ましくは５～６０質量％であり、さらに好ましくは１０～５５質量％である。重合性化合物（Ｃ）の含有率が、前記の範囲内にあると、着色パターン形成時の残膜率及びカラーフィルタの耐薬品性が向上する傾向がある。 The content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, further preferably 10 to 55% by mass, based on the total amount of the solid content. is there. When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.
＜重合開始剤（Ｄ）＞
　重合開始剤（Ｄ）は、光や熱の作用により活性ラジカル、酸等を発生し、重合を開始しうる化合物であれば特に限定されることなく、公知の重合開始剤を用いることができる。
活性ラジカルを発生する重合開始剤としては、例えば、Ｏ－アシルオキシム化合物、アルキルフェノン化合物、トリアジン化合物、アシルホスフィンオキサイド化合物及びビイミダゾール化合物が挙げられる。 <Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of polymerization initiators that generate active radicals include O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.
　前記Ｏ－アシルオキシム化合物としては、例えば、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）ブタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロペンチルプロパン－１－オン－２－イミン、Ｎ－アセチルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－１－オン－２－イミン等のジフェニルスルフィド骨格を有するＯ－アシルオキシム化合物；Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－｛２－メチル－４－（３，３－ジメチル－２，４－ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－イミン、Ｎ－ベンゾイルオキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－オン－２－イミン等のカルバゾール骨格を有するＯ－アシルオキシム化合物；１－［７－（２－メチルベンゾイル）－９，９－ジプロピル－９Ｈ－フルオレン－２－イル］エタノン　Ｏ-アセチルオキシム等のフルオレン骨格を有するＯ－アシルオキシム化合物；等が挙げられる。イルガキュア（登録商標）ＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ－１９１９（ＡＤＥＫＡ社製）、ＤＦＩ－０９１（ダイトーケミックス株式会社製）等の市販品を用いてもよい。中でも、Ｏ－アシルオキシム化合物は、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－アセチルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－１－オン－２－イミン、Ｎ－アセトキシ－１－［９－エチル－６－｛２－メチル－４－（３，３－ジメチル－２，４－ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝－９Ｈ－カルバゾール－３－イル］エタン－１－イミン及び１－［７－（２－メチルベンゾイル）－９，９－ジプロピル－９Ｈ－フルオレン－２－イル］エタノン　Ｏ-アセチルオキシムからなる群から選ばれる少なくとも１種が好ましい。これらのＯ－アシルオキシム化合物であると、高明度なカラーフィルタが得られる傾向にある。 Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane. 1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl )-3-Cyclohexylpropan-1-one-2-imine and other O-acyl oxime compounds having a diphenyl sulfide skeleton; N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) Benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane Carbazoles such as 1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine O-acyl oxime compound having a skeleton; 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acyl oxime having a fluorene skeleton such as O-acetyloxime Compounds; and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA), and DFI-091 (manufactured by Daito Chemix Co., Ltd.) may be used. Among them, the O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3- Cyclohexylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) Benzoyl}-9H-carbazol-3-yl]ethane-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime At least one selected from the group is preferable. With these O-acyl oxime compounds, a color filter with high brightness tends to be obtained.
　前記アルキルフェノン化合物としては、例えば、２－メチル－２－モルホリノ－１－（４－メチルスルファニルフェニル）プロパン－１－オン、２－ジメチルアミノ－１－（４－モルホリノフェニル）－２－ベンジルブタン－１－オン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］ブタン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－〔４－（２－ヒドロキシエトキシ）フェニル〕プロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－（４－イソプロペニルフェニル）プロパン－１－オンのオリゴマー、α，α－ジエトキシアセトフェノン、ベンジルジメチルケタール等が挙げられる。イルガキュア（登録商標）３６９、９０７、３７９（以上、ＢＡＳＦ社製）等の市販品を用いてもよい。 Examples of the alkylphenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane. 1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl Examples thereof include oligomers of 1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethylketal. Commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (all manufactured by BASF) may be used.
　前記トリアジン化合物としては、例えば、２，４－ビス（トリクロロメチル）－６－（４－メトキシフェニル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－（４－メトキシナフチル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－ピペロニル－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－(４－メトキシスチリル)－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（５－メチルフラン－２－イル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（フラン－２－イル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（４－ジエチルアミノ－２－メチルフェニル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（３，４－ジメトキシフェニル）エテニル〕－１，３，５－トリアジン等が挙げられる。 Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-(4- Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy Styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4 -Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-Methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. Are listed.
　前記アシルホスフィンオキサイド化合物としては、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド等が挙げられる。イルガキュア（登録商標）８１９（ＢＡＳＦ社製）等の市販品を用いてもよい。 Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. A commercially available product such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.
　前記ビイミダゾール化合物としては、例えば、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（２，３－ジクロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール（例えば、特開平６－７５３７２号公報、特開平６－７５３７３号公報等参照。）、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（アルコキシフェニル）ビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（ジアルコキシフェニル）ビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（トリアルコキシフェニル）ビイミダゾール（例えば、特公昭４８－３８４０３号公報、特開昭６２－１７４２０４号公報等参照。）、４，４’，５，５’－位のフェニル基がカルボアルコキシ基により置換されているビイミダゾール化合物（例えば、特開平７－１０９１３号公報等参照）等が挙げられる。 Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3-dichlorophenyl)- 4,4′,5,5′-Tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis(2-chlorophenyl)-4 ,4',5,5'-Tetraphenylbiimidazole,2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole,2,2'-bis (2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(tri Alkoxyphenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4′,5,5′-position is substituted with a carboalkoxy group. And the like (see, for example, JP-A-7-10913).
　酸を発生する重合開始剤としては、例えば、４－ヒドロキシフェニルジメチルスルホニウムｐ－トルエンスルホナート、４－ヒドロキシフェニルジメチルスルホニウムヘキサフルオロアンチモネート、４－アセトキシフェニルジメチルスルホニウムｐ－トルエンスルホナート、４－アセトキシフェニル・メチル・ベンジルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムｐ－トルエンスルホナート、トリフェニルスルホニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムｐ－トルエンスルホナート、ジフェニルヨードニウムヘキサフルオロアンチモネート等のオニウム塩類や、ニトロベンジルトシレート類、ベンゾイントシレート類等が挙げられる。 Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate and 4-acetoxy. Onium salts such as phenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate and nitrobenzyl Examples thereof include tosylates and benzoin tosylates.
　さらに重合開始剤（Ｄ）としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン化合物；ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、３，３’，４，４’－テトラ（ｔｅｒｔ－ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６－トリメチルベンゾフェノン等のベンゾフェノン化合物；９，１０－フェナンスレンキノン、２－エチルアントラキノン、カンファーキノン等のキノン化合物；１０－ブチル－２－クロロアクリドン、ベンジル、フェニルグリオキシル酸メチル、チタノセン化合物等が挙げられる。 Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.
　重合開始剤（Ｄ）としては、Ｏ－アシルオキシム化合物、アルキルフェノン化合物、トリアジン化合物、アシルホスフィンオキサイド化合物及びビイミダゾール化合物からなる群から選ばれる少なくとも１種を含む重合開始剤が好ましく、Ｏ－アシルオキシム化合物を含む重合開始剤がより好ましい。 The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds. A polymerization initiator containing a vinyl compound is more preferable.
　重合開始剤（Ｄ）の含有量は、樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、好ましくは０．１～３０質量部であり、より好ましくは１～２０質量部である。重合開始剤（Ｄ）の含有量が、前記の範囲内にあると、高感度化して露光時間が短縮される傾向があるためカラーフィルタの生産性が向上する。 The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.
＜溶剤（Ｅ）＞
　溶剤（Ｅ）は、特に限定されず、当該分野で通常使用される溶剤を用いることができる。例えば、エステル溶剤（分子内に－ＣＯＯ－を含み、－Ｏ－を含まない溶剤）、エーテル溶剤（分子内に－Ｏ－を含み、－ＣＯＯ－を含まない溶剤）、エーテルエステル溶剤（分子内に－ＣＯＯ－と－Ｏ－とを含む溶剤）、ケトン溶剤（分子内に－ＣＯ－を含み、－ＣＯＯ－を含まない溶剤）、アルコール溶剤（分子内にＯＨを含み、－Ｏ－、－ＣＯ－及び－ＣＯＯ－を含まない溶剤）、芳香族炭化水素溶剤、アミド溶剤、ジメチルスルホキシドが挙げられる。 <Solvent (E)>
The solvent (E) is not particularly limited, and a solvent commonly used in this field can be used. For example, ester solvents (solvents containing -COO- and not -O- in the molecule), ether solvents (solvents containing -O- and not -COO-), ether ester solvents (intramolecular) A solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule but not -COO-), an alcohol solvent (containing OH in the molecule, -O-,- CO- and -COO--free solvents), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.
　エステル溶剤としては、乳酸メチル、乳酸エチル、乳酸ブチル、２－ヒドロキシイソブタン酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル、ギ酸ペンチル、酢酸イソペンチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、シクロヘキサノールアセテート及びγ－ブチロラクトンなどが挙げられる。 Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.
　エーテル溶剤としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、３－メトキシ－１－ブタノール、３－メトキシ－３－メチルブタノール、テトラヒドロフラン、テトラヒドロピラン、１，４－ジオキサン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、アニソール、フェネトール及びメチルアニソールなどが挙げられる。 As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methylanisole.
　エーテルエステル溶剤としては、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート及びジエチレングリコールモノブチルエーテルアセテートなどが挙げられる。 Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and 3-ethoxy. Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.
　ケトン溶剤としては、４－ヒドロキシ－４－メチル－２－ペンタノン、アセトン、２－ブタノン、２－ヘプタノン、３－ヘプタノン、４－ヘプタノン、４－メチル－２－ペンタノン、シクロペンタノン、シクロヘキサノン及びイソホロンなどが挙げられる。 Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. And so on.
　アルコール溶剤としては、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール及びグリセリンなどが挙げられる。 Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.
　芳香族炭化水素溶剤としては、ベンゼン、トルエン、キシレン及びメシチレンなどが挙げられる。 Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene and the like.
　アミド溶剤としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド及びＮ－メチルピロリドンなどが挙げられる。 Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
　上記の溶剤のうち、塗布性、乾燥性の点から、１ａｔｍにおける沸点が１２０℃以上１８０℃以下である有機溶剤が好ましい。溶剤としては、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル、プロピレングリコールモノメチルエーテル、３－エトキシプロピオン酸エチル、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、４－ヒドロキシ－４－メチル－２－ペンタノン及びＮ，Ｎ－ジメチルホルムアミドが好ましく、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、４－ヒドロキシ－４－メチル－２－ペンタノン、乳酸エチル及び３－エトキシプロピオン酸エチルがより好ましい。 Among the above solvents, organic solvents having a boiling point of 120° C. or more and 180° C. or less at 1 atm are preferable from the viewpoints of coating properties and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone And N,N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.
　溶剤（Ｅ）の含有率は、本発明の着色硬化性樹脂組成物の総量に対して、好ましくは７０～９５質量％であり、より好ましくは７５～９２質量％である。言い換えると、着色硬化性樹脂組成物の固形分の総含有率は、好ましくは５～３０質量％、より好ましくは８～２５質量％である。溶剤（Ｅ）の含有率が前記の範囲内にあると、塗布時の平坦性が良好になり、またカラーフィルタを形成した際に色濃度が不足しないために表示特性が良好となる傾向がある。 The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the display characteristics tend to become good because the color density is not insufficient when the color filter is formed. ..
＜レベリング剤（Ｆ）＞
　レベリング剤（Ｆ）としては、シリコーン系界面活性剤、フッ素系界面活性剤及びフッ素原子を有するシリコーン系界面活性剤等が挙げられる。これらは、側鎖に重合性基を有していてもよい。
　シリコーン系界面活性剤としては、分子内にシロキサン結合を有する界面活性剤等が挙げられる。具体的には、トーレシリコーンＤＣ３ＰＡ、同ＳＨ７ＰＡ、同ＤＣ１１ＰＡ、同ＳＨ２１ＰＡ、同ＳＨ２８ＰＡ、同ＳＨ２９ＰＡ、同ＳＨ３０ＰＡ、同ＳＨ８４００（東レ・ダウコーニング（株）製）、ＫＰ３２１、ＫＰ３２２、ＫＰ３２３、ＫＰ３２４、ＫＰ３２６、ＫＰ３４０、ＫＰ３４１（信越化学工業（株）製）、ＴＳＦ４００、ＴＳＦ４０１、ＴＳＦ４１０、ＴＳＦ４３００、ＴＳＦ４４４０、ＴＳＦ４４４５、ＴＳＦ４４４６、ＴＳＦ４４５２及びＴＳＦ４４６０（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）等が挙げられる。 <Leveling agent (F)>
Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, Examples include KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).
　前記のフッ素系界面活性剤としては、分子内にフルオロカーボン鎖を有する界面活性剤等が挙げられる。具体的には、フロラード（登録商標）ＦＣ４３０、同ＦＣ４３１（住友スリーエム（株）製）、メガファック（登録商標）Ｆ１４２Ｄ、同Ｆ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７７、同Ｆ１８３、同Ｆ５５４、同Ｒ３０、同ＲＳ－７１８－Ｋ（ＤＩＣ（株）製）、エフトップ（登録商標）ＥＦ３０１、同ＥＦ３０３、同ＥＦ３５１、同ＥＦ３５２（三菱マテリアル電子化成（株）製）、サーフロン（登録商標）Ｓ３８１、同Ｓ３８２、同ＳＣ１０１、同ＳＣ１０５（旭硝子（株）製）及びＥ５８４４（（株）ダイキンファインケミカル研究所製）等が挙げられる。 Examples of the above-mentioned fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F543. R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).
　前記のフッ素原子を有するシリコーン系界面活性剤としては、分子内にシロキサン結合及びフルオロカーボン鎖を有する界面活性剤等が挙げられる。具体的には、メガファック（登録商標）Ｒ０８、同ＢＬ２０、同Ｆ４７５、同Ｆ４７７及び同Ｆ４４３（ＤＩＣ（株）製）等が挙げられる。 Examples of the above-mentioned silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megafac (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).
　レベリング剤（Ｆ）の含有率は、着色硬化性樹脂組成物の総量に対して、好ましくは０．００１質量％以上０.２質量％以下であり、より好ましくは０.００２質量％以上０．２質量％以下、さらに好ましくは０.００５質量％以上０．２質量％以下である。尚、この含有率に、前記分散剤の含有率は含まれない。レベリング剤（Ｆ）の含有率が前記の範囲内にあると、カラーフィルタの平坦性を良好にすることができる。 The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.02% by mass or less with respect to the total amount of the colored curable resin composition. It is 2% by mass or less, and more preferably 0.005% by mass or more and 0.2% by mass or less. The content of the dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.
＜その他の成分＞
　本発明の着色硬化性樹脂組成物は、必要に応じて、重合開始助剤、充填剤、他の高分子化合物、密着促進剤、光安定剤、連鎖移動剤等、当該技術分野で公知の添加剤を含んでもよい。
　密着促進剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、３－グリシジルオキシプロピルトリメトキシシラン、３－グリシジルオキシプロピルメチルジメトキシシラン、３－グリシジルオキシプロピルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－クロロプロピルメチルジメトキシシラン、３－クロロプロピルトリメトキシシラン、３－メタクリロイルオキシプロピルトリメトキシシラン、３－スルファニルプロピルトリメトキシシラン、３－イソシアナトプロピルトリエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン及びＮ－フェニル－３－アミノプロピルトリエトキシシラン等が挙げられる。 <Other ingredients>
The colored curable resin composition of the present invention, if necessary, a polymerization initiation auxiliary agent, a filler, another polymer compound, an adhesion promoter, a light stabilizer, a chain transfer agent, etc., which are known additives in the technical field. An agent may be included.
Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiene. Ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane , 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-( Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxy Examples thereof include silane.
＜着色硬化性樹脂組成物の製造方法＞
　本発明の着色硬化性樹脂組成物は、例えば、着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）、及び重合開始剤（Ｄ）並びに必要に応じて用いられる溶剤（Ｅ）、レベリング剤（Ｆ）及びその他の成分を混合することにより調製できる。 <Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary, It can be prepared by mixing the leveling agent (F) and other components.
＜カラーフィルタの製造方法＞
　本発明の着色硬化性樹脂組成物から着色パターンを製造する方法としては、フォトリソグラフ法、インクジェット法、印刷法等が挙げられる。中でも、フォトリソグラフ法が好ましい。フォトリソグラフ法は、前記着色硬化性樹脂組成物を基板に塗布し、乾燥させて着色組成物層を形成し、フォトマスクを介して該着色組成物層を露光して、現像する方法である。フォトリソグラフ法において、露光の際にフォトマスクを用いないこと、及び／又は現像しないことにより、上記着色組成物層の硬化物である着色塗膜を形成することができる。このように形成した着色パターンや着色塗膜が本発明のカラーフィルタである。
　作製するカラーフィルタの膜厚は、特に限定されず、目的や用途等に応じて適宜調整することができ、例えば、０．１～３０μｍ、好ましくは０．１～２０μｍ、さらに好ましくは０．５～６μｍである。 <Method of manufacturing color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, a printing method and the like. Among them, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithographic method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and/or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited and may be appropriately adjusted depending on the purpose and application. For example, it is 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5. ˜6 μm.
　基板としては、石英ガラス、ホウケイ酸ガラス、アルミナケイ酸塩ガラス、表面をシリカコートしたソーダライムガラスなどのガラス板や、ポリカーボネート、ポリメタクリル酸メチル、ポリエチレンテレフタレートなどの樹脂板、シリコン、前記基板上にアルミニウム、銀、銀／銅／パラジウム合金薄膜などを形成したものが用いられる。これらの基板上には、別のカラーフィルタ層、樹脂層、トランジスタ、回路等が形成されていてもよい。 As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass whose surface is coated with silica, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate Aluminum, silver, silver/copper/palladium alloy thin film, etc. are used. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.
　フォトリソグラフ法による各色画素の形成は、公知又は慣用の装置や条件で行うことができる。例えば、下記のようにして作製することができる。
　まず、着色硬化性樹脂組成物を基板上に塗布し、加熱乾燥（プリベーク）及び／又は減圧乾燥することにより溶剤等の揮発成分を除去して乾燥させ、平滑な着色組成物層を得る。
　塗布方法としては、スピンコート法、スリットコート法、スリット　アンド　スピンコート法等が挙げられる。
　加熱乾燥を行う場合の温度は、３０～１２０℃が好ましく、５０～１１０℃がより好ましい。また加熱時間としては、１０秒間～６０分間であることが好ましく、３０秒間～３０分間であることがより好ましい。
　減圧乾燥を行う場合は、５０～１５０Ｐａの圧力下、２０～２５℃の温度範囲で行うことが好ましい。
　着色組成物層の膜厚は、特に限定されず、目的とするカラーフィルタの膜厚に応じて適宜選択すればよい。 The formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be manufactured as follows.
First, the colored curable resin composition is applied onto a substrate, and dried by heating (prebaking) and/or vacuum drying to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.
Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.
The temperature for heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferable to perform the drying under a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C.
The thickness of the coloring composition layer is not particularly limited and may be appropriately selected according to the intended thickness of the color filter.
　次に、着色組成物層は、目的の着色パターンを形成するためのフォトマスクを介して露光される。該フォトマスク上のパターンは特に限定されず、目的とする用途に応じたパターンが用いられる。
　露光に用いられる光源としては、２５０～４５０ｎｍの波長の光を発生する光源が好ましい。例えば、３５０ｎｍ未満の光を、この波長域をカットするフィルタを用いてカットしたり、４３６ｎｍ付近、４０８ｎｍ付近、３６５ｎｍ付近の光を、これらの波長域を取り出すバンドパスフィルタを用いて選択的に取り出したりしてもよい。具体的には、水銀灯、発光ダイオード、メタルハライドランプ、ハロゲンランプ等が挙げられる。
　露光面全体に均一に平行光線を照射したり、フォトマスクと着色組成物層が形成された基板との正確な位置合わせを行うことができるため、マスクアライナ及びステッパ等の露光装置を使用することが好ましい。 Next, the colored composition layer is exposed through a photomask for forming an intended colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that emits light having a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You may Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.
Use an exposure device such as a mask aligner or stepper because it can irradiate parallel rays uniformly on the entire exposed surface and can perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed. Is preferred.
　露光後の着色組成物層を現像液に接触させて現像することにより、基板上に着色パターンが形成される。現像により、着色組成物層の未露光部が現像液に溶解して除去される。
現像液としては、例えば、水酸化カリウム、炭酸水素ナトリウム、炭酸ナトリウム、水酸化テトラメチルアンモニウム等のアルカリ性化合物の水溶液が好ましい。これらのアルカリ性化合物の水溶液中の濃度は、好ましくは０．０１～１０質量％であり、より好ましくは０．０３～５質量％である。さらに、現像液は、界面活性剤を含んでいてもよい。
　現像方法は、パドル法、ディッピング法及びスプレー法等のいずれでもよい。さらに現像時に基板を任意の角度に傾けてもよい。
　現像後は、水洗することが好ましい。 A colored pattern is formed on the substrate by bringing the colored composition layer after exposure into contact with a developing solution for development. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developing solution.
As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be a paddle method, a dipping method, a spray method or the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.
　さらに、得られた着色パターンに、ポストベークを行うことが好ましい。ポストベーク温度は、１５０～２５０℃が好ましく、１６０～２３５℃がより好ましい。ポストベーク時間は、１～１２０分間が好ましく、１０～６０分間がより好ましい。 Furthermore, it is preferable to post-bake the obtained coloring pattern. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.
　以下、実施例によって本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。例中、含有量ないし使用量を表す％及び部は、特に断らない限り質量基準である。
　以下の合成例において、化合物は、ＮＭＲ（ＪＮＭ－ＥＸ－２７０；（日本電子(株)製））で同定した。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples,% and parts indicating the content or the amount used are based on mass unless otherwise specified.
In the following synthesis examples, compounds were identified by NMR (JNM-EX-270; (manufactured by JEOL Ltd.)).
（着色剤合成例１）
　２，４－ジメチルアニリン（東京化成工業（株）製）１０．０部、２－エチルヘキサンブロミド（東京化成工業（株）製）１７．０部、及びテトラブチルアンモニウムブロミド（和光化学工業（株）製）４４．０部を混合した。得られた混合物を、９０℃で８時間撹拌した。反応終了後、５０部の１０％重曹水を加えた後、酢酸エチル１００部を加えて水層を廃棄した。水、１０％塩酸で洗う操作を２回繰り返した後、溶剤を溜去した。得られたオイルを６０℃で２４時間減圧乾燥し、下記式（ａ－１）で表される化合物９．３部を得た。 (Colorant Synthesis Example 1)
2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts, 2-ethylhexane bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 17.0 parts, and tetrabutylammonium bromide (Wako Chemical Industry Co., Ltd.) )) 44.0 parts were mixed. The resulting mixture was stirred at 90°C for 8 hours. After completion of the reaction, 50 parts of 10% aqueous sodium hydrogen carbonate was added, 100 parts of ethyl acetate was added, and the aqueous layer was discarded. After washing twice with water and 10% hydrochloric acid was repeated, the solvent was distilled off. The obtained oil was dried under reduced pressure at 60° C. for 24 hours to obtain 9.3 parts of a compound represented by the following formula (a-1).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　式（ａ－１）で示される化合物の1Ｈ－ＮＭＲ（２７０ＭＨｚ、δ値（ｐｐｍ、ＴＭＳ基準）、ＤＭＳＯ－ｄ６）
δ　０．８５（ｍ，６Ｈ）、１．２３－１．４２（ｂｒ，８Ｈ）、１．５９（ｂｒ，１Ｈ）、２．０４（ｓ，３Ｈ）、２．１２（ｓ，３Ｈ）、２．９１（ｄ，２Ｈ）、４．３７（ｂｒ，１Ｈ）、６．３８（ｄ，１Ｈ）、６．７５（ｓ，１Ｈ）、６．７７（ｄ，１Ｈ） 1 H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d 6 ) of the compound represented by the formula (a-1)
δ 0.85 (m, 6H), 1.23 to 1.42 (br, 8H), 1.59 (br, 1H), 2.04 (s, 3H), 2.12 (s, 3H), 2.91 (d, 2H), 4.37 (br, 1H), 6.38 (d, 1H), 6.75 (s, 1H), 6.77 (d, 1H)
　上記で得られた式（ａ－１）で表される化合物３．０部、３－ブロモフェノール（東京化成工業（株）製）２．２部、酢酸パラジウム０．０１５部、ｔｅｒｔ－ブトキシナトリウム（東京化成工業（株）製）３．２部、トリｔｅｒｔ－ブチルホスフィン（東京化成工業（株）製）０．０５５部、及びトルエン２５．６部を混合し、１００℃で１５時間撹拌した。得られた混合物に、酢酸エチル３０部、水１００部を加えて水層を廃棄した。水で洗う操作を2回繰り返した後、溶剤を溜去した。残渣をシリカゲルクロマトグラフィー（クロロホルム／ヘキサン＝１／１）で精製し、得られたオイルを６０℃で２４時間減圧乾燥し、下記式（ａ－２）で表される化合物で示される化合物１．９部を得た。 3.0 parts of the compound represented by the formula (a-1) obtained above, 2.2 parts of 3-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.015 part of palladium acetate, tert-butoxy sodium salt 3.2 parts (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.055 parts tri-tert-butylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 25.6 parts toluene were mixed and stirred at 100° C. for 15 hours. .. 30 parts of ethyl acetate and 100 parts of water were added to the obtained mixture, and the aqueous layer was discarded. After the operation of washing with water was repeated twice, the solvent was distilled off. The residue was purified by silica gel chromatography (chloroform/hexane=1/1), the obtained oil was dried under reduced pressure at 60° C. for 24 hours, and the compound represented by the following formula (a-2): 1. 9 parts were obtained.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（ａ－２）で示される化合物の1Ｈ－ＮＭＲ（２７０ＭＨｚ、δ値（ｐｐｍ、ＴＭＳ基準）、ＤＭＳＯ－ｄ６）
δ　０．８５（ｍ，６Ｈ）、１．２３－１．４２（ｂｒ，８Ｈ）、１．５５（ｂｒ，１Ｈ）、１．９４（ｓ，３Ｈ）、２．２７（ｓ，３Ｈ）、２．９０（ｄ，２Ｈ）、６．３７（ｄ，１Ｈ）、６．７５（ｓ，１Ｈ）、６．７６（ｄ，１Ｈ）、６．９２－７．１４（ｍ，４Ｈ）、８．９３（ｓ，１Ｈ） 1 H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d 6 ) of the compound represented by the formula (a-2)
δ 0.85 (m, 6H), 1.23-1.42 (br, 8H), 1.55 (br, 1H), 1.94 (s, 3H), 2.27 (s, 3H), 2.90 (d, 2H), 6.37 (d, 1H), 6.75 (s, 1H), 6.76 (d, 1H), 6.92-7.14 (m, 4H), 8 .93 (s, 1H)
　上記で得られた式（ａ－２）で示される化合物４．４部、３，４－ジヒドロキシ－３－シクロブテン－１，２－ジオン（東京化成工業（株）製）０．８部、１－ブタノール９０．０部及びトルエン６０．０部を混合した。得られた混合物を、Ｄｅａｎ－Ｓｔａｒｋ管を用いて生成した水を除きながら１２５℃で３時間撹拌した。反応終了後、溶剤を溜去し、酢酸を１５部加えた後、１８％食塩水１００部に滴下し、析出した固体を濾取した。
濾取した固体をヘキサンで洗浄した。得られた固体を６０℃で２４時間減圧乾燥し、式（ＡＩＩ－１０）で示される化合物４．９部を得た。 4.4 parts of the compound represented by the formula (a-2) obtained above, 0.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 1 -Butanol 90.0 parts and toluene 60.0 parts were mixed. The resulting mixture was stirred at 125° C. for 3 hours while removing the water produced using a Dean-Stark tube. After the reaction was completed, the solvent was distilled off, 15 parts of acetic acid was added, and the mixture was added dropwise to 100 parts of 18% saline, and the precipitated solid was collected by filtration.
The solid collected by filtration was washed with hexane. The obtained solid was dried under reduced pressure at 60° C. for 24 hours to obtain 4.9 parts of a compound represented by the formula (AII-10).
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（ＡＩＩ－１０）で示される化合物の1Ｈ－ＮＭＲ（２７０ＭＨｚ、δ値（ｐｐｍ、ＴＭＳ基準）、ＤＭＳＯ－ｄ６）
δ　０．８７（ｍ，１２Ｈ）、１．２１－１．５７（ｍ，１６Ｈ）、１．７２（ｂｒ，２Ｈ）、２．０５（ｓ，６Ｈ）、２．３６（ｓ，６Ｈ）、３．３７（ｂｒ，２Ｈ）、３．７８（ｂｒ，２Ｈ）、６．００（ｂｒ，４Ｈ）、６．９７－７．１２（ｍ，６Ｈ）、７．７７－７．９５（ｍ，２Ｈ）、１１．３５（ｓ，１Ｈ）、１２．０６（ｓ，１Ｈ） 1 H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d 6 ) of the compound represented by the formula (AII-10)
δ 0.87 (m, 12H), 1.21-1.57 (m, 16H), 1.72 (br, 2H), 2.05 (s, 6H), 2.36 (s, 6H), 3.37 (br, 2H), 3.78 (br, 2H), 6.00 (br, 4H), 6.97-7.12 (m, 6H), 7.77-7.95 (m, 2H), 11.35 (s, 1H), 12.06 (s, 1H)
　以下において、化合物の構造は質量分析（ＬＣ；Ａｇｉｌｅｎｔ製１２００型、ＭＡＳＳ；Ａｇｉｌｅｎｔ製ＬＣ／ＭＳＤ型）で確認した。 In the following, the structure of the compound was confirmed by mass spectrometry (LC: 1200 type manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).
（着色剤合成例２）
　ｍ－ブロモフェノール（東京化成工業（株）製）５０部及びイミダゾール（東京化成工業（株）製）３０部をジクロロメタン（関東化学（株）製）５００部に溶解させ０℃に冷却後、ｔｅｒｔ－ブチルジメチルクロロシラン（東京化成工業（株）製）４８部を滴下した。滴下終了後２３℃へ昇温し１６時間撹拌した。反応終了後水を加えて有機層を抽出し、溶剤を濃縮後シリカゲルカラムクロマトグラフィーで分離精製を行い、式（ａ－３）で表される化合物を７４部得た。 (Colorant Synthesis Example 2)
50 parts of m-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.), cooled to 0° C., and then tert. -Butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 48 parts was dropped. After the dropping was completed, the temperature was raised to 23° C. and the mixture was stirred for 16 hours. After completion of the reaction, water was added to extract the organic layer, the solvent was concentrated, and the residue was separated and purified by silica gel column chromatography to obtain 74 parts of the compound represented by the formula (a-3).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+２８７．０
Ｅｘａｃｔ　Ｍａｓｓ：＋２８６．０ Identification :( mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 287.0
Exact Mass: +286.0
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　２，４－ジメチルアニリン（東京化成工業（株）製）１５部、式（ａ－３）で表される化合物３５部、水酸化カリウム（和光純薬工業（株）製）１４部、テトラブチルアンモニウムブロミド（東京化成工業（株）製）２部及びビス（トリ－ｔｅｒｔ－ブチルホスフィン）パラジウム（０）（アルドリッチ（株）製）０．６部をトルエン（関東化学（株）製）２５０部及び水１５部に溶解させ、９０℃に加熱して３０分撹拌した。反応終了後有機層を抽出して濃縮し、シリカゲルカラムクロマトグラフィーで分離精製を行い式（ａ－４）で表される化合物を１４部得た。 15 parts of 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 35 parts of the compound represented by the formula (a-3), 14 parts of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), tetrabutyl 2 parts of ammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.6 part of bis(tri-tert-butylphosphine)palladium(0) (manufactured by Aldrich Co.) 250 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) And 15 parts of water, and the mixture was heated to 90° C. and stirred for 30 minutes. After the reaction was completed, the organic layer was extracted, concentrated, and separated and purified by silica gel column chromatography to obtain 14 parts of the compound represented by the formula (a-4).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+３２８．３
Ｅｘａｃｔ　Ｍａｓｓ：＋３２７．２ Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] + 328.3
Exact Mass: +327.2
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　式（ａ－４）で表される化合物１４部及び４－クロロ－４－オキソ酪酸メチル１０部（東京化成工業（株）製）をトルエン（関東化学（株）製）２５５部に溶解させ、９０℃に昇温して１時間撹拌した。反応終了後、水を加えて有機層を抽出し、溶剤を濃縮後シリカゲルクロマトグラフィーで分離精製を行い、式（ａ－５）で表される化合物を１５部得た。 14 parts of the compound represented by the formula (a-4) and 10 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 255 parts of toluene (manufactured by Kanto Chemical Co., Ltd.), It heated up at 90 degreeC and stirred for 1 hour. After completion of the reaction, water was added to extract the organic layer, the solvent was concentrated, and the mixture was separated and purified by silica gel chromatography to obtain 15 parts of the compound represented by the formula (a-5).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+４４２．３
Ｅｘａｃｔ　Ｍａｓｓ：＋４４１．２ Identification :( mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 442.3
Exact Mass: +441.2
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　式（ａ－５）で表される化合物１５部をテトラヒドロフラン（関東化学（株）製）１５０部に溶解させ、０℃に冷却後にフッ化テトラ－ｎ－ブチルアンモニウム１Ｍテトラヒドロフラン溶液（東京化成工業（株）製）１５部を滴下した。滴下終了後２３℃に昇温し、２時間撹拌した。反応終了後、溶剤を濃縮し、シリカゲルカラムクロマトグラフィーで分離精製を行い、式（ａ－６）で表される化合物を１２部得た。 15 parts of the compound represented by the formula (a-5) was dissolved in 150 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.), cooled to 0° C., and then tetra-n-butylammonium fluoride 1M tetrahydrofuran solution (Tokyo Chemical Industry ( 15 parts). After the dropping was completed, the temperature was raised to 23° C. and the mixture was stirred for 2 hours. After completion of the reaction, the solvent was concentrated, and the residue was separated and purified by silica gel column chromatography to obtain 12 parts of the compound represented by the formula (a-6).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+３２８．２
Ｅｘａｃｔ　Ｍａｓｓ：＋３２７．２ Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] + 328.2
Exact Mass: +327.2
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　式（ａ－６）で表される化合物１２部をテトラヒドロフラン（関東化学（株）製）２４０部に溶解させ０℃に冷却後、ボラン－１Ｍテトラヒドロフラン溶液（関東化学（株）製）１８０部を滴下した。滴下終了後３０分撹拌し、水を加えたのちテトラヒドロフランを濃縮し、酢酸エチルで有機層を抽出した。溶剤を濃縮後シリカゲルカラムクロマトグラフィーで分離精製を行い、式（ａ－７）で表される化合物を６部得た。 After dissolving 12 parts of the compound represented by the formula (a-6) in 240 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.) and cooling to 0° C., 180 parts of borane-1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.) Dropped. After completion of dropping, the mixture was stirred for 30 minutes, water was added, tetrahydrofuran was concentrated, and the organic layer was extracted with ethyl acetate. The solvent was concentrated and then purified by silica gel column chromatography to obtain 6 parts of the compound represented by the formula (a-7).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+３１４．２
Ｅｘａｃｔ　Ｍａｓｓ：＋３１３．２ Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] + 314.2
Exact Mass: +313.2
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　式（ａ－７）で表される化合物６部及び水酸化リチウムー水和物（和光純薬工業（株））０．２部をメタノール（関東化学（株）製）２０部、テトラヒドロフラン（関東化学（株）製）２０部、水１０部に溶解させ、２３℃で１時間撹拌した。反応終了後、有機溶剤を濃縮し、酢酸エチルで有機層を抽出し、シリカゲルカラムクロマトグラフィーで分離精製を行って式（ａ－８）で表される化合物を４部得た。 6 parts of the compound represented by the formula (a-7) and 0.2 part of lithium hydroxide monohydrate (Wako Pure Chemical Industries, Ltd.), 20 parts of methanol (manufactured by Kanto Chemical Co., Inc.), tetrahydrofuran (Kanto Chemical Co., Inc.) (Manufactured by K.K.) 20 parts and water 10 parts, and the mixture was stirred at 23° C. for 1 hour. After completion of the reaction, the organic solvent was concentrated, the organic layer was extracted with ethyl acetate, and separated and purified by silica gel column chromatography to obtain 4 parts of the compound represented by the formula (a-8).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+３００．２
Ｅｘａｃｔ　Ｍａｓｓ：＋２９９．２ Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] + 300.2
Exact Mass: +299.2
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　式（ａ－８）で表される化合物４部及び３，４－ジヒドロキシ－３－シクロブテン－１，２－ジオン（和光純薬工業（株）製）０．８部をトルエン（関東化学（株）製）４０部、ｎ－ブタノール（関東化学（株）製）１０部に溶解させ、１４０℃に昇温し、２時間撹拌した。溶剤を濃縮後、シリカゲルカラムクロマトグラフィーで分離精製を行い、式（ＡＩＩ－１７）で表される化合物を１．６部得た。 4 parts of the compound represented by the formula (a-8) and 0.8 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed with toluene (Kanto Chemical Co., Inc. 40 parts) and 10 parts of n-butanol (manufactured by Kanto Chemical Co., Inc.) were dissolved, the temperature was raised to 140° C. and the mixture was stirred for 2 hours. After the solvent was concentrated, the residue was separated and purified by silica gel column chromatography to obtain 1.6 parts of the compound represented by the formula (AII-17).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+６７７．３
Ｅｘａｃｔ　Ｍａｓｓ：＋６７６．３ Identification :( mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 677.3
Exact Mass: +676.3
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
（着色剤合成例３）
　３－ブロモアニソール（東京化成工業（株）製）５０部を２，４，６－トリメチルアニリン（東京化成工業（株）製）３６．１部とトルエン（関東化学（株）製）４３４部に溶解させ、この溶液に水酸化カリウム（関東化学（株）製）３０部、水２５部、テトラブチルアンモニウムブロミド（東京化成工業（株）製）２部、ビス(トリ－ｔｅｒｔ－ブチルホスフィン)パラジウム（０）（東京化成工業（株）製）１．４部を混合した。９０℃に昇温して５時間撹拌した後、有機層を抽出により取得し、溶剤を留去し粗生成物を５２．１部得た。得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（ａ－９）で表される化合物を５０．２部得た。 (Colorant Synthesis Example 3)
50 parts of 3-bromoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) to 36.1 parts of 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 434 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) Dissolve, 30 parts of potassium hydroxide (manufactured by Kanto Chemical Co., Inc.), 25 parts of water, 2 parts of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), bis(tri-tert-butylphosphine)palladium in this solution. (0) 1.4 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed. After heating to 90° C. and stirring for 5 hours, the organic layer was obtained by extraction, and the solvent was distilled off to obtain 52.1 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 50.2 parts of the compound represented by the formula (a-9).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+２４２．３
Ｅｘａｃｔ　Ｍａｓｓ：＋２４１．２ Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] + 242.3
Exact Mass: +241.2
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　式（ａ－９）で表される化合物３３部、４－クロロ－４－オキソ酪酸メチル（東京化成工業（株）製）２６．８部及びトルエン（関東化学（株）製）２８６部を混合し、１００℃で１６時間撹拌しながら加熱した。反応終了後溶剤を留去し、得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（ａ－１０）で表される化合物を３０．７部得た。 33 parts of the compound represented by the formula (a-9), 26.8 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 286 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) are mixed. And heated at 100° C. for 16 hours with stirring. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 30.7 parts of the compound represented by the formula (a-10).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+３５６．２
Ｅｘａｃｔ　Ｍａｓｓ：＋３５５．２
Figure JPOXMLDOC01-appb-C000032
 Identification :( mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 356.2
Exact Mass: +355.2
Figure JPOXMLDOC01-appb-C000032
　式（ａ－１０）で表される化合物１０部を塩化メチレン（関東化学（株）製）９５部に溶解させ撹拌しながら０℃に冷却した。撹拌しながら三臭化ホウ素（富士フイルム和光純薬（株）製）２８．２部を滴下投入した。滴下終了後、徐々に昇温し１０℃で４時間撹拌した。反応終了後溶剤を減圧留去し、水－有機溶剤抽出操作を施し、溶剤を留去して９．１部の粗生成物を得た。この中に式（ａ－１１）で表される化合物が４８％、式（ａ－１２）で表される化合物が３６％含まれていた。 10 parts of the compound represented by the formula (a-10) was dissolved in 95 parts of methylene chloride (manufactured by Kanto Chemical Co., Inc.) and cooled to 0° C. with stirring. With stirring, 28.2 parts of boron tribromide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added dropwise. After the dropping was completed, the temperature was gradually raised and the mixture was stirred at 10° C. for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, water-organic solvent extraction operation was carried out, and the solvent was distilled off to obtain 9.1 parts of a crude product. In this, 48% of the compound represented by the formula (a-11) and 36% of the compound represented by the formula (a-12) were contained.
Figure JPOXMLDOC01-appb-C000033
 同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+３４２．２
Ｅｘａｃｔ　Ｍａｓｓ：＋３４１．２
Figure JPOXMLDOC01-appb-C000034
 同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+３２８．１
Ｅｘａｃｔ　Ｍａｓｓ：＋３２７．２
Figure JPOXMLDOC01-appb-C000033
 Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] + 342.2
Exact Mass: +341.2.
Figure JPOXMLDOC01-appb-C000034
 Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] + 328.1
Exact Mass: +327.2
　チオニルクロライド（東京化成工業（株）製）１３．２部を７２部のメタノール（関東化学（株）製）に溶かした溶液を０℃に冷却し撹拌しながら、上記で得られた式（ａ－１１）で表される化合物と式（ａ－１２）で表される化合物とを含む粗生成物９．１部を投入した。室温まで昇温し１６時間反応させた。溶剤を減圧留去し、式（ａ－１１）で表される化合物を含む８．３部の粗生成物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製し、式（ａ－１１）で表される化合物を７．４部得た。 A solution of 13.2 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 72 parts of methanol (manufactured by Kanto Kagaku Co., Ltd.) was cooled to 0° C. with stirring, and the formula (a) obtained above was used. 9.1 parts of a crude product containing the compound represented by -11) and the compound represented by formula (a-12) was added. The temperature was raised to room temperature and the reaction was performed for 16 hours. The solvent was distilled off under reduced pressure to obtain 8.3 parts of a crude product containing the compound represented by the formula (a-11). The obtained crude product was purified by silica gel column chromatography to obtain 7.4 parts of the compound represented by the formula (a-11).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+３４２．２
Ｅｘａｃｔ　Ｍａｓｓ：＋３４１．２ Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] + 342.2
Exact Mass: +341.2.
　式（ａ－１１）で表される化合物２部、ボラン１Ｍテトラヒドロフラン溶液（関東化学（株）製）２６．３部、テトラヒドロフラン（関東化学（株）製）１８部を０℃で混合し１０℃まで昇温し５時間撹拌した。反応終了後、水を加えてクエンチし、有機溶剤で抽出した。溶剤を留去して得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製し、式（ａ－１３）で表される化合物を１．６４部得た。 2 parts of the compound represented by the formula (a-11), 26.3 parts of borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Inc.) and 18 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) were mixed at 0° C. and 10° C. The temperature was raised to and stirred for 5 hours. After completion of the reaction, water was added to quench the reaction, and the mixture was extracted with an organic solvent. The crude product obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 1.64 parts of the compound represented by the formula (a-13).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+３００．２
Ｅｘａｃｔ　Ｍａｓｓ：＋２９９．２ Identification: (mass spectrometry) ionization mode=ESI+: m/z=[M+H] + 300.2
Exact Mass: +299.2
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　式（ａ－１３）で表される化合物２．５部及び３，４－ジヒドロキシ－３－シクロブテン－１，２－ジオン（富士フイルム和光純薬（株）製）０．５５部をトルエン（関東化学（株）製）５０部、ｎ－ブタノール（関東化学（株）製）５０部に溶解させ、１１０℃で６時間撹拌しながら加熱した。反応終了後、溶剤を留去し得られた粗生成物をシリカゲルカラムクロマトグラフィーで分離精製を行い、式（ＡＩＩ－１８）で表される化合物を２．７部得た。 2.5 parts of the compound represented by the formula (a-13) and 0.55 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) are added to toluene (Kanto). It was dissolved in 50 parts of Chemical Co., Ltd. and 50 parts of n-butanol (Kanto Chemical Co., Ltd.) and heated at 110° C. for 6 hours with stirring. After completion of the reaction, the solvent was distilled off and the obtained crude product was separated and purified by silica gel column chromatography to obtain 2.7 parts of a compound represented by the formula (AII-18).
同定：（質量分析）イオン化モード＝ＥＳＩ＋：m/z=[M+H]+６７７．４
Ｅｘａｃｔ　Ｍａｓｓ：＋６７６．４ Identification :( mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 677.4
Exact Mass: +676.4
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
（樹脂合成例１）
　還流冷却器、滴下ロート及び撹拌機を備えたフラスコ内に窒素を適量流して窒素雰囲気に置換し、３－メトキシブタノール２２３部、及び３－メトキシブチルアセテート１１０部を入れ、撹拌しながら７０℃まで加熱した。次いで、該フラスコ内に、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－９－イルアクリレートの混合物（混合割合は１：１）１８０部、アクリル酸５４部、Ｎ－シクロヘキシルマレイミド６７部、並びに３－メトキシブタノール１８０部の混合溶液を滴下ポンプを用いて５時間かけて滴下した。
　一方、重合開始剤２，２’－アゾビス（２，４－ジメチルバレロニトリル）６部を３－メトキシブチルアセテート１５０部に溶解した混合溶液を別の滴下ポンプを用いて５時間かけてフラスコ内に滴下した。重合開始剤の滴下が終了した後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）１３０ｍＰａｓ、固形分３０．９％の共重合体（樹脂（Ｂ－１））の溶液を得た。生成した共重合体の重量平均分子量（Ｍｗ）は８８００、固形分換算の酸価は１３７ｍｇ－ＫＯＨ／ｇ、分散度１．７６であった。樹脂（Ｂ－１）は下記構造単位を有する。 (Resin synthesis example 1)
An appropriate amount of nitrogen was flown into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 223 parts of 3-methoxybutanol and 110 parts of 3-methoxybutylacetate were added, and the mixture was stirred until the temperature reached 70°C. Heated. Then, in the flask, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2, 6 ] A mixed solution of 180 parts of a mixture of decan-9-yl acrylate (mixing ratio is 1:1), 54 parts of acrylic acid, 67 parts of N-cyclohexylmaleimide, and 180 parts of 3-methoxybutanol was added using a dropping pump to obtain 5 parts. It dripped over time.
On the other hand, a mixed solution prepared by dissolving 6 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 150 parts of 3-methoxybutylacetate was placed in a flask for 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 130 mPas and a solid content of 30.9% (resin (B-1 )) was obtained. The produced copolymer had a weight average molecular weight (Mw) of 8,800, an acid value in terms of solid content of 137 mg-KOH/g, and a dispersity of 1.76. The resin (B-1) has the following structural unit.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　樹脂のポリスチレン換算の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）の測定は、ＧＰＣ法により以下の条件で行った。
　　　装置　　　　　　；HLC-8120GPC（東ソー（株）製）
　　　カラム　　　　　；TSK-GELG2000HXL
　　　カラム温度　　　；40℃
　　　溶剤　　　　　　；THF
　　　流速　　　　　　；1.0mL/min
　　　被検液固形分濃度；0.001～0.01質量％
　　　注入量　　　　　；50μL
　　　検出器　　　　　；RI
　　　校正用標準物質　；TSK STANDARD POLYSTYRENE
　　　　　　　　　　F-40、F-4、F-288、A-2500、A-500（東ソー（株）製）
　上記で得られたポリスチレン換算の重量平均分子量及び数平均分子量の比（Ｍｗ／Ｍｎ）を分散度とした。 The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column ；TSK-GELG2000HXL
Column temperature: 40℃
Solvent: THF
Flow rate ；1.0mL/min
Test solution solid content concentration: 0.001 to 0.01 mass%
Injection volume: 50 μL
Detector ；RI
Calibration standard ；TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene equivalent weight average molecular weight and number average molecular weight ratio (Mw/Mn) obtained above was taken as the dispersity.
（樹脂合成例２）
　還流冷却器、滴下ロート及び撹拌機を備えたフラスコ内に窒素を適量流して窒素雰囲気に置換し、３－メトキシブタノール１８５部、及びプロピレングリコールモノメチルエーテルアセテート２１６部を入れ、撹拌しながら７０℃まで加熱した。次いで、該フラスコ内に、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－９－イルアクリレートの混合物（混合割合は１：１）１４９部、アクリル酸４５部、Ｎ－シクロヘキシルマレイミド５６部、並びに３－メトキシブタノール１５８部の混合溶液を滴下ポンプを用いて５時間かけて滴下した。
　一方、重合開始剤２，２’－アゾビス（２，４－ジメチルバレロニトリル）８部をプロピレングリコールモノメチルエーテルアセテート１８３部に溶解した混合溶液を別の滴下ポンプを用いて５時間かけてフラスコ内に滴下した。重合開始剤の滴下が終了した後、４時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）２２ｍＰａｓ、固形分２６．１％の共重合体（樹脂（Ｂ－２））の溶液を得た。生成した共重合体の重量平均分子量（Ｍｗ）は８９００、固形分換算の酸価は１４３ｍｇ－ＫＯＨ／ｇ、分散度１．９２であった。樹脂（Ｂ－２）は樹脂（Ｂ－１）と同様の構造単位を有する。 (Resin synthesis example 2)
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 185 parts of 3-methoxybutanol and 216 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 70°C with stirring. Heated. Then, in the flask, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2, 6 ] A mixed solution of 149 parts of a mixture of decan-9-yl acrylate (mixing ratio is 1:1), 45 parts of acrylic acid, 56 parts of N-cyclohexylmaleimide, and 158 parts of 3-methoxybutanol was added using a dropping pump to obtain 5 parts. It dripped over time.
On the other hand, a mixed solution prepared by dissolving 8 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 183 parts of propylene glycol monomethyl ether acetate was placed in the flask for 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 22 mPas and a solid content of 26.1% (resin (B-2 )) was obtained. The produced copolymer had a weight average molecular weight (Mw) of 8900, an acid value in terms of solid content of 143 mg-KOH/g, and a dispersity of 1.92. The resin (B-2) has the same structural unit as the resin (B-1).
（樹脂合成例３）
　還流冷却器、滴下ロート及び撹拌機を備えたフラスコ内に窒素を適量流して窒素雰囲気に置換し、プロピレングリコールモノメチルエーテルアセテート２４８部を入れ、撹拌しながら８０℃まで加熱した。次いで、該フラスコ内に、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－９－イルアクリレートの混合物（混合割合は１：１）５２部、アクリル酸４２部、Ｎ－シクロヘキシルマレイミド１４１部、並び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３５２部の混合溶液を滴下ポンプを用いて５時間かけて滴下した。
　一方、重合開始剤２，２’－アゾビス（２，４－ジメチルバレロニトリル）２０部をプロピレングリコールモノメチルエーテルアセテート１４５部に溶解した混合溶液を別の滴下ポンプを用いて５時間かけてフラスコ内に滴下した。重合開始剤の滴下が終了した後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）１８ｍＰａｓ、固形分２５．７％の共重合体（樹脂（Ｂ－３））の溶液を得た。生成した共重合体の重量平均分子量（Ｍｗ）は８０００、固形分換算の酸価は１１９ｍｇ－ＫＯＨ／ｇ、分散度２．０９であった。樹脂（Ｂ－３）は樹脂（Ｂ－１）と同様の構造単位を有する。 (Resin synthesis example 3)
An appropriate amount of nitrogen was flown into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, 248 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80° C. with stirring. Then, in the flask, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2, 6 ] A mixed solution of 52 parts of a mixture of decan-9-yl acrylate (mixing ratio is 1:1), 42 parts of acrylic acid, 141 parts of N-cyclohexylmaleimide, and 352 parts of propylene glycol monomethyl ether acetate was added using a dropping pump. It dripped over 5 hours.
On the other hand, a mixed solution prepared by dissolving 20 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 145 parts of propylene glycol monomethyl ether acetate was placed in the flask for 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 18 mPas and a solid content of 25.7% (resin (B-3 )) was obtained. The resulting copolymer had a weight average molecular weight (Mw) of 8,000, an acid value in terms of solid content of 119 mg-KOH/g, and a dispersity of 2.09. The resin (B-3) has the same structural unit as the resin (B-1).
（樹脂合成例４）
　還流冷却器、滴下ロート及び撹拌機を備えたフラスコ内に窒素を適量流して窒素雰囲気に置換し、プロピレングリコールモノメチルエーテルアセテート１９１部、及びプロピレングリコールモノメチルエーテル７９部を入れ、撹拌しながら８０℃まで加熱した。次いで、該フラスコ内に、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－９－イルアクリレートの混合物（混合割合は１：１）１１２部、アクリル酸８０部、Ｎ－シクロヘキシルマレイミド１２８部、並びにプロピレングリコールモノメチルエーテル２５８部の混合溶液を滴下ポンプを用いて５時間かけて滴下した。
　一方、重合開始剤２，２’－アゾビス（２，４－ジメチルバレロニトリル）７部をプロピレングリコールモノメチルエーテルアセテート１４５部に溶解した混合溶液を別の滴下ポンプを用いて５時間かけてフラスコ内に滴下した。重合開始剤の滴下が終了した後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）７５ｍＰａｓ、固形分３４．７％の共重合体（樹脂（Ｂ－４））の溶液を得た。生成した共重合体の重量平均分子量（Ｍｗ）は８８００、固形分換算の酸価は１８１ｍｇ－ＫＯＨ／ｇ、分散度２．２０であった。樹脂（Ｂ－４）は樹脂（Ｂ－１）と同様の構造単位を有する。 (Resin synthesis example 4)
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 191 parts of propylene glycol monomethyl ether acetate and 79 parts of propylene glycol monomethyl ether were added, and the mixture was heated to 80°C with stirring. Heated. Then, in the flask, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2, 6 ] A mixed solution of 112 parts of a mixture of decan-9-yl acrylate (mixing ratio 1:1), 80 parts of acrylic acid, 128 parts of N-cyclohexylmaleimide, and 258 parts of propylene glycol monomethyl ether was added using a dropping pump to obtain 5 parts. It dripped over time.
On the other hand, a mixed solution prepared by dissolving 7 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 145 parts of propylene glycol monomethyl ether acetate was placed in the flask for 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23° C.) of 75 mPas and a solid content of 34.7% (resin (B-4 )) was obtained. The produced copolymer had a weight average molecular weight (Mw) of 8,800, an acid value in terms of solid content of 181 mg-KOH/g, and a dispersity of 2.20. The resin (B-4) has the same structural unit as the resin (B-1).
（樹脂合成例５）
　還流冷却器、滴下ロート及び撹拌機を備えたフラスコ内に窒素を適量流して窒素雰囲気に置換し、ジエチレングリコールエチルメチルエーテル１４９部、及びプロピレングリコールモノメチルエーテル１１０部を入れ、撹拌しながら７０℃まで加熱した。次いで、該フラスコ内に、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－９－イルアクリレートの混合物（混合割合は１：１）４５部、アクリル酸７５部、Ｎ－シクロヘキシルマレイミド１８０部、並びにジエチレングリコールメチルエーテル３０９部の混合溶液を滴下ポンプを用いて５時間かけて滴下した。
　一方、重合開始剤２，２’－アゾビス（２，４－ジメチルバレロニトリル）５部をプロピレングリコールモノメチルエーテル１２７部に溶解した混合溶液を別の滴下ポンプを用いて５時間かけてフラスコ内に滴下した。重合開始剤の滴下が終了した後、４時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）６６ｍＰａｓ、固形分３４．５％の共重合体（樹脂（Ｂ－５））の溶液を得た。生成した共重合体の重量平均分子量（Ｍｗ）は９０００、固形分換算の酸価は１８３ｍｇ－ＫＯＨ／ｇ、分散度２．０６であった。
樹脂（Ｂ－５）は樹脂（Ｂ－１）と同様の構造単位を有する。 (Resin synthesis example 5)
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, 149 parts of diethylene glycol ethyl methyl ether and 110 parts of propylene glycol monomethyl ether were added, and the mixture was heated to 70° C. with stirring. did. Then, in the flask, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2, 6 ] A mixed solution of 45 parts of a mixture of decan-9-yl acrylate (mixing ratio is 1:1), 75 parts of acrylic acid, 180 parts of N-cyclohexylmaleimide, and 309 parts of diethylene glycol methyl ether was added for 5 hours using a dropping pump. It dripped over.
On the other hand, a mixed solution prepared by dissolving 5 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 127 parts of propylene glycol monomethyl ether was dropped into the flask over 5 hours by using another dropping pump. did. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for 4 hours, then cooled to room temperature, and the copolymer having a B-type viscosity (23° C.) of 66 mPas and a solid content of 34.5% (resin (B-5 )) was obtained. The weight average molecular weight (Mw) of the produced copolymer was 9000, the acid value in terms of solid content was 183 mg-KOH/g, and the dispersity was 2.06.
The resin (B-5) has the same structural unit as the resin (B-1).
（樹脂合成例６）
　還流冷却器、滴下ロート及び撹拌機を備えたフラスコ内に窒素を適量流して窒素雰囲気に置換し、プロピレングリコールモノメチルエーテルアセテート１００部を入れ、撹拌しながら８５℃まで加熱した。次いで、該フラスコ内に、メタクリル酸１９部、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－９－イルアクリレートの混合物（混合割合は１：１）１７１部をプロピレングリコールモノメチルエーテルアセテート４０部に溶解した溶液を滴下ポンプを用いて約５時間かけて滴下した。
　一方、重合開始剤２，２’－アゾビス（２，４－ジメチルバレロニトリル）２６部をプロピレングリコールモノメチルエーテルアセテート１２０部に溶解した溶液を別の滴下ポンプを用いて約５時間かけてフラスコ内に滴下した。重合開始剤の滴下が終了した後、約３時間同温度で保持した後、その後室温まで冷却して、固形分４３．５％の共重合体（樹脂（Ｂ－６））の溶液を得た。得られた樹脂（Ｂ－２）の重量平均分子量は８０００、分散度は１．９８、固形分換算の酸価は５３ｍｇ－ＫＯＨ／ｇであった。樹脂（Ｂ－６）は下記構造単位を有する。 (Resin synthesis example 6)
An appropriate amount of nitrogen was flown into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85° C. with stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2. A solution of 171 parts of a mixture of 1.0 2,6 ]decane-9-yl acrylate (mixing ratio is 1:1) in 40 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours by using a dropping pump. ..
On the other hand, a solution prepared by dissolving 26 parts of the polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was put into the flask for about 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (B-6)) having a solid content of 43.5%. .. The obtained resin (B-2) had a weight average molecular weight of 8,000, a dispersity of 1.98 and an acid value in terms of solid content of 53 mg-KOH/g. The resin (B-6) has the following structural unit.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
［実施例１～９、比較例１］
［着色硬化性樹脂組成物の調製］
　表２に示す組成となるように各成分を混合して着色硬化性樹脂組成物を得た。 [Examples 1 to 9 and Comparative Example 1]
[Preparation of colored curable resin composition]
Each component was mixed so as to have the composition shown in Table 2 to obtain a colored curable resin composition.
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000039
　表２中、各成分は以下の化合物を表す。
着色剤（Ａ－１）：式（ＡＩＩ－１０）で表される化合物
着色剤（Ａ－２）：式（ＡＩＩ－１７）で表される化合物
着色剤（Ａ－３）：式（ＡＩＩ－１８）で表される化合物
樹脂（Ｂ－１）：樹脂（Ｂ－１）（固形分換算）
樹脂（Ｂ－２）：樹脂（Ｂ－２）（固形分換算）
樹脂（Ｂ－３）：樹脂（Ｂ－３）（固形分換算）
樹脂（Ｂ－４）：樹脂（Ｂ－４）（固形分換算）
樹脂（Ｂ－５）：樹脂（Ｂ－５）（固形分換算）
樹脂（Ｂ－６）：樹脂（Ｂ－６）（固形分換算）
重合性化合物（Ｃ－１）：ジペンタエリスリトールヘキサアクリレート（ＫＡＹＡＲＡＤ（登録商標）　ＤＰＨＡ；日本化薬（株）製）
重合開始剤（Ｄ－１）：Ｎ－１９１９（ＡＤＥＫＡ社製；Ｏ－アシルオキシム化合物）
重合開始剤（Ｄ－２）：ＤＦＩ－０９１（ダイトーケミックス社製；Ｏ－アシルオキシム化合物）
重合開始剤（Ｄ－３）：Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン（イルガキュア（登録商標）ＯＸＥ－０１；ＢＡＳＦ社製；Ｏ－アシルオキシム化合物）
溶剤（Ｅ－１）：４－ヒドロキシ－４－メチル－２－ペンタノン
溶剤（Ｅ－２）：プロピレングリコールモノメチルエーテルアセテート
溶剤（Ｅ－３）：３－メトキシブチルアセテート
溶剤（Ｅ－４）：３－メトキシ－１－ブタノール
溶剤（Ｅ－５）：ジエチレングリコールメチルエチルエーテル 
溶剤（Ｅ－６）：プロピレングリコールモノメチルエーテル
レベリング剤（Ｆ－１）：ポリエーテル変性シリコーンオイル（東レ・ダウコーニング（株）製「トーレシリコーンＳＨ８４００」） In Table 2, each component represents the following compound.
Colorant (A-1): Compound Colorant (A-2) represented by Formula (AII-10): Compound Colorant (A-3) represented by Formula (AII-17): Formula (AII-) Compound (18)) Resin (B-1): Resin (B-1) (as solid content)
Resin (B-2): Resin (B-2) (solid content conversion)
Resin (B-3): Resin (B-3) (solid content conversion)
Resin (B-4): Resin (B-4) (solid content conversion)
Resin (B-5): Resin (B-5) (solid content conversion)
Resin (B-6): Resin (B-6) (solid content conversion)
Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D-1): N-1919 (manufactured by ADEKA; O-acyl oxime compound)
Polymerization initiator (D-2): DFI-091 (manufactured by Daito Chemix Co.; O-acyl oxime compound)
Polymerization initiator (D-3): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Ltd.; O-acyl oxime Compound)
Solvent (E-1): 4-hydroxy-4-methyl-2-pentanone solvent (E-2): propylene glycol monomethyl ether acetate solvent (E-3): 3-methoxybutyl acetate solvent (E-4): 3 -Methoxy-1-butanol solvent (E-5): diethylene glycol methyl ethyl ether
Solvent (E-6): Propylene glycol monomethyl ether leveling agent (F-1): Polyether-modified silicone oil ("Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)
［着色塗膜の作製］
　５ｃｍ角のガラス基板（イーグル２０００；コーニング社製）上に、着色硬化性樹脂組成物を、ポストベーク後の膜厚が２．０μｍになるようにスピンコート法で塗布したのち、１００℃で３分間プリベークして着色組成物層を形成した。放冷後、露光機（ＴＭＥ－１５０ＲＳＫ；トプコン（株）製）を用いて、大気雰囲気下、１００ｍＪ／ｃｍ2の露光量（３６５ｎｍ基準）で着色組成物層に光照射を行った。その後、オーブン中２３０℃で３０分間ポストベークを行い、着色塗膜を得た。 [Preparation of colored coating film]
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by a spin coating method so that the film thickness after post-baking would be 2.0 μm, and then 3 at 100° C. It was prebaked for a minute to form a colored composition layer. After allowing to cool, the colored composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon Corp.) in an air atmosphere at an exposure dose of 100 mJ/cm 2 (365 nm standard). Then, post-baking was performed in an oven at 230° C. for 30 minutes to obtain a colored coating film.
［工程性評価］
１．吸光度保持率
　プリベーク後及びポストベーク後に測定した分光から極大吸光度を求め、下記式に従って極大吸光度の保持率を計算した。結果を表３に示す。
　吸光度保持率（ΔＡｂｓ.Ｍａｘ）＝ポストベーク後の極大吸光度／プリベーク後の極大吸光度
　吸光度保持率が高いほど、成膜工程における適性が高いことを意味する。 [Processability evaluation]
1. Absorbance retention The maximum absorbance was obtained from the spectra measured after pre-baking and post-baking, and the absorbance retention was calculated according to the following formula. The results are shown in Table 3.
Absorbance retention rate (ΔAbs.Max)=maximum absorbance after post-baking/maximum absorbance after pre-baking The higher the absorbance retention rate, the higher the suitability in the film forming step.
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
２．色度
　実施例１、３、及び比較例１の着色硬化性樹脂組成物から形成された着色塗膜の色度は、測色機（ＯＳＰ－ＳＰ－２００；オリンパス（株）製）を用いて測定した分光と、Ｃ光源の特性関数とから、ＣＩＥのＸＹＺ表色系におけるｘｙ色度座標（ｘ、ｙ）とＹとして求めた。結果を表４に示す。Ｙの値が大きいほど明度が高いことを表す。 2. Chromaticity The chromaticity of the colored coating film formed from the colored curable resin compositions of Examples 1 and 3 and Comparative Example 1 was measured by using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). From the measured spectrum and the characteristic function of the C light source, xy chromaticity coordinates (x, y) in the XYZ color system of CIE and X were obtained. The results are shown in Table 4. The larger the value of Y, the higher the brightness.
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
　本発明の着色樹脂組成物によれば、吸光度保持率に優れるカラーフィルタを形成することができる。 According to the colored resin composition of the present invention, a color filter having excellent absorbance retention can be formed.

Claims (3)

  1. 　着色剤、樹脂、重合性化合物、及び重合開始剤を含み、
    　前記着色剤が、式（Ｉ）で表されるスクアリリウム染料を含む着色剤であり、
    　前記樹脂が、Ｎ－置換マレイミドに由来する構造単位を含む樹脂である着色硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式（Ｉ）中、
    　Ｒ1～Ｒ4は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基又は置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。
    　Ｒ5～Ｒ8は、それぞれ独立に、水素原子又はヒドロキシ基を表す。
    　Ａｒ1及びＡｒ2は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は式（ｉ）で表される基を表す。
    Figure JPOXMLDOC01-appb-C000002
     ［式（ｉ）中、
    　Ｒ12は、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は置換基を有していてもよい炭素数２～２０の１価の不飽和炭化水素基を表し、ｍは０～５の整数を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。ｍが２以上のとき、複数のＲ12は、それぞれ同一であっても異なっていてもよい。＊は、窒素原子との結合手を表す。］
    　Ｒ9及びＲ10は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は式（ｉ）で表される基を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。］     Including a colorant, a resin, a polymerizable compound, and a polymerization initiator,
    The colorant is a colorant containing a squarylium dye of formula (I),
    A colored curable resin composition, wherein the resin is a resin containing a structural unit derived from an N-substituted maleimide.
    Figure JPOXMLDOC01-appb-C000001
     [In the formula (I),
    R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group.
    R 5 to R 8 each independently represent a hydrogen atom or a hydroxy group.
    Ar 1 and Ar 2 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, or a group represented by the formula (i).
    Figure JPOXMLDOC01-appb-C000002
     [In formula (i),
    R 12 is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent. And m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. When m is 2 or more, a plurality of R 12's may be the same or different. * Represents a bond with the nitrogen atom. ]
    R 9 and R 10 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i). An oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the monovalent saturated hydrocarbon group. ]
  2. 　請求項１に記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。 A color filter formed from the colored curable resin composition according to claim 1.
  3. 　請求項２に記載のカラーフィルタを含む表示装置。 A display device including the color filter according to claim 2.
PCT/JP2019/047175 2019-02-08 2019-12-03 Colored curable resin composition WO2020162009A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201980088648.XA CN113286828B (en) 2019-02-08 2019-12-03 Colored curable resin composition
KR1020217027733A KR20210124315A (en) 2019-02-08 2019-12-03 Colored curable resin composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-021919 2019-02-08
JP2019021919A JP7203626B2 (en) 2019-02-08 2019-02-08 Colored curable resin composition

Publications (1)

Publication Number Publication Date
WO2020162009A1 true WO2020162009A1 (en) 2020-08-13

Family

ID=71947069

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/047175 WO2020162009A1 (en) 2019-02-08 2019-12-03 Colored curable resin composition

Country Status (5)

Country Link
JP (1) JP7203626B2 (en)
KR (1) KR20210124315A (en)
CN (1) CN113286828B (en)
TW (1) TWI816003B (en)
WO (1) WO2020162009A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3761078A4 (en) * 2018-02-26 2021-11-10 Sumitomo Chemical Company Limited Green colored resin composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016104860A (en) * 2014-11-25 2016-06-09 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Compound
JP2016117858A (en) * 2014-12-22 2016-06-30 住友化学株式会社 Colored curable resin composition
JP2016170282A (en) * 2015-03-12 2016-09-23 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Colored curable resin composition
JP2017008287A (en) * 2014-11-25 2017-01-12 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Compound
JP2018081210A (en) * 2016-11-16 2018-05-24 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Coloration curable resin composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6149353B2 (en) * 2011-07-08 2017-06-21 住友化学株式会社 Colored photosensitive resin composition
US9350676B2 (en) 2012-12-11 2016-05-24 Qualcomm Incorporated Method and apparatus for classifying flows for compression
JP5869536B2 (en) 2013-08-08 2016-02-24 Ｋｙｂ株式会社 Manufacturing data management method for casting products
CN104513510B (en) * 2013-09-26 2018-07-06 东友精细化工有限公司 Colored curable resin composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016104860A (en) * 2014-11-25 2016-06-09 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Compound
JP2017008287A (en) * 2014-11-25 2017-01-12 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Compound
JP2016117858A (en) * 2014-12-22 2016-06-30 住友化学株式会社 Colored curable resin composition
JP2016170282A (en) * 2015-03-12 2016-09-23 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. Colored curable resin composition
JP2018081210A (en) * 2016-11-16 2018-05-24 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Coloration curable resin composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3761078A4 (en) * 2018-02-26 2021-11-10 Sumitomo Chemical Company Limited Green colored resin composition

Also Published As

Publication number Publication date
CN113286828B (en) 2023-04-28
CN113286828A (en) 2021-08-20
JP2020128496A (en) 2020-08-27
TW202039699A (en) 2020-11-01
TWI816003B (en) 2023-09-21
JP7203626B2 (en) 2023-01-13
KR20210124315A (en) 2021-10-14

Similar Documents

Publication Publication Date Title
JP6028326B2 (en) Colored curable resin composition
JP6167680B2 (en) Colored photosensitive resin composition
JP6742698B2 (en) Colored curable resin composition, color filter, and liquid crystal display device
JP6461453B2 (en) Red colored curable resin composition
JP6098113B2 (en) Colored photosensitive resin composition
JP2021113971A (en) Colored curable composition
JP7075724B2 (en) Compounds, coloring compositions, textile materials, color filters, and display devices
JP2019152852A (en) Colored photosensitive resin composition
KR102701187B1 (en) Colored curable resin composition
CN113383020B (en) Colored curable resin composition
JP2013068941A (en) Colored photosensitive resin composition
JP7203626B2 (en) Colored curable resin composition
JP6971055B2 (en) Blue curable resin composition, color filter, and display device
JP7203625B2 (en) Colored curable resin composition
JP7497998B2 (en) Colored curable resin composition, color filter and solid-state imaging device
JP2021143326A (en) Colored curable resin composition
JP2021187913A (en) Phenothiazine-based compound and curable resin composition containing the same
JP2013203956A (en) Colored curable resin composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19914319

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20217027733

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 19914319

Country of ref document: EP

Kind code of ref document: A1