WO2020100646A1 - Colored curable resin composition - Google Patents

Colored curable resin composition Download PDF

Info

Publication number
WO2020100646A1
WO2020100646A1 PCT/JP2019/043190 JP2019043190W WO2020100646A1 WO 2020100646 A1 WO2020100646 A1 WO 2020100646A1 JP 2019043190 W JP2019043190 W JP 2019043190W WO 2020100646 A1 WO2020100646 A1 WO 2020100646A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
carbon atoms
mass
acid
Prior art date
Application number
PCT/JP2019/043190
Other languages
French (fr)
Japanese (ja)
Inventor
紘也 竹田
岡本　信之
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
Priority claimed from JP2019088862A external-priority patent/JP7292963B2/en
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020217012920A priority Critical patent/KR20210090620A/en
Priority to CN201980075082.7A priority patent/CN113166338B/en
Publication of WO2020100646A1 publication Critical patent/WO2020100646A1/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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • 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, and further relates to a color filter, a display device and a solid-state imaging device.
  • a colored curable resin composition containing a colorant, a binder resin, a polymerizable compound and a polymerization initiator is known as a colored curable resin composition for forming a color filter included in a display device, a solid-state imaging device, or the like ( Patent Document 1).
  • An object of the present invention is to provide a colored curable resin composition capable of forming a colored coating film having excellent light resistance.
  • the present invention provides a colored curable resin composition, a color filter, a display device and a solid-state imaging device shown below.
  • [1] Contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the resin (B) is represented by the following formula (B1).
  • a curable colored resin composition containing a resin is represented by the following formula (B1).
  • Z represents a residue of tetracarboxylic acid having an alicyclic skeleton.
  • G represents a hydrogen atom or —CO—X— (CO 2 H) x
  • X represents a residue of a (x + 1) -valent polycarboxylic acid
  • x represents an integer of 1 or more and 3 or less.
  • R 1 represents a hydrogen atom or a methyl group, and a plurality of R 1 may be the same as or different from each other.
  • R 2 represents an alkyl group or a halogen atom having 1 to 5 carbon atoms, if R 2 there are a plurality, R 2 of the plurality of may well, or different and the same as each other.
  • a colored curable resin composition capable of forming a colored coating film having excellent light resistance is provided.
  • Colorant (A) The colored curable resin composition contains a colorant (A).
  • the colorant (A) contains at least one selected from the group consisting of dyes and pigments.
  • the colorant (A) preferably comprises a combination of two dyes or a combination of at least one dye and at least one pigment, and more preferably a combination of two dyes or one dye and one dye. In combination with a pigment.
  • dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes.
  • solvent dyes for example, color index (The Society of Dyers and Colorists publication) solvent, acid, basic, Examples thereof include compounds classified into dyes such as reactive, direct, disperse, moldant, and vat, and known dyes described in Dyeing Note (Shikiso Co., Ltd.).
  • the dye may be appropriately selected according to the desired spectrum of the color filter. These dyes may be used alone or in combination of two or more.
  • the dye is preferably an organic solvent-soluble dye.
  • the dye examples include C.I. I. Solvent Yellow 4, 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 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.
  • C.I. 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.
  • triarylmethane dye As the dye, according to the chemical structure, triarylmethane dye, xanthene dye, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, Examples thereof include squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline dye, nitro dye and tetraazaporphyrin dye.
  • the dyes are preferably the following dyes (A1) to (A4).
  • the dye (A1) contains a salt represented by the formula (A-VI).
  • the dye (A1) also includes its tautomer.
  • R 1A to R 8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxy group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, An oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group.
  • R 9A to R 12A are each independently a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 20 carbon atoms which may have a substituent.
  • the aryl group and the substituent that the aralkyl group may have may be a —SO 3 — or —SO 2 —N — —SO 2 —R f , which represents a saturated hydrocarbon group having 1 to 20 carbon atoms. It may be present, an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group, the hydrogen atom contained in the saturated hydrocarbon group may have a halogen atom or a substituent. It may be substituted with a good amino group.
  • R 9A and R 10A may combine to form a ring with the nitrogen atom to which they are bonded, or R 11A and R 12A may combine to form a ring with the nitrogen atom to which they are bonded.
  • A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent.
  • the substituent which the hydrocarbon group and the aromatic heterocyclic group may have may be —SO 3 — or —SO 2 —N — —SO 2 —R f .
  • m represents an arbitrary natural number.
  • n is, -SO 3 has - as a substituent, or -SO 2 -N - represents the number of -SO 2 -R f, is 0 or 1.
  • R f represents a fluoroalkyl group having 1 to 12 carbon atoms.
  • the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 1A to R 12A may be linear, branched or cyclic and includes, for example, a methyl group, an ethyl group and a propyl group. , Isopropyl group, pentyl group, hexyl group, 2-ethylhexyl group, decyl group, dodecyl group, icosyl group, cyclohexyl group and adamantyl group.
  • the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 1A to R 12A , in which an oxygen atom is inserted between the methylene groups constituting the saturated hydrocarbon group, is represented by the following formula. And the groups mentioned below.
  • * represents a bond with a carbon atom or a nitrogen atom.
  • a saturated hydrocarbon group having 1 to 10 carbon atoms in which an oxygen atom is inserted between methylene groups constituting the saturated hydrocarbon group is preferable, and a saturated hydrocarbon group having 1 to 6 carbon atoms is preferable.
  • a group in which an oxygen atom is inserted between methylene groups constituting the saturated hydrocarbon group is more preferable.
  • Examples of the aryl group having 6 to 20 carbon atoms in R 9A to R 12A include a phenyl group, a toluyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group and a phenylphenyl group.
  • Examples of the aralkyl group having 7 to 20 carbon atoms in R 9A to R 12A include a benzyl group, a phenylethyl group and a methylphenylethyl group.
  • the amino group which may have a substituent in R 9A to R 12A is an amino group having one alkyl group having 1 to 4 carbon atoms such as a methylamino group and an ethylamino group; a dimethylamino group, a diethylamino group , An amino group having two alkyl groups having 1 to 4 carbon atoms such as an ethylmethylamino group; and an amino group.
  • Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms and having a halogen atom or an amino group which may have a substituent in R 9A to R 12A include, for example, trifluoromethyl group, trifluoroethyl group and chloroethyl group.
  • the substituent may be the above-mentioned —SO 3 — or —SO 2 —
  • a halogen atom such as a fluorine atom, a chlorine atom and an iodine atom
  • an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group
  • a hydroxy group such as a sulfo group
  • a sulfamoyl group examples thereof include an alkylsulfonyl group having 1 to 6 carbon atoms such as a sulfonyl group.
  • Examples of the C 1-12 fluoroalkyl group represented by R f include a trifluoromethyl group and a 2,2,2-trifluoroethyl group.
  • aryl group which may have a substituent and the aralkyl group which may have a substituent include groups represented by the following formulas.
  • * represents a bond with a nitrogen atom.
  • the ring formed by combining R 9A and R 10A together with the nitrogen atom to which they are bonded and the ring formed by combining R 11A and R 12A together with the nitrogen atom to which they are bonded are a pyrrolidine ring, a morpholine ring, Examples thereof include a piperidine ring and a piperazine ring.
  • R 1A to R 8A are preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and each independently, a hydrogen atom or a methyl group. More preferably, it is a group, a fluorine atom or a chlorine atom.
  • R 9A to R 12A are preferably each independently a saturated hydrocarbon group having 1 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms which may have a substituent.
  • Group or an optionally substituted aryl group having 6 to 20 carbon atoms and more preferably, each independently, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an optionally substituted carbon number.
  • a phenyl group or a benzyl group, and the hydrogen atom contained in the phenyl group and the benzyl group is a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a sulfo group or It may be substituted with an alkylsulfonyl group having 1 to 4 carbon atoms.
  • Examples of such a phenyl group or a benzyl group include groups represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.
  • Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms in A include phenyl group, toluyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group and phenylphenyl group.
  • Examples of the aromatic hydrocarbon group which may have a substituent represented by A include groups represented by the following formulas. * Represents a bond with a carbon atom.
  • the aromatic heterocyclic group represented by A means an aromatic group having at least one hetero atom as a ring constituent element.
  • the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom.
  • A is preferably an aromatic heterocyclic group having at least one nitrogen atom as a ring constituent.
  • the aromatic heterocyclic group include a 5-membered aromatic heterocyclic group having a nitrogen atom such as a pyrrolyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, and a triazolyl group; a pyridyl group, a pyridinyl group and a pyridazinyl group.
  • 6-membered aromatic heterocyclic group having a nitrogen atom and condensed ring aromatic heterocyclic groups such as benzimidazolyl group and indolyl group.
  • Examples of the substituent in A include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a sulfo group, a sulfamoyl group, an alkylsulfonyl group having 1 to 6 carbon atoms, and an amino group which may have a substituent. And specifically, the same substituents as those exemplified for R 9A to R 12A can be mentioned.
  • A is preferably a group represented by formula (t1).
  • R 56 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.
  • X2 represents -O-, -N (R 57 )-or -S-.
  • R 57 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 45 and R 46 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a saturated hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.
  • Examples of the aromatic heterocyclic group which may have a substituent, which represents A, include groups represented by the following formulas. * Represents a bond with a carbon atom.
  • X2 is preferably -S-.
  • R 56 is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and more preferably a phenyl group which may have a substituent.
  • R 45 and R 46 are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent.
  • a hydrocarbon group is preferable, and an alkyl group having 1 to 6 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent.
  • one is an alkyl group having 1 to 6 carbon atoms which may have a substituent, and the other is an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent.
  • A is preferably a group represented by formula (A1-12) or formula (A1-13).
  • [Y] m- includes known anions, but from the viewpoint of heat resistance, at least one selected from the group consisting of boron-containing anions, aluminum-containing anions, fluorine-containing anions, and tungsten, molybdenum, silicon and phosphorus. Anions containing one element and oxygen are preferred.
  • Examples of the boron-containing anion and the aluminum-containing anion include anions represented by the following formula (4).
  • W 1 and W 2 each independently represent a group having at least two monovalent proton-donating substituents and two substituents formed by releasing a proton from the group.
  • M represents a boron atom or an aluminum atom.
  • the group having at least two monovalent proton-donating substituents and having two substituents formed by releasing a proton from the group is a monovalent proton-donating substituent (eg, hydroxy group, carboxy group, etc.).
  • a group obtained by releasing a proton from each of two proton-donating substituents from a compound having at least two of The compound is preferably catechol 2,3-dihydroxynaphthalene, 2,2′-biphenol, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, binaphthol. , Salicylic acid, benzylic acid, or mandelic acid as a substituent, which may have a substituent.
  • substituents examples include a halogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a nitro group; a hydroxy group; and an amino group.
  • Examples of the anion represented by the formula (4) include anions represented by the following formula.
  • R 61 , R 62 , R 63 and R 64 are each independently a hydrogen atom, a hydroxy group, an amino group, a nitro group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
  • 4 represents a haloalkyl group having 4 or an alkoxy group having 1 to 4 carbon atoms.
  • anions (BC-1) to anions (BC-28) described below can be mentioned.
  • M represents a boron atom or an aluminum atom.
  • TBu in Table 1 represents a tert-butyl group.
  • fluorine-containing anion examples include anions represented by the following formula (6), (7), (8), or (9).
  • W 3 and W 4 each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W 3 and W 4 are bonded to each other to have 1 to 4 carbon atoms.
  • the fluorinated alkanediyl group of 4 is formed.
  • W 5 , W 6 and W 7 each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.
  • Y 1 represents a fluoroalkanediyl group having 1 to 4 carbon atoms.
  • Y 2 represents a fluorinated alkyl group having 1 to 4 carbon atoms.
  • the fluoroalkyl group having 1 to 4 carbon atoms represented by W 3 to W 7 in the formulas (6) and (7) is preferably a perfluoroalkyl group, for example, —CF 3 , —CF 2 CF 3 , Examples thereof include CF 2 CF 2 CF 3 , —CF (CF 3 ) 2 , —CF 2 CF 2 CF 2 CF 3 , —CF 2 CF (CF 3 ) 2 and —C (CF 3 ) 3 .
  • the fluoroalkanediyl group having 2 to 4 carbon atoms formed by combining W 3 and W 4 is preferably a perfluoroalkanediyl group, for example, —CF 2 CF 2 —, —CF 2 CF 2 CF 2 —, —CF 2 CF 2 CF 2 — and the like can be mentioned.
  • perfluoro alkanediyl group is preferred, for example, -CF 2 -, - CF 2 CF2 -, - CF 2 CF 2 Examples thereof include CF 2 —, —C (CF 3 ) 2 —, —CF 2 CF 2 CF 2 CF 2 — and the like.
  • a perfluoroalkyl group is preferable, and —CF 3 , —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —CF (CF 3 ) 2 , —CF 2 CF 2 CF 2 CF 3 , —CF 2 CF (CF 3 ) 2 , —C (CF 3 ) 3 and the like.
  • anion (6) examples include the following anions (6-1) to (6-6).
  • anion (7) examples include the following anions (7-1).
  • anion (8) examples include the following anions (8-1) to (8-4).
  • anion (9) examples include the following anions (9-1) to (9-4).
  • [Y] m-in includes an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and oxygen.
  • anions of heteropolyacid or isopolyacid are preferable, and anions of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid are more preferable.
  • the anions of such a heteropoly acid or isopoly acid containing tungsten include Keggin-type phosphotungstic acid ion ⁇ - [PW 12 O 40 ] 3- , Dawson-type phosphotungstic acid ion ⁇ - [P 2 W 18 O 62 ].
  • Examples of anions composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus include SiO 3 2 — and PO 4 3 —.
  • heteropoly acid anions such as Keggin-type phosphotungstate ion, Dawson-type phosphotungstate ion and Keggin-type silicotungstate ion, and isopoly acid anion such as [W 10 O 32 ] 4- preferable.
  • salt represented by the formula (A-VI) include salts represented by the following formulas (A-VI-1) to (A-VI-27).
  • the dye (A1) preferably contains a salt represented by the formula (A-VI-27).
  • the hydrone When it has a sulfo group (—SO 3 H) as a substituent, the hydrone may be exchanged with an arbitrary cation to form a salt.
  • the optional cation include an alkali metal ion, an organic ammonium ion, and an imidazolium ion which may have a substituent.
  • it When it has a plurality of sulfo groups, it may form a salt with a divalent or higher valent metal ion.
  • the dye (A2) includes a xanthene dye.
  • a known substance can be used as the xanthene dye.
  • the dye (A2) is also referred to as a xanthene dye (A2).
  • the xanthene dye (A2) is a dye containing a compound having a xanthene skeleton in the molecule.
  • Examples of the xanthene dye (A2) include C.I. I. Acid Red 51 (hereinafter, CI Acid Red is omitted and only numbers are described. The same applies to the others.), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10, 11, C.I. I. Basic Violet 10 (Rhodamine B), 11, C.I. I. Solvent Red 218, C.I. I. Mordant Red 27, C.I. I.
  • Reactive Red 36 (Rose Bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999A and xanthene dyes described in Japanese Patent No. 4492760. Those that are soluble in organic solvents are preferred.
  • the xanthene dye (A2) is preferably a dye containing a compound represented by the formula (1a) (hereinafter, sometimes referred to as “compound (1a)”).
  • the compound (1a) may be a tautomer thereof.
  • the content of the compound (1a) in the xanthene dye (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye (A2).
  • R 1a to R 4a each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent.
  • R 1a and R 2a may together form a ring containing a nitrogen atom
  • R 3a and R 4a may together form a ring containing a nitrogen atom.
  • R 5a is, -OH, -SO 3 -, -SO 3 H, -SO 3 - Za +, -CO 2 H, -CO 2 - Za +, -CO 2 R 8a, -SO 3 R 8a or -SO 2 NR 9a represents R 10a .
  • R 6a and R 7a each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • m represents an integer of 0 to 5. When m is 2 or more, plural R 5a 's may be the same or different.
  • a represents an integer of 0 or 1.
  • Xa represents a halogen atom.
  • Za + represents + N (R 11a ) 4 , Na + or K + , and four R 11a 's may be the same or different.
  • R 8a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
  • R 9a and R 10a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH 2 contained in the saturated hydrocarbon group.
  • R 9a and R 10a are each a 3- to 10-membered ring containing a nitrogen atom bonded to each other. It may form a heterocycle.
  • R 11a represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1a to R 4a include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.
  • the aromatic hydrocarbon group substituent which may have a halogen atom, a carboxyl group, -R 8a, -OH, -OR 8a , -SO 3 -, -SO 3 H, -SO 3 - Za + , -CO 2 H, -CO 2 R 8a , -SR 8a , -SO 2 R 8a , -SO 3 R 8a or -SO 2 NR 9a R 10a may be mentioned.
  • substituent -SO 3 -, -SO 3 H , -SO 3 - Za + and -SO 2 NR 9a R 10a is preferably, -SO 3 - Za + and -SO 2 NR 9a R 10a Is more preferable.
  • the color curable resin composition of the present invention containing the compound (1a) can form a color filter with less generation of foreign matter and excellent heat resistance.
  • Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1a to R 4a and R 8a to R 11a include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group.
  • a linear alkyl group such as an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, and an icosyl group; a branched chain alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; Examples thereof include alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and cyclodecyl group.
  • the hydrogen atom contained in the saturated hydrocarbon group in R 1a to R 4a may be substituted with, for example, a carboxy group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom.
  • the hydrogen atom contained in the saturated hydrocarbon group for R 9a and R 10a may be substituted with, for example, a hydroxy group or a halogen atom.
  • Examples of the ring formed by R 1a and R 2a together and the ring formed by R 3a and R 4a together include the following.
  • Examples of —OR 8a include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an icosyloxy group.
  • Examples of —CO 2 R 8a include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group.
  • Examples of —SR 8a include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
  • Examples of —SO 2 R 8a include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
  • Examples of —SO 3 R 8a include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.
  • R 10a includes, for example, a sulfamoyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1
  • R 5a is, -CO 2 H, -CO 2 - Za +, -CO 2 R 8a, -SO 3 -, -SO 3 - Za +, -SO 3 H or SO 2 NHR 9a are preferred, SO 3 -, -SO 3 - Za +, -SO 3 H or SO 2 NHR 9a is more preferable.
  • m is preferably 1 to 4, and more preferably 1 or 2.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 6a and R 7a include the alkyl groups having 1 to 6 carbon atoms among the alkyl groups listed above.
  • Examples of the aralkyl group having 7 to 10 carbon atoms in R 11a include a benzyl group, a phenylethyl group and a phenylbutyl group.
  • Za + is + N (R 11a ) 4 , Na + or K + , and preferably + N (R 11a ) 4 .
  • the + N (R 11a ) 4 it is preferable that at least two of the four R 11a are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms.
  • the total carbon number of the four R 11a is preferably 20 to 80, more preferably 20 to 60.
  • the compound (1a) is preferably a compound represented by the formula (2a) (hereinafter sometimes referred to as “compound (2a)”).
  • the compound (2a) may be a tautomer thereof.
  • R 21a to R 24a each independently represents a hydrogen atom, —R 26a or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. .. R 21a and R 22a may together form a ring containing a nitrogen atom, and R 23a and R 24a may together form a ring containing a nitrogen atom.
  • R 25a represents —SO 3 ⁇ , —SO 3 H, —SO 3 — Z1 + or —SO 2 NHR 26a .
  • m1 represents an integer of 0 to 5. When m1 is 2 or more, a plurality of R 25a may be the same or different.
  • a1 represents an integer of 0 or 1.
  • X1 represents a halogen atom.
  • R 26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a halogen atom or a carboxy group.
  • Z1 + represents + N (R 27a ) 4 , Na + or K + , and four R 27a may be the same or different.
  • R 27a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 21a to R 24a include the same groups as those mentioned above as the aromatic hydrocarbon group of R 1a to R 4a . Hydrogen atoms contained in the aromatic hydrocarbon group, -SO 3 -, -SO 3 H , -SO 3 - Z1 +, it may be substituted by -SO 3 R 26a or -SO 2 NHR 26a.
  • R 21a to R 24a , R 21a and R 23a are independently of each other a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms (the saturated hydrocarbon group has a halogen atom or a carboxy group).
  • R 22a and R 24a are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is —SO 3 — , -SO 3 H, -SO 3 - Z1 +, which is substituted by -SO 3 R 26a or -SO 2 NHR 26a is preferable.
  • R 21a and R 23a are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (the alkyl group may have a halogen atom or a carboxy group), and R 22a and R 24a are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is replaced with —SO 3 — Z1 + or —SO 2 NHR 26a . It has been done.
  • R 21a to R 24a are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).
  • the ring containing a nitrogen atom formed by R 21a and R 22a together, and the ring containing a nitrogen atom formed by R 23a and R 24a together are R 1a and R 2a together.
  • the same as the ring to be formed is mentioned.
  • an aliphatic heterocycle is preferable. Examples of the aliphatic heterocycle include the followings.
  • Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 26a and R 27a include the same groups as those mentioned as the saturated hydrocarbon group in R 8a to R 11a .
  • -R 26a is preferably each independently a methyl group or an ethyl group.
  • R 26a in -SO 3 R 26a and -SO 2 NHR 26a preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6-12 carbon atoms, A 2-ethylhexyl group is more preferred.
  • R 26a is any of these groups, a color filter with less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).
  • Z1 + is + N (R 27a ) 4 , Na + or K + , and preferably + N (R 27a ) 4 .
  • + N (R 27a ) 4 it is preferable that at least two of the four R 27a are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms.
  • the total carbon number of the four R 27a is preferably 20 to 80, more preferably 20 to 60.
  • M1 is preferably 1 to 4, and more preferably 1 or 2.
  • compound (3a) a compound represented by the formula (3a) (hereinafter sometimes referred to as “compound (3a)”) is also preferable.
  • the compound (3a) may be a tautomer thereof.
  • R 31a and R 32a each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group has 6 to 10 carbon atoms.
  • 10 aromatic hydrocarbon groups, a carboxy group or a halogen atom may be substituted, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, —CH 2 — contained in the saturated hydrocarbon group may be replaced by —O—, —CO— or —NR 11a —.
  • R 33a and R 34a each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
  • R 31a and R 33a may together form a ring containing a nitrogen atom
  • R 32a and R 34a may together form a ring containing a nitrogen atom.
  • p and q each independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R 33a may be the same or different, and when q is 2 or more, a plurality of R 34a may be the same or different.
  • R 11a has the same meaning as above. ]
  • Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R 31a and R 32a include groups having 1 to 10 carbon atoms among those in R 8a .
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted the same groups as those for R 1a can be mentioned.
  • the alkoxy group having 1 to 3 carbon atoms include methoxy group, ethoxy group and propoxy group. It is preferable that R 31a and R 32a each independently represent a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (the saturated hydrocarbon group may have a halogen atom or a carboxy group).
  • Examples of the alkyl group having 1 to 4 carbon atoms in R 33a and R 34a include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.
  • Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R 33a and R 34a include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.
  • Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R 33a and R 34a include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.
  • R 33a and R 34a are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
  • integers of 0 and 2 are preferable for p and q, and 0 or 1 is preferable.
  • Examples of the compound (1a) include compounds represented by the formula (1-1) to the formula (1-43).
  • R 40a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.
  • R 26a has the same meaning as in formula (2a).
  • Examples of such a compound include compounds represented by Formula (1-1) to Formula (1-8), Formula (1-11), and Formula (1-12).
  • the compounds represented by the formula (1-24) to the formula (1-33) are also preferable in terms of excellent solubility in an organic solvent.
  • the compounds represented by Formula (1-32), Formula (1-44) and Formula (1-97) are also preferable from the viewpoint of improving the chromaticity range and the transmittance of the obtained coating film.
  • xanthene dye (A2) a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Co., Ltd.) is used. be able to.
  • a commercially available xanthene dye can be used as a starting material and can be synthesized with reference to JP 2010-32999 A.
  • the dye (A3) contains an anthraquinone dye.
  • a known substance may be used as the anthraquinone dye.
  • the anthraquinone dye for example, C. I. Solvent Yellow 117 (hereinafter, CI Solvent Yellow and the like are omitted and only the numbers are described), 163, 167, 189, C. I. Solvent Orange 77, 86, C. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C. I.
  • the anthraquinone dye is preferably one that dissolves in an organic solvent.
  • the dye (A4) includes a tetraazaporphyrin dye.
  • the tetraazaporphyrin dye is a compound having a tetraazaporphyrin skeleton in the molecule.
  • the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.
  • Examples of the pigment include organic pigments and inorganic pigments, and compounds included in the pigments according to the color index (published by The Society of Dyers and Colorists).
  • the pigments may be used alone or in combination of two or more.
  • 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, 185, 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 particle size of the pigment is preferably uniform.
  • the pigment can be made into a pigment dispersion liquid that is uniformly dispersed in the pigment dispersant solution by performing a dispersion treatment with the pigment dispersant included.
  • Each of the pigments may be subjected to a dispersion treatment alone or a mixture of a plurality of pigments may be subjected to a dispersion treatment.
  • pigment dispersant examples include cationic, anionic, nonionic, amphoteric, polyester, polyamine and acrylic pigment dispersants. 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 BASF Co., Ltd.
  • Azisper trade names
  • the amount used is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the pigment.
  • the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniform dispersion state tends to be obtained.
  • the content of the colorant (A) in the colored curable resin composition is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass based on the total amount of solids in the colored curable resin composition. It is from 60% by mass to 60% by mass, more preferably from 5% by mass to 50% by mass. When the content of the colorant (A) is within the above range, desired spectrum and color density can be obtained.
  • the “total amount of solids in the colored curable resin composition” refers to the total amount of components excluding the solvent (E) from 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 colorant (A) preferably contains at least one selected from the group consisting of dyes (A1) to (A4), and more preferably contains dyes (A1) and (A2).
  • the colorant (A) preferably comprises a salt represented by the above formula (A-VI), more preferably a salt represented by the above formula (A-VI-27).
  • the colorant (A) can be contained as a dispersion liquid in which the dye (A1) is dispersed in a solvent.
  • the colorant (A) preferably contains a xanthene dye (A2), more preferably a compound represented by the above formula (1a), and even more preferably a compound represented by the above formula (2a).
  • the colorant (A) preferably contains a salt represented by the above formula (A-VI) and a compound represented by the above formula (1a), and more preferably the above formula (A).
  • -VI-27 a compound represented by the formula (1-32), a compound represented by the formula (1-44) and a compound represented by the formula (1-97) And at least one selected from the group.
  • the colorant (A) comprises a combination of at least one pigment, preferably selected from the group consisting of dyes (A1) to (A4), and more preferably at least one pigment. It contains a combination of the dye (A1) or the dye (A2) and at least one pigment, more preferably the compound represented by the formula (1a) and at least one red pigment, particularly preferably At least one selected from the group consisting of the compound represented by the formula (1-32), the compound represented by the formula (1-44), and the compound represented by the formula (1-97); I. Pigment Red, and more preferably a compound represented by the formula (1-97): C.I. I. Pigment Red 269 in combination.
  • the colorant (A) contains a pigment
  • the colorant (A) can be contained as a dispersion liquid in which the pigment is dispersed in a solvent.
  • the content of the dye (A1) in the colorant (A) is preferably 0.5% by mass or more and 100% by mass or less, more preferably 61% by mass. Or more and 99.5 mass% or less, and more preferably 81 mass% or more and 99 mass% or less.
  • the content of the dye (A2) in the colorant (A) is preferably 0.1% by mass or more and 80% by mass or less, more preferably 0.3% by mass or more. It is from 40% by mass to 40% by mass, more preferably from 0.5% by mass to 20% by mass.
  • the mass ratio [(A1) :( A2)] of the dye (A1) and the dye (A2) in the colorant (A) is, for example, It may be 0.01: 99.99 to 99.99: 0.01, preferably 50:50 to 99.95: 0.05, and more preferably 90:10 to 99.9: 0.1. Is.
  • the mass ratio [(A1): pigment] of the dye (A2) and the pigment in the colorant (A) is, for example, 1:99 to 99: 1. May be, preferably 5:95 to 50:50, more preferably 10:90 to 30:70.
  • the colored curable resin composition contains a solvent (hereinafter, also referred to as a solvent (E))
  • a colorant-containing solution containing a colorant (A) and a solvent (E) is prepared in advance, and then the colorant-containing solution is contained.
  • a colored curable resin composition may be prepared using a liquid.
  • the colorant-containing liquid can be prepared as a dispersion by dispersing the colorant (A) in the solvent (E) and mixing them.
  • the colorant-containing liquid may contain a part or all of the solvent (E) contained in the colored curable resin composition.
  • the content of the solid content in the colorant-containing liquid is preferably 0.1% by mass or more and 99.9% by mass or less, more preferably 1% by mass or more and 90% by mass or less, based on the total amount of the colorant-containing liquid. Yes, more preferably 1% by mass or more and 60% by mass or less, and particularly preferably 3% by mass or more and 50% by mass or less.
  • the content of the colorant (A) in the colorant-containing liquid is preferably 0.01% by mass or more and 100% by mass or less, more preferably 0.1% by mass in the total amount of solids in the colorant-containing liquid. % Or more and 99.9 mass% or less, more preferably 1 mass% or more and 99 mass% or less, and particularly preferably 10 mass% or more and 90 mass% or less.
  • the “total amount of solids in the colorant-containing liquid” refers to the total amount of components excluding the solvent (E) from the colorant-containing liquid.
  • 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 colorant (A) can be made to be in a state of being uniformly dispersed in the colorant-containing liquid by subjecting the colorant (A) to a dispersant and performing a dispersion treatment.
  • dispersant examples include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples thereof include polyester-based, polyamine-based, and acrylic-based surfactants. You may use these dispersants individually or in combination of 2 or more types.
  • dispersant KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Sols Perth (registered trademark) (manufactured by Zeneca Corporation), and EFKA (registered trademark) are trade names.
  • the amount of the dispersant (solid content) used is preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the colorant (A). And more preferably 5 parts by mass or more and 50 parts by mass or less.
  • the amount of the dispersant used is in the above range, a more uniformly dispersed colorant-containing liquid tends to be obtained.
  • Resin (B) In the colored curable resin composition, the resin (B) contains a resin represented by the following formula [hereinafter, also referred to as resin (B1)].
  • Z represents a residue of tetracarboxylic acid having an alicyclic skeleton.
  • G represents a hydrogen atom or -CO-X- (CO 2 H) x
  • X represents a residue of a (x + 1) -valent polycarboxylic acid
  • x represents an integer of 1 or more and 3 or less.
  • R 1 represents a hydrogen atom or a methyl group, and a plurality of R 1 may be the same as or different from each other.
  • R 2 represents an alkyl group or a halogen atom having 1 to 5 carbon atoms, if R 2 there are a plurality, R 2 of the plurality of may well, or different and the same as each other.
  • k represents an integer of 0 or more and 10 or less
  • n represents an integer of 0 or more and 4 or less
  • m represents an integer of 1 or more and 50 or less.
  • tetracarboxylic acid having an alicyclic skeleton in Z examples include a tetracarboxylic acid having at least one alicyclic skeleton having 4 to 12 carbon atoms.
  • cycloalkanetetracarboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid.
  • Carboxylic acid bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, dicyclohexyl 3,3′-4,4′-tetracarboxylic acid and their positional isomers, etc. Is mentioned.
  • the tetracarboxylic acid residue having an alicyclic skeleton in Z is preferably a tetracarboxylic acid residue having an alicyclic skeleton having 4 to 10 carbon atoms, and having an alicyclic skeleton having 4 to 6 carbon atoms.
  • the residue of tetracarboxylic acid is more preferable, the structure represented by the following formulas (Z-1) to (Z-5) is further preferable, and the residue of tetracarboxylic acid having a saturated alicyclic skeleton having 4 to 6 carbon atoms is preferable.
  • a group is even more preferable, and a structure represented by formula (Z-1) is particularly preferable.
  • * represents a bond with —CO (O) — in the main chain
  • ** represents a bond with a carboxy group.
  • Z is a structure represented by formula (Z-1).
  • examples of the (x + 1) -valent polycarboxylic acid in X include malonic acid, succinic acid, glutaric acid, adipic acid, tricarballylic acid, t-aconitic acid, and trimellitic acid.
  • x represents an integer of 1 or more and 3 or less.
  • Examples of X include a structure represented by the following formula.
  • * represents a bond with a carbon atom of —CO—
  • ** represents a bond with a carboxy group.
  • Examples of —CO—X— (CO 2 H) x in G are structures represented by the following formulas (G-1) to (G-7).
  • * represents a bond with an oxygen atom
  • R represents a carboxy group.
  • alkyl group having 1 to 5 carbon atoms in R 2 examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group and the like. ..
  • halogen atom in R 2 examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • ⁇ represents an integer from 0 to 10 inclusive.
  • N represents an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less, and more preferably 0.
  • ⁇ m represents an integer from 1 to 50.
  • resin (B1) examples include resins represented by the formulas (B1-1) to (B1-19) shown in the table below.
  • the resin (B1) is preferably a resin represented by the formula (B1-1), the formula (B1-6) to the formula (B1-19).
  • the acid value of the resin (B1) in terms of solid content may be, for example, 80 mg-KOH / g or more and 140 mg-KOH / g or less, and 100 mg-KOH / g or more and 130 mg-KOH / g or less, 100 mg-KOH / g. It may be 120 mg-KOH / g or less, or 120 mg-KOH / g or more and 130 mg-KOH / g or less.
  • the weight average molecular weight (Mw) in terms of polystyrene may be, for example, 1,000 or more and 15,000 or less, the weight average molecular weight (Mw) may be 5,000 or more and 13,000 or less, and the weight average molecular weight (Mw) is It may be 6000 or more and 8000 or less, and the weight average molecular weight (Mw) may be 9000 or more and 12000 or less.
  • the resin (B1) is a bisphenol A type epoxy (meth) acrylate or a modified product ( ⁇ ) of a divalent to tetravalent carboxylic acid thereof [hereinafter, also simply referred to as “( ⁇ )”. ], And a tetracarboxylic dianhydride ( ⁇ ) having an alicyclic skeleton [hereinafter, also simply referred to as “( ⁇ )”. ] It is obtained by reacting with.
  • the “(meth) acrylate” represents at least one selected from the group consisting of acrylate and methacrylate. The same applies to other terms with "(meta)”.
  • the divalent to tetravalent carboxylic acid is, for example, the (x + 1) -valent polyvalent carboxylic acid exemplified in the description of G in the above formula (B1), such as malonic acid, succinic acid, glutaric acid, adipic acid, tricarballylic acid, and t. -Aconitic acid, trimellitic acid and the like can be mentioned.
  • ( ⁇ ) include anhydrides of tetracarboxylic acids having an alicyclic skeleton exemplified for Z in the above formula (1).
  • Specific examples thereof include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride.
  • Cycloalkanetetracarboxylic acid dianhydrides such as acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, dicyclohexyl 3,3 ′, 4,4′-tetracarboxylic dianhydride and positional isomers thereof are included.
  • Examples of the method for producing the resin (B1) include a method in which a predetermined amount of ( ⁇ ) and ( ⁇ ), a solvent and the like are charged into a reaction vessel, and stirring, heating, and heat retaining are performed in a deoxygenated atmosphere. ..
  • the solvent any solvent capable of dissolving ( ⁇ ) and ( ⁇ ) may be used, and examples thereof include propylene glycol monomethyl ether.
  • the obtained resin (B1) may be used as the solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. May be used.
  • the solvent (E) described below is used as a solvent in this polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.
  • the reaction can be carried out, for example, by adding 1 to 50 parts by mass of ( ⁇ ) to 100 parts by mass of ( ⁇ ).
  • the polystyrene equivalent weight average molecular weight (Mw) of the resin (B1) is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 50,000 or less, and further preferably 3,000 or more. It is 30,000 or less, and particularly preferably 5,000 or more and 15,000 or less.
  • Mw weight average molecular weight
  • the acid value of the resin (B1) in terms of solid content is preferably 5 mg-KOH / g or more and 200 mg-KOH / g or less, more preferably 50 mg-KOH / g or more and 180 mg-KOH / g or less. It is preferably 80 mg-KOH / g or more and 150 mg-KOH / g or less.
  • the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by, for example, titration with an aqueous potassium hydroxide solution.
  • the content of the resin (B1) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less in 100% by mass of the solid content of the colored curable resin composition. It is more preferably 15% by mass or more and 40% by mass or less. When the content of the resin (B1) is in the above range, the solubility of the unexposed portion in the developing solution tends to be high.
  • the resin (B) may further contain one kind or two or more kinds of resin different from the resin (B1) (hereinafter, also referred to as resin (B2)).
  • the resin (B2) is preferably an alkali-soluble resin.
  • Alkali-soluble refers to the property of being dissolved in a developer which is an aqueous solution of an alkali compound.
  • Examples of the resin (B2) include the following resins [K1] to [K6].
  • Resin [K1] at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides [hereinafter, sometimes referred to as "monomer (a)”. ] And a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "monomer (b)". ) With a copolymer.
  • Resin [K2] a monomer (a), a monomer (b), and a monomer copolymerizable with the monomer (a) (however, the monomer (a) and the monomer (b)) The following may be referred to as "monomer (c)".
  • Resin [K3] Copolymer of monomer (a) and monomer (c).
  • Resin [K4] A resin obtained by reacting the copolymer of the monomer (a) and the monomer (c) with the monomer (b).
  • Resin [K5] A resin obtained by reacting the copolymer of the monomer (b) and the monomer (c) with the monomer (a).
  • Resin [K6] A resin obtained by reacting the copolymer of the monomer (b) and the monomer (c) with the monomer (a) and further reacting with a carboxylic acid anhydride.
  • Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-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-
  • (a) is preferably (meth) acrylic acid, maleic anhydride or the like, from the viewpoint of copolymerization reactivity and the solubility in an alkaline aqueous solution.
  • (meth) acrylic means at least one selected from the group consisting of acrylic and methacrylic. The same applies to expressions such as “(meth) acryloyl” and “(meth) acrylate”.
  • the monomer (b) includes 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 (oxolane ring)) and an ethylenically unsaturated bond.
  • a polymerizable compound having The monomer (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
  • the monomer (b) may be a monomer having an oxiranyl group and an ethylenically unsaturated bond [hereinafter, referred to as "monomer (b1)". ] (B2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as a monomer "(b2)”. ], A monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as “monomer (b3)”]. ] Etc. are mentioned.
  • (B1) may be a monomer having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter, referred to as “monomer (b1-1)”. ] A monomer having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon [hereinafter, sometimes referred to as "monomer (b1-2)”. ] Is mentioned.
  • Examples of the monomer (b1-1) include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, ⁇ -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, and m-vinylbenzylglycidyl.
  • Examples of the monomer (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth). Acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) And a compound represented by the formula (II).
  • vinylcyclohexene monooxide for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.
  • Acrylate for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.
  • 3,4-epoxycyclohexylmethyl (meth) acrylate for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.
  • R aa and R ab independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. May be replaced with.
  • X a1 and X a2 are each independently a single bond, * - R ac -, * - R ac -O -, * - R ac -S-, or * -R represents the ac -NH-.
  • R ac 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.
  • R aa and R ab are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.
  • the alkanediyl group constituting R ac is a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-group. Examples thereof include a diyl group and a hexane-1,6-diyl group.
  • X a1 and X a2 are preferably a single bond, a methylene group, an ethylene group, a * —CH 2 —O— (* represents a bond with O) group, or a * —CH 2 CH 2 —O— group. , And more preferably a single bond or a * —CH 2 CH 2 —O— group.
  • Specific examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15), preferably the formula (I-1) and the formula (I-3). ), The formula (I-5), the formula (I-7), the formula (I-9), the formula (I-11) to the formula (I-15), and more preferably the formula (I-15). Examples thereof include compounds represented by I-1), formula (I-7), formula (I-9) and formula (I-15).
  • the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15), preferably the formula (II-1) and the formula (II- 3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15), and more preferably Formula Examples thereof include compounds represented by (II-1), formula (II-7), formula (II-9) and formula (II-15).
  • the compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can be mixed in any ratio.
  • the mixing ratio is represented by the formula (I): formula (II) [molar ratio], preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and further preferably 20 :. 80 to 80:20.
  • the monomer (b2) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.
  • Preferred examples of the monomer (b2) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxy. Examples thereof include ethyl oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.
  • the monomer (b3) is preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.
  • Preferred examples of the monomer (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.
  • Tricyclodecyl (meth) acrylate It may also be called “tricyclodecyl (meth) acrylate”. ] Tricyclo [5.2.1.0 2,6 ] decen-8-yl (meth) acrylate [in the art, commonly known as “dicyclopentenyl (meth) acrylate”.
  • Dicyclopentanyloxyethyl (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) acrylic acid ester such as (meth) acrylate; Hydroxy group-containing (meth) acrylic acid ester 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 [
  • examples of (c) include benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, Bicyclo [2.2.1] hept-2-ene and the like are preferable. Further, benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferable as (c) because they are excellent in developability during pattern formation.
  • the ratio of the structural units derived from each is preferably in the following range in all the structural units constituting the resin [K1].
  • the resin [K1] is described in the literature “Experimental method for polymer synthesis” (Takayuki Otsu, Kagaku Dojin, 1st edition, 1st edition, published on March 1, 1972) and the literature. It can be manufactured by referring to the cited references. Specifically, a predetermined amount of the monomer (a) and the monomer (b) (particularly the monomer (b1)), a polymerization initiator, a solvent and the like are charged into a reaction vessel, and the reaction is performed under a deoxygenated atmosphere. , Stirring, heating, and heat retention.
  • the polymerization initiator, solvent and the like used here are not particularly limited, and any of those commonly used in the art can be used.
  • the polymerization initiator examples include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Be done.
  • the solvent any solvent capable of dissolving each monomer may be used, and the solvent (E) described later or the like can be used as the solvent of the colored curable resin composition.
  • the obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. May be used.
  • the solvent (E) described below is used as a solvent in this polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.
  • the ratio of the structural units derived from each is preferably in the following range in all the structural units constituting the resin [K2].
  • the resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1]. Specifically, the reaction vessel is charged with a predetermined amount of the monomer (a), the monomer (b) (particularly the monomer (b1)) and the monomer (c), a polymerization initiator and a solvent. A method of stirring, heating, and keeping heat under a deoxygenated atmosphere can be mentioned.
  • the obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. May be used.
  • the ratio of the structural units derived from each is preferably in the following range in all the structural units constituting the resin [K3].
  • the resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1].
  • the resin [K4] is a cyclic ether structure having 2 to 4 carbon atoms contained in the monomer (b) obtained by obtaining a copolymer of the monomer (a) and the monomer (c), particularly a monomer. It can be produced by adding the oxirane ring of (b1) to the carboxylic acid and / or carboxylic acid anhydride of the monomer (a). Specifically, first, a copolymer of the monomer (a) and the monomer (c) is produced in the same manner as the method described as the method for producing the resin [K1].
  • the ratio of the structural units derived from each is preferably in the following range in all structural units constituting the copolymer of the monomer (a) and the monomer (c).
  • a part of the carboxylic acid and / or carboxylic acid anhydride derived from the monomer (a) in the above copolymer has a cyclic ether structure having 2 to 4 carbon atoms, which the monomer (b) has.
  • the oxirane ring of the monomer (b1) is reacted.
  • the atmosphere in the flask is replaced with nitrogen from air to obtain the monomer (b) (particularly, the monomer).
  • the resin [K4] can be obtained by reacting at 130 ° C. for 1 to 10 hours.
  • the amount of the monomer (b) used, particularly the amount of the monomer (b1) used, is preferably 5 mol or more and 80 mol or less, more preferably 10 mol or more 75 with respect to 100 mol of the monomer (a). It is less than or equal to mol.
  • the monomer (b1) is preferable as the monomer (b) used in the resin [K4] because the reactivity of the cyclic ether structure is high and the unreacted monomer (b) is unlikely to remain.
  • the body (b1-1) is more preferable.
  • the reaction catalyst is used in an amount of 0.001% by mass or more and 5 with respect to the total amount of the monomer (a), the monomer (b) (particularly the monomer (b1)) and the monomer (c). It is preferably not more than mass%.
  • the amount of the polymerization inhibitor used is preferably 0.001% by mass or more and 5% by mass or less based on the total amount of the monomers (a), (b) and (c). ..
  • Reaction conditions such as a charging method, a reaction temperature and a time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the 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 [K5] is a copolymer of the monomer (b) (particularly the monomer (b1)) and the monomer (c) in the same manner as in the above-mentioned method for producing the resin [K1].
  • a polymer is obtained.
  • 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 ratio of the structural units derived from the monomer (b) (particularly the monomer (b1)) and the monomer (c) is based on the total number of moles of all structural units constituting the above copolymer.
  • the resin [K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in the monomer (a) with the cyclic ether structure derived from The amount of the monomer (a) to be reacted with the above copolymer is 5 mol or more and 80 mol or less with respect to 100 mol of the monomer (b) (particularly the monomer (b1)). preferable.
  • the monomer (b1) is preferably used as the monomer (b) used in the resin [K5] because the cyclic ether structure has high reactivity and the unreacted monomer (b) is unlikely to remain.
  • the body (b1-1) is more preferable.
  • the resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride.
  • the carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction between the cyclic ether structure and the carboxylic acid or the carboxylic acid anhydride.
  • carboxylic acid anhydride examples include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride) and the like. Be done.
  • the resin preferable as the resin (B) is [K1] or [K2].
  • the resin (B2) may be composed of one kind of resin or may contain two or more kinds of resins.
  • the polystyrene equivalent weight average molecular weight (Mw) of the resin (B2) is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, and further preferably 5,000 or more. It is 30,000 or less.
  • the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B2) is preferably 1.1 to 6, and more preferably 1.2 to 4.
  • the acid value of the resin (B2) in terms of solid content is preferably 5 mg-KOH / g or more and 200 mg-KOH / g or less, more preferably 50 mg-KOH / g or more and 180 mg-KOH / g or less. It is preferably 60 mg-KOH / g or more and 140 mg-KOH / g or less.
  • the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by, for example, titration with an aqueous potassium hydroxide solution.
  • the content of the resin (B2) in the solid content of the colored curable resin composition is preferably 1% by mass or more and 50% by mass or less, and 3% by mass. % To 40% by mass.
  • the content of the resin (B2) is in the above range, the solubility of the unexposed area in the developing solution tends to be high.
  • the content of the resin (B) in the solid content of the colored curable resin composition is preferably 7% by mass or more and 65% by mass or less, more preferably 13% by mass or more and 60% by mass or less, and further preferably It is 17% by mass or more and 55% by mass or less.
  • 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 colorant-containing liquid is a resin (described below) contained in the colored curable resin composition ( Part or all of B), preferably part, may be contained in advance.
  • the resin (B) in advance, the dispersion stability of the colorant-containing liquid can be further improved.
  • the colorant-containing liquid contains the resin (B2) in advance.
  • the content of the resin (B) in the colorant-containing liquid may be, for example, 10000 parts by mass or less, preferably 5000 parts by mass or less, and more preferably 1000 parts by mass with respect to 100 parts by mass of the coloring agent (A).
  • the amount is not more than 1 part by mass, more preferably not less than 1 part by mass and not more than 500 parts by mass, particularly preferably not less than 5 parts by mass and not more than 200 parts by mass, particularly preferably not less than 10 parts by mass and not more than 100 parts by mass.
  • the polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical or the like generated from the polymerization initiator (D) by light irradiation or the like, and a compound having a polymerizable ethylenically unsaturated bond and the like. Is mentioned.
  • the weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less, and more preferably 1,500 or less.
  • the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and 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 Examples thereof include pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipenta
  • the colored curable resin composition of the present invention may contain one or more polymerizable compounds (C).
  • the content of the polymerizable compound (C) is preferably 20 parts by mass or more and 150 parts by mass or less, more preferably 40 parts by mass or more, with respect to 100 parts by mass of the resin (B) in the colored curable resin composition. It is 110 parts by mass or less.
  • the content of the polymerizable compound (C) is preferably 7% by mass or more and 65% by mass or less, more preferably 13% by mass or more and 60% by mass or less, and further preferably, based on the total amount of the solid content. It is 17% by mass or more and 55% by mass or less.
  • 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 that can generate an active radical, an acid or the like by the action of light or heat and initiates polymerization, and a known polymerization initiator can be used.
  • Examples of the polymerization initiator (D) include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.
  • the polymerization initiator (D) may be used in combination of two or more in consideration of sensitivity, formability of precise pattern shape, and the like.
  • the polymerization initiator (D) preferably contains an oxime compound such as an O-acyl oxime compound because it is advantageous in precisely forming a pattern shape having sensitivity and a desired line width.
  • the O-acyl oxime compound is a compound having a structure represented by the formula (d).
  • * represents a bond.
  • 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 compound is N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- From the group consisting of 1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine At least one selected is preferable.
  • Commercially available products such as Irgacure OXE01, OXE02, OXE03 (all manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may be used. When these O-acyl oxime compounds are used, a color filter having excellent photolithographic performance tends to be obtained.
  • the alkylphenone compound is a compound having a structure represented by the formula (d4) or a structure represented by the formula (d5). * Represents a bond.
  • the benzene ring may have a substituent.
  • Examples of the compound having the structure represented by the formula (d4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl ) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one and the like. Be done.
  • Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF Corp.) may be used.
  • Examples of the compound having the structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy). ) Phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, ⁇ , ⁇ -diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal. From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d4).
  • biimidazole compound examples include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-Tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4'.
  • triazine compound examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl).
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • 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, 2 -Quinone compounds such as ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenyl
  • the content of the polymerization initiator (D) is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 2 parts by mass or more and 20 parts by mass or less.
  • the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time is shortened, so that the productivity of the color filter tends to be improved.
  • the polymerization initiation aid (D1) is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator.
  • the polymerization initiator auxiliary agent (D1) is contained, it is used in combination with the polymerization initiator (D).
  • the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds. Of these, thioxanthone compounds are preferable. You may use together 2 or more types of polymerization initiation assistants (D1).
  • amine compound triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly called Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Examples include ethylmethylamino) benzophenone, and among them, 4,4′-bis (diethylamino) benzophenone is preferable.
  • EAB-F manufactured by Hodogaya Chemical Co., Ltd.
  • alkoxyanthracene compound examples include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and 9,10-dibutoxy. Examples thereof include anthracene and 2-ethyl-9,10-dibutoxyanthracene.
  • thioxanthone compound examples include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.
  • phenylsulfanyl acetic acid methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.
  • the content of the polymerization initiation aid (D1) is preferably 0.1 part by mass or more and 30 parts by mass or less, and more preferably 1 part by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is from 20 parts by mass to 20 parts by mass.
  • the content of the polymerization initiation aid (D1) is within the above range, a blue pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.
  • the colored curable resin composition of the present invention preferably contains one or more solvents (E).
  • an ester solvent a solvent containing —COO—
  • an ether solvent other than the ester solvent a solvent containing —O—
  • an ether ester solvent a solvent containing —COO— and —O—
  • examples thereof include ketone solvents (solvents containing —CO—) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.
  • 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 solvents 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, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.
  • Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Etc.
  • alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.
  • aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.
  • amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
  • the solvent (E) preferably contains an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm from the viewpoint of coating property and drying property.
  • the solvent (E) is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3 -Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferably contained, and at least one selected from the group consisting of propylene glycol monomethyl ether acetate and propylene glycol monomethyl is preferred.
  • At least one selected from the group consisting of ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate is included.
  • the content of the solvent (E) in the colored curable resin composition is preferably 70% by mass or more and 95% by mass or less, more preferably 75% by mass or more and 92% by mass or less.
  • the solid content of the colored curable resin composition is preferably 5% by mass or more and 30% by mass or less, more preferably 8% by mass or more and 25% by mass or less.
  • Leveling agent (F) The colored curable resin composition of the present invention may contain one kind or two or more kinds of leveling agents (F).
  • leveling agent (F) include silicone-based surfactants (having no fluorine atom), fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
  • silicone-based surfactants include surfactants having a siloxane bond in the molecule.
  • Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324. , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 (manufactured by Momentive Performance Materials Japan LLC), etc. Can be mentioned.
  • fluorinated surfactant examples include surfactants having a fluorocarbon chain in the molecule.
  • Florade registered trademark
  • FC430 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 include Megafac (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).
  • the content of the leveling agent (F) is usually 0.001% by mass or more and 0.6% by mass or less, preferably 0.002% by mass or more and 0.4% by mass or less, in the colored curable resin composition. Preferably it is 0.005 mass% or more and 0.3 mass% or less.
  • the content of the pigment dispersant is not included in this content.
  • a filler if necessary, a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an antioxidant, an aggregation preventive agent.
  • a filler if necessary, a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an antioxidant, an aggregation preventive agent.
  • One or more kinds of additives such as an agent, an organic acid, an organic amine compound, and a curing agent can be contained.
  • the colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and optionally a solvent (E) and a leveling agent ( It can be prepared by mixing F), the polymerization initiation aid (D1) and other components.
  • the colored curable resin composition of the present invention is useful as a material for a color filter.
  • a color filter formed from the colored curable resin composition of the present invention also falls within the scope of the present invention.
  • the color filter may form a colored pattern.
  • 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, and a photolithographic method is preferable.
  • the photolithographic method is a method in which a colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed.
  • a colored coating film that is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and / or not developing.
  • a colored pattern or a colored coating film formed from the colored curable resin composition of the present invention is the color filter of the present invention.
  • the color filter according to the present invention is typically used as a colored pixel.
  • each colored pixel by the photolithography method can be performed by a known or commonly used apparatus and conditions, and can be produced, for example, as follows.
  • a 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 5 minutes, more preferably 30 seconds to 3 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 a desired 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.
  • examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
  • the exposure since it is possible to uniformly illuminate the entire exposed surface with parallel light rays and perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed, exposure of the mask aligner and stepper, etc. Preference is given to using the device.
  • a colored pattern is formed on the substrate by bringing the colored composition layer after exposure into contact with a developing solution for development.
  • the developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide.
  • 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 developing solution 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. Furthermore, it is preferable to perform post-baking on the obtained colored pattern.
  • the post-baking temperature is preferably 150 ° C or higher and 250 ° C or lower, more preferably 160 ° C or higher and 235 ° C or lower.
  • the post-baking time is preferably 1 minute or more and 120 minutes or less, more preferably 10 minutes or more and 60 minutes or less.
  • the thickness of the obtained colored pattern affects adjacent pixels, so it is preferable that the thickness is as thin as possible. Especially when a thick film is used, light from a light source may leak through pixels of two or more colors when a liquid crystal panel is manufactured. May be lost.
  • the film thickness of the colored pattern after post-baking is preferably 3 ⁇ m or less, and more preferably 2.8 ⁇ m or less.
  • the lower limit of the thickness of the colored pattern is not particularly limited, but is usually 0.2 ⁇ m or more, and may be 0.5 ⁇ m or more.
  • the colored curable resin composition of the present invention is excellent as a material for a color filter because it exhibits excellent developability during the production of a colored pattern.
  • the colored coating film formed from the colored curable resin composition of the present invention has excellent light resistance and preferably also heat resistance.
  • the colored coating film formed from the colored curable resin composition of the present invention may have a light resistance ( ⁇ Eab * ) of, for example, less than 5.0, preferably 4.9 or less, more preferably 4.8 or less. is there.
  • a colored coating formed from a colored curable resin composition not containing the same colorant according to the present invention in a colored coating film formed from a colored curable resin composition containing a specific colorant, a colored coating formed from a colored curable resin composition not containing the same colorant according to the present invention.
  • the light resistance ( ⁇ Eab * ) of the colored coating film can be reduced by, for example, 0.5 or more, preferably 1.0 or more, and more preferably 2.0 or more, as compared with the film.
  • the light resistance ( ⁇ Eab * ) can be measured according to the method described in the Examples section below.
  • the color filter according to the present invention has excellent light resistance, preferably heat resistance and developability, and thus is used for display devices such as liquid crystal display devices, organic EL devices, electronic papers, and solid-state imaging devices. It is useful as a filter.
  • 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.
  • Device HLC-8120GPC (manufactured by Tosoh Corporation) Column; TSK-GELG2000HXL Column temperature: 40 ° C Solvent; THF Flow rate: 1.0 mL / min Test liquid solid content concentration: 0.001 to 0.01% by mass Injection volume: 50 ⁇ L 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.
  • the acid value in terms of solid content of the resin is a value obtained by titrating a solution containing the resin with an aqueous solution of potassium hydroxide to obtain the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin.
  • k represents an integer of 0 or more and 10 or less
  • m represents an integer of 1 or more and 50 or less.
  • the resin (B2-2) has the following structural units.
  • the obtained colored curable resin composition was evaluated by the following method. The results are shown in Table 3.
  • a colored curable resin composition was applied onto a 2-inch square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer.
  • an exposure device (TME-150RSK; manufactured by Topcon Corp.) was used to irradiate the colored composition layer with light at an exposure amount of 60 mJ / cm 2 (365 nm standard) in an air atmosphere.
  • post-baking was performed in an oven at 230 ° C. for 20 minutes to obtain a colored coating film.
  • the film thickness of the obtained colored coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 3.0 ⁇ m.
  • a colored coating film having excellent light resistance can be formed, which is extremely useful industrially.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention addresses the problem of providing a colored curable resin composition which is capable of forming a colored coating film that has excellent light resistance.　The present invention relates to a colored curable resin composition which contains (A) a coloring agent, (B) a resin, (C) a polymerizable compound and (D) a polymerization initiator, and which is configured such that the resin (B) contains a resin represented by formula (B1).

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し、さらにはカラーフィルタ、表示素子及び固体撮像素子にも関する。 The present invention relates to a colored curable resin composition, and further relates to a color filter, a display device and a solid-state imaging device.
　表示装置や固体撮像素子等に含まれるカラーフィルタを形成する着色硬化性樹脂組成物として、着色剤、バインダー樹脂、重合性化合物及び重合開始剤を含む着色硬化性樹脂組成物が知られている（特許文献１）。 A colored curable resin composition containing a colorant, a binder resin, a polymerizable compound and a polymerization initiator is known as a colored curable resin composition for forming a color filter included in a display device, a solid-state imaging device, or the like ( Patent Document 1).
特開２０１６－１０８２８８号公報JP, 2016-108288, A
　本発明の目的は、耐光性に優れた着色塗膜を形成することができる着色硬化性樹脂組成物を提供することである。 An object of the present invention is to provide a colored curable resin composition capable of forming a colored coating film having excellent light resistance.
　本発明は、以下に示す着色硬化性樹脂組成物、カラーフィルタ、表示素子及び固体撮像素子を提供する。 The present invention provides a colored curable resin composition, a color filter, a display device and a solid-state imaging device shown below.
［１］　着色剤（Ａ）と、樹脂（Ｂ）と、重合性化合物（Ｃ）と、重合開始剤（Ｄ）と、を含有し、前記樹脂（Ｂ）は下記式（Ｂ１）で表される樹脂を含む、着色硬化性樹脂組成物。 [1] Contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the resin (B) is represented by the following formula (B1). A curable colored resin composition containing a resin.
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-I000002
［式中、
　Ｚは、脂環式骨格を有するテトラカルボン酸の残基を表す。
　Ｇは、水素原子又は－ＣＯ－Ｘ－（ＣＯ2Ｈ）ｘを表し、Ｘは（ｘ＋１）価の多価カルボン酸の残基を表し、ｘは１以上３以下の整数を表す。
　Ｒ1は、水素原子又はメチル基を表し、複数のＲ1は、互いに同一であってよく、又は異なっていてもよい。
　Ｒ2は、炭素原子数１以上５以下のアルキル基又はハロゲン原子を表し、Ｒ2が複数存在する場合、該複数のＲ2は、互いに同一であってよく、又は異なっていてもよい。
　ｋは０以上１０以下の整数を表し、ｎは０以上４以下の整数を表し、ｍは１以上５０以下の整数を表す。］
［２］　前記式（Ｂ１）において、Ｚは炭素数４～１０の脂環式骨格を有するテトラカルボン酸の残基である、［１］に記載の着色硬化性樹脂組成物。
［３］　前記式（Ｂ１）において、Ｚは炭素数４～６の飽和脂環式骨格を有するテトラカルボン酸の残基である、［１］又は［２］に記載の着色硬化性樹脂組成物。
［４］　［１］～［３］のいずれかに記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［５］　［４］に記載のカラーフィルタを含む表示素子。
［６］　［５］に記載のカラーフィルタを含む固体撮像素子。 [In the formula,
Z represents a residue of tetracarboxylic acid having an alicyclic skeleton.
G represents a hydrogen atom or —CO—X— (CO 2 H) x, X represents a residue of a (x + 1) -valent polycarboxylic acid, and x represents an integer of 1 or more and 3 or less.
R 1 represents a hydrogen atom or a methyl group, and a plurality of R 1 may be the same as or different from each other.
R 2 represents an alkyl group or a halogen atom having 1 to 5 carbon atoms, if R 2 there are a plurality, R 2 of the plurality of may well, or different and the same as each other.
k represents an integer of 0 or more and 10 or less, n represents an integer of 0 or more and 4 or less, and m represents an integer of 1 or more and 50 or less. ]
[2] The colored curable resin composition according to [1], wherein in the formula (B1), Z is a residue of a tetracarboxylic acid having an alicyclic skeleton having 4 to 10 carbon atoms.
[3] In the formula (B1), Z is a residue of a tetracarboxylic acid having a saturated alicyclic skeleton having 4 to 6 carbon atoms, and the colored curable resin composition according to [1] or [2]. ..
[4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].
[5] A display device including the color filter according to [4].
[6] A solid-state image sensor including the color filter according to [5].
　本発明によれば、耐光性に優れた着色塗膜を形成することができる着色硬化性樹脂組成物が提供される。 According to the present invention, a colored curable resin composition capable of forming a colored coating film having excellent light resistance is provided.
　〔１〕着色剤（Ａ）
　着色硬化性樹脂組成物は、着色剤（Ａ）を含む。着色剤（Ａ）は、染料及び顔料からなる群から選択される少なくとも１種を含む。着色剤（Ａ）は、好ましくは２種の染料の組合せ又は少なくとも１種の染料と少なくとも１種の顔料との組合せを含み、より好ましくは２種の染料の組合せ又は１種の染料と１種の顔料との組合せを含む。 [1] Colorant (A)
The colored curable resin composition contains a colorant (A). The colorant (A) contains at least one selected from the group consisting of dyes and pigments. The colorant (A) preferably comprises a combination of two dyes or a combination of at least one dye and at least one pigment, and more preferably a combination of two dyes or one dye and one dye. In combination with a pigment.
　〔染料〕
　染料としては、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、例えば、カラーインデックス（The Society of Dyers and Colourists出版）でソルベント、アシッド、ベーシック、リアクティブ、ダイレクト、ディスパース、モルダント、又はバット等の染料に分類されている化合物や、染色ノート（色染社）に記載されている公知の染料が挙げられる。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。これらの染料は、単独で用いても２種以上を併用してもよい。染料は、有機溶剤可溶性染料が好ましい。 〔dye〕
As the dye, known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. For example, color index (The Society of Dyers and Colorists publication) solvent, acid, basic, Examples thereof include compounds classified into dyes such as reactive, direct, disperse, moldant, and vat, and known dyes described in Dyeing Note (Shikiso Co., Ltd.). The dye may be appropriately selected according to the desired spectrum of the color filter. These dyes may be used alone or in combination of two or more. The dye is preferably an organic solvent-soluble dye.
　染料の具体例としては、Ｃ．Ｉ．ソルベントイエロー４、１４、１５、２３、２４、３８、６２、６３、６８、８２、９４、９８、９９、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。 Specific examples of the dye include C.I. I. Solvent Yellow 4, 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. Direct greens 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like C.I. 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 Mordant 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.
　また、染料としては、化学構造によれば、トリアリールメタン系染料、キサンテン染料、アゾ染料、シアニン染料、トリフェニルメタン染料、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、スクワリリウム染料、アクリジン染料、スチリル染料、クマリン染料、キノリン染料、ニトロ染料、テトラアザポルフィリン染料等が挙げられる。 As the dye, according to the chemical structure, triarylmethane dye, xanthene dye, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, Examples thereof include squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline dye, nitro dye and tetraazaporphyrin dye.
　染料は、好ましくは以下の染料（Ａ１）～（Ａ４）である。 The dyes are preferably the following dyes (A1) to (A4).
　〔染料（Ａ１）〕
　染料（Ａ１）は、式（Ａ－ＶＩ）で表される塩を含む。染料（Ａ１）には、その互変異性体も含まれる。 [Dye (A1)]
The dye (A1) contains a salt represented by the formula (A-VI). The dye (A1) also includes its tautomer.
Figure JPOXMLDOC01-appb-I000003
Figure JPOXMLDOC01-appb-I000003
［式（Ａ－ＶＩ）中、Ｒ1A～Ｒ8Aは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、スルホニル基、ヒドロキシ基、又は炭素数１～２０の飽和炭化水素基を表し、該飽和炭化水素基を構成するメチレン基間に酸素原子が挿入されていてもよい。
　Ｒ9A～Ｒ12Aは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数６～２０のアリール基、置換基を有していてもよい炭素数７～２０のアラルキル基又は炭素数１～２０の飽和炭化水素基を表し、該アリール基及び該アラルキル基が有していてもよい置換基は、－ＳＯ3 -又は－ＳＯ2－Ｎ-－ＳＯ2－Ｒfであってもよく、該飽和炭化水素基を構成するメチレン基間に酸素原子が挿入されていてもよく、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子又は置換基を有していてもよいアミノ基で置換されていてもよい。Ｒ9AとＲ10Aとが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ11AとＲ12Aとが結合してそれらが結合する窒素原子とともに環を形成してもよい。
　Ａは、置換基を有していてもよい炭素数６～２０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の芳香族複素環基を表し、該芳香族炭化水素基及び該芳香族複素環基が有していてもよい置換基は、－ＳＯ3 -又は－ＳＯ2－Ｎ-－ＳＯ2－Ｒfであってもよい。
　［Ｙ］(m-n)-は、任意の（ｍ－ｎ）価のアニオンを表す。
　ｍは任意の自然数を表す。
　ｎは、置換基として有する－ＳＯ3 -又は－ＳＯ2－Ｎ-－ＳＯ2－Ｒfの数を表し、０又は１である。
　Ｒfは、炭素数１～１２のフルオロアルキル基を表す。］ [In the formula (A-VI), R 1A to R 8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxy group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, An oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group.
R 9A to R 12A are each independently a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 20 carbon atoms which may have a substituent. Alternatively, the aryl group and the substituent that the aralkyl group may have may be a —SO 3 — or —SO 2 —N — —SO 2 —R f , which represents a saturated hydrocarbon group having 1 to 20 carbon atoms. It may be present, an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group, the hydrogen atom contained in the saturated hydrocarbon group may have a halogen atom or a substituent. It may be substituted with a good amino group. R 9A and R 10A may combine to form a ring with the nitrogen atom to which they are bonded, or R 11A and R 12A may combine to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent. The substituent which the hydrocarbon group and the aromatic heterocyclic group may have may be —SO 3 — or —SO 2 —N — —SO 2 —R f .
[Y] (mn) -represents an arbitrary (mn) -valent anion.
m represents an arbitrary natural number.
n is, -SO 3 has - as a substituent, or -SO 2 -N - represents the number of -SO 2 -R f, is 0 or 1.
R f represents a fluoroalkyl group having 1 to 12 carbon atoms. ]
　Ｒ1A～Ｒ12Aで表される、炭素数１～２０の飽和炭化水素基は、直鎖状、分枝鎖状及び環状のいずれであってもよく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ペンチル基、ヘキシル基、２－エチルヘキシル基、デシル基、ドデシル基、イコシル基、シクロヘキシル基、アダマンチル基が挙げられる。 The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 1A to R 12A may be linear, branched or cyclic and includes, for example, a methyl group, an ethyl group and a propyl group. , Isopropyl group, pentyl group, hexyl group, 2-ethylhexyl group, decyl group, dodecyl group, icosyl group, cyclohexyl group and adamantyl group.
　Ｒ1A～Ｒ12Aで表される炭素数１～２０の飽和炭化水素基であって、該飽和炭化水素基を構成するメチレン基間に酸素原子が挿入されている基としては、下記式で表される基が挙げられる。下記式中、＊は炭素原子又は窒素原子との結合手を表す。
なかでも、炭素数１～１０の飽和炭化水素基であって、該飽和炭化水素基を構成するメチレン基間に酸素原子が挿入されている基が好ましく、炭素数１～６の飽和炭化水素基であって、該飽和炭化水素基を構成するメチレン基間に酸素原子が挿入されている基がより好ましい。 The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 1A to R 12A , in which an oxygen atom is inserted between the methylene groups constituting the saturated hydrocarbon group, is represented by the following formula. And the groups mentioned below. In the following formula, * represents a bond with a carbon atom or a nitrogen atom.
Of these, a saturated hydrocarbon group having 1 to 10 carbon atoms in which an oxygen atom is inserted between methylene groups constituting the saturated hydrocarbon group is preferable, and a saturated hydrocarbon group having 1 to 6 carbon atoms is preferable. And a group in which an oxygen atom is inserted between methylene groups constituting the saturated hydrocarbon group is more preferable.
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000004
　Ｒ9A～Ｒ12Aにおける炭素数６～２０のアリール基としては、フェニル基、トルイル基、キシリル基、ナフチル基、アントリル基、フェナントリル基、フェニルフェニル基等が挙げられる。
　Ｒ9A～Ｒ12Aにおける炭素数７～２０のアラルキル基としては、ベンジル基、フェニルエチル基、メチルフェニルエチル基等が挙げられる。
　Ｒ9A～Ｒ12Aにおける置換基を有していてもよいアミノ基としては、メチルアミノ基、エチルアミノ基などの炭素数１～４のアルキル基を１つ有するアミノ基；ジメチルアミノ基、ジエチルアミノ基、エチルメチルアミノ基等の炭素数１～４のアルキル基を２つ有するアミノ基；アミノ基等が挙げられる。
　Ｒ9A～Ｒ12Aにおける、ハロゲン原子又は置換基を有していてもよいアミノ基を有する炭素数１～２０の飽和炭化水素基としては、例えば、トリフルオロメチル基、トリフルオロエチル基、クロロエチル基、ブロモエチル基、ヨードエチル基、Ｎ，Ｎ－ジメチルアミノエチル基、ペンタフルオロプロピル基、クロロヘキシル基、ブロモヘキシル基、ヨードヘキシル基、Ｎ，Ｎ－ジメチルアミノヘキシル基が挙げられる。 Examples of the aryl group having 6 to 20 carbon atoms in R 9A to R 12A include a phenyl group, a toluyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group and a phenylphenyl group.
Examples of the aralkyl group having 7 to 20 carbon atoms in R 9A to R 12A include a benzyl group, a phenylethyl group and a methylphenylethyl group.
The amino group which may have a substituent in R 9A to R 12A is an amino group having one alkyl group having 1 to 4 carbon atoms such as a methylamino group and an ethylamino group; a dimethylamino group, a diethylamino group , An amino group having two alkyl groups having 1 to 4 carbon atoms such as an ethylmethylamino group; and an amino group.
Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms and having a halogen atom or an amino group which may have a substituent in R 9A to R 12A include, for example, trifluoromethyl group, trifluoroethyl group and chloroethyl group. , Bromoethyl group, iodoethyl group, N, N-dimethylaminoethyl group, pentafluoropropyl group, chlorohexyl group, bromohexyl group, iodohexyl group, N, N-dimethylaminohexyl group.
　Ｒ9A～Ｒ12Aで表される置換基を有していてもよいアリール基及び置換基を有していてもよいアラルキル基において、置換基としては、上述の－ＳＯ3 -又は－ＳＯ2－Ｎ-－ＳＯ2－Ｒf以外に、フッ素原子、塩素原子、ヨウ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；ヒドロキシ基；スルホ基；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等が挙げられる。
　Ｒfで示される炭素数１～１２のフルオロアルキル基としては、例えばトリフルオロメチル基、２，２，２－トリフルオロエチル基等が挙げられる。 In the aryl group which may have a substituent and the aralkyl group which may have a substituent represented by R 9A to R 12A , the substituent may be the above-mentioned —SO 3 — or —SO 2 — In addition to N − —SO 2 —R f , a halogen atom such as a fluorine atom, a chlorine atom and an iodine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; a sulfo group; a sulfamoyl group; methyl Examples thereof include an alkylsulfonyl group having 1 to 6 carbon atoms such as a sulfonyl group.
Examples of the C 1-12 fluoroalkyl group represented by R f include a trifluoromethyl group and a 2,2,2-trifluoroethyl group.
　置換基を有していてもよいアリール基及び置換基を有していてもよいアラルキル基の具体例としては、下記式で表される基が挙げられる。下記式中、＊は窒素原子との結合手を表す。 Specific examples of the aryl group which may have a substituent and the aralkyl group which may have a substituent include groups represented by the following formulas. In the following formula, * represents a bond with a nitrogen atom.
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000007
　Ｒ9AとＲ10Aとが結合してそれらが結合する窒素原子とともに形成する環及びＲ11AとＲ12Aとが結合してそれらが結合する窒素原子とともに形成する環としては、ピロリジン環、モルホリン環、ピペリジン環、ピペラジン環等が挙げられる。 The ring formed by combining R 9A and R 10A together with the nitrogen atom to which they are bonded and the ring formed by combining R 11A and R 12A together with the nitrogen atom to which they are bonded are a pyrrolidine ring, a morpholine ring, Examples thereof include a piperidine ring and a piperazine ring.
　Ｒ1A～Ｒ8Aは、合成の容易さの点から、それぞれ独立して、水素原子、ハロゲン原子、又は炭素数１～８のアルキル基であることが好ましく、それぞれ独立して、水素原子、メチル基、フッ素原子又は塩素原子であることがより好ましい。 From the viewpoint of ease of synthesis, R 1A to R 8A are preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and each independently, a hydrogen atom or a methyl group. More preferably, it is a group, a fluorine atom or a chlorine atom.
　Ｒ9A～Ｒ12Aは、合成の容易さの点から、好ましくは、それぞれ独立して、炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数７～２０のアラルキル基又は置換されていてもよい炭素数６～２０のアリール基であり、より好ましくは、それぞれ独立して、炭素数１～８の飽和炭化水素基、置換基を有していてもよい炭素数７～１５のアラルキル基又は置換されていてもよい炭素数６～１２のアリール基であって、該アラルキル基及び該アリール基に含まれる水素原子は、ハロゲン原子、炭素数１～４のハロアルキル基、炭素数１～４のアルコキシ基、ヒドロキシ基、スルホ基又は炭素数１～４のアルキルスルホニル基で置換されていてもよく、さらに好ましくは、それぞれ独立して、炭素数１～８のアルキル基、フェニル基又はベンジル基であり、該フェニル基及び該ベンジル基に含まれる水素原子は、ハロゲン原子、炭素数１～４のハロアルキル基、炭素数１～４のアルコキシ基、ヒドロキシ基、スルホ基又は炭素数１～４のアルキルスルホニル基で置換されていてもよい。かかるフェニル基又はベンジル基としては、下記式で表される基が挙げられる。下記式中、＊は窒素原子との結合手を表す。 From the viewpoint of ease of synthesis, R 9A to R 12A are preferably each independently a saturated hydrocarbon group having 1 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms which may have a substituent. Group or an optionally substituted aryl group having 6 to 20 carbon atoms, and more preferably, each independently, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an optionally substituted carbon number. 7 to 15 aralkyl group or an optionally substituted aryl group having 6 to 12 carbon atoms, wherein the hydrogen atom contained in the aralkyl group and the aryl group is a halogen atom or a haloalkyl group having 1 to 4 carbon atoms. , An alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a sulfo group, or an alkylsulfonyl group having 1 to 4 carbon atoms, and more preferably, each independently, an alkyl group having 1 to 8 carbon atoms. , A phenyl group or a benzyl group, and the hydrogen atom contained in the phenyl group and the benzyl group is a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a sulfo group or It may be substituted with an alkylsulfonyl group having 1 to 4 carbon atoms. Examples of such a phenyl group or a benzyl group include groups represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000009
　Ａにおける炭素数６～２０の芳香族炭化水素基としては、フェニル基、トルイル基、キシリル基、ナフチル基、アントリル基、フェナントリル基、フェニルフェニル基等が挙げられる。
　Ａで表される置換基を有していてもよい芳香族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。＊は炭素原子との結合手を表す。 Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms in A include phenyl group, toluyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group and phenylphenyl group.
Examples of the aromatic hydrocarbon group which may have a substituent represented by A include groups represented by the following formulas. * Represents a bond with a carbon atom.
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000010
　Ａを表す芳香族複素環基とは、ヘテロ原子を環の構成要素として少なくとも１つ有する芳香族基を意味する。ヘテロ原子としては、窒素原子、酸素原子及び硫黄原子等が挙げられる。 The aromatic heterocyclic group represented by A means an aromatic group having at least one hetero atom as a ring constituent element. Examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom.
　Ａは、環の構成要素として少なくとも１つの窒素原子を有する芳香族複素環基であることが好ましい。かかる芳香族複素環基としては、ピロリル基、イミダゾリル基、ピラゾリル基、オキサゾリル基、チアゾリル基、及びトリアゾリル基等の、窒素原子を有する５員芳香族複素環基；ピリジル基、ピリジニル基及びピリダジニル基等の、窒素原子を有する６員芳香族複素環基；ベンズイミダゾリル基、インドリル基等の縮合環芳香族複素環基が挙げられる。
　Ａにおける置換基としては、ハロゲン原子、炭素数１～６のアルコキシ基、ヒドロキシ基、スルホ基、スルファモイル基、炭素数１～６のアルキルスルホニル基及び置換基を有していてもよいアミノ基等が挙げられ、具体的にはＲ9A～Ｒ12Aで例示したのと同様の置換基が挙げられる。 A is preferably an aromatic heterocyclic group having at least one nitrogen atom as a ring constituent. Examples of the aromatic heterocyclic group include a 5-membered aromatic heterocyclic group having a nitrogen atom such as a pyrrolyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, and a triazolyl group; a pyridyl group, a pyridinyl group and a pyridazinyl group. 6-membered aromatic heterocyclic group having a nitrogen atom; and condensed ring aromatic heterocyclic groups such as benzimidazolyl group and indolyl group.
Examples of the substituent in A include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a sulfo group, a sulfamoyl group, an alkylsulfonyl group having 1 to 6 carbon atoms, and an amino group which may have a substituent. And specifically, the same substituents as those exemplified for R 9A to R 12A can be mentioned.
　Ａは、式（ｔ１）で表される基であることが好ましい。 A is preferably a group represented by formula (t1).
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-I000011
［式（ｔ１）中、
　Ｒ56は、水素原子、炭素数１～２０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６～２０の芳香族炭化水素基を表す。
　Ｘ２は、－Ｏ－、－Ｎ（Ｒ57）－又は－Ｓ－を表す。
　Ｒ57は、水素原子又は炭素数１～１０のアルキル基を表す。
　Ｒ45及びＲ46は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０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７～３０のアラルキル基を表し、該飽和炭化水素基の炭素数が２～２０である場合、該飽和炭化水素基に含まれる－ＣＨ2－は－Ｏ－及び－ＣＯ－の少なくとも一方に置き換わっていてもよい。ただし、該炭素数２～２０の飽和炭化水素基において、隣接する－ＣＨ2－が同時に－Ｏ－に置換されることはなく、末端の－ＣＨ2－が－Ｏ－又は－ＣＯ－に置換されることはない。Ｒ45とＲ46とが結合してそれらが結合する窒素原子とともに環を形成してもよい。
　＊は、カルボカチオンとの結合手を表す。］ [In formula (t1),
R 56 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.
X2 represents -O-, -N (R 57 )-or -S-.
R 57 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R 45 and R 46 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a saturated hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, it is included in the saturated hydrocarbon group. —CH 2 — may be replaced with at least one of —O— and —CO—. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent --CH 2 --is not simultaneously replaced with --O--, and terminal --CH 2 --is replaced with --O-- or --CO--. It will not be done. R 45 and R 46 may combine to form a ring with the nitrogen atom to which they are attached.
* Represents a bond with a carbocation. ]
　Ａを表す置換基を有していてもよい芳香族複素環基としては、下記式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。 Examples of the aromatic heterocyclic group which may have a substituent, which represents A, include groups represented by the following formulas. * Represents a bond with a carbon atom.
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000012
　Ｘ２は－Ｓ－であるのが好ましい。
　Ｒ56は、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基であるのが好ましく、置換基を有していてもよいフェニル基であるのがより好ましい。
　Ｒ45及びＲ46は、それぞれ独立して、置換基を有していてもよい炭素数１～２０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６～２０の芳香族炭化水素基であるのが好ましく、置換基を有していてもよい炭素数１～６のアルキル基又は置換基を有していてもよい炭素数６～１２の芳香族炭化水素基であるのがより好ましく、一方が置換基を有していてもよい炭素数１～６のアルキル基であり、他方が置換基を有していてもよい炭素数６～１２の芳香族炭化水素基であるのがさらに好ましい。
　Ａは、式（Ａ１－１２）及び式（Ａ１－１３）で表される基が好ましい。 X2 is preferably -S-.
R 56 is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and more preferably a phenyl group which may have a substituent.
R 45 and R 46 are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. A hydrocarbon group is preferable, and an alkyl group having 1 to 6 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. Is more preferable, one is an alkyl group having 1 to 6 carbon atoms which may have a substituent, and the other is an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. Is more preferable.
A is preferably a group represented by formula (A1-12) or formula (A1-13).
　［Ｙ］m-としては公知のアニオンが挙げられるが、耐熱性の点から、含ホウ素アニオン、含アルミニウムアニオン、含フッ素アニオン、及び、タングステン、モリブデン、ケイ素及びリンからなる群から選ばれる少なくとも１つの元素と酸素とを含有するアニオンが好ましい。 [Y] m- includes known anions, but from the viewpoint of heat resistance, at least one selected from the group consisting of boron-containing anions, aluminum-containing anions, fluorine-containing anions, and tungsten, molybdenum, silicon and phosphorus. Anions containing one element and oxygen are preferred.
　含ホウ素アニオン及び含アルミニウムアニオンとしては、下記式（４）で表されるアニオンが挙げられる。 Examples of the boron-containing anion and the aluminum-containing anion include anions represented by the following formula (4).
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000013
［式（４）中、Ｗ1及びＷ2は、それぞれ独立に、１価のプロトン供与性置換基を少なくとも２つ有し、該基からプロトンを放出してなる置換基２つを有する基を表す。Ｍは、ホウ素原子又はアルミニウム原子を表す。］ [In the formula (4), W 1 and W 2 each independently represent a group having at least two monovalent proton-donating substituents and two substituents formed by releasing a proton from the group. Represent M represents a boron atom or an aluminum atom. ]
　１価のプロトン供与性置換基を少なくとも２つ有し、該基からプロトンを放出してなる置換基２つを有する基としては１価のプロトン供与性置換基（例えばヒドロキシ基、カルボキシ基等）を少なくとも２つ有する化合物から２つのプロトン供与性置換基それぞれからプロトンが放出されてなる基が挙げられる。該化合物として、好ましくは、カテコール２，３－ジヒドロキシナフタレン、２，２’－ビフェノール、３－ヒドロキシ－２－ナフトエ酸、２－ヒドロキシ－１－ナフトエ酸、１－ヒドロキシ－２－ナフトエ酸、ビナフトール、サリチル酸、ベンジル酸又は置換基をマンデル酸が挙げられ、これらは置換基を有していてもよい。 The group having at least two monovalent proton-donating substituents and having two substituents formed by releasing a proton from the group is a monovalent proton-donating substituent (eg, hydroxy group, carboxy group, etc.). A group obtained by releasing a proton from each of two proton-donating substituents from a compound having at least two of The compound is preferably catechol 2,3-dihydroxynaphthalene, 2,2′-biphenol, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, binaphthol. , Salicylic acid, benzylic acid, or mandelic acid as a substituent, which may have a substituent.
　置換基としては、ハロゲン原子；炭素数１～６のアルキル基；炭素数１～６のアルコキシ基；ニトロ基；ヒドロキシ基；アミノ基が挙げられる。 Examples of the substituent include a halogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a nitro group; a hydroxy group; and an amino group.
　式（４）で表されるアニオンとしては、下記式で表されるアニオンが挙げられる。 Examples of the anion represented by the formula (4) include anions represented by the following formula.
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000014
［式中、Ｒ61、Ｒ62、Ｒ63及びＲ64は、それぞれ独立して、水素原子、ヒドロキシ基、アミノ基、ニトロ基、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のハロアルキル基又は炭素数１～４のアルコキシ基を表す。］ [Wherein R 61 , R 62 , R 63 and R 64 are each independently a hydrogen atom, a hydroxy group, an amino group, a nitro group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. 4 represents a haloalkyl group having 4 or an alkoxy group having 1 to 4 carbon atoms. ]
　例えば、下記に記載のアニオン（ＢＣ－１）～アニオン（ＢＣ－２８）が挙げられる。
Ｍは、ホウ素原子又はアルミニウム原子を表す。表１におけるｔＢｕは、ｔｅｒｔ－ブチル基を表す。 For example, anions (BC-1) to anions (BC-28) described below can be mentioned.
M represents a boron atom or an aluminum atom. TBu in Table 1 represents a tert-butyl group.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000017
Figure JPOXMLDOC01-appb-I000017
Figure JPOXMLDOC01-appb-I000018
Figure JPOXMLDOC01-appb-I000018
Figure JPOXMLDOC01-appb-I000019
Figure JPOXMLDOC01-appb-I000019
　含フッ素アニオンとしては、下記式（６）、（７）、（８）、又は（９）で表されるアニオンが挙げられる。 Examples of the fluorine-containing anion include anions represented by the following formula (6), (7), (8), or (9).
Figure JPOXMLDOC01-appb-I000020
Figure JPOXMLDOC01-appb-I000020
［式（６）中、Ｗ3及びＷ4はそれぞれ独立に、フッ素原子又は炭素数１～４のフッ化アルキル基を表すか、又は、Ｗ3とＷ4とが結合して炭素数１～４のフッ化アルカンジイル基を形成する。］ [In the formula (6), W 3 and W 4 each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W 3 and W 4 are bonded to each other to have 1 to 4 carbon atoms. The fluorinated alkanediyl group of 4 is formed. ]
Figure JPOXMLDOC01-appb-I000021
Figure JPOXMLDOC01-appb-I000021
［式（７）中、Ｗ5、Ｗ6及びＷ7はそれぞれ独立に、フッ素原子又は炭素数１～４のフッ化アルキル基を表す。］ [In the formula (7), W 5 , W 6 and W 7 each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. ]
Figure JPOXMLDOC01-appb-I000022
Figure JPOXMLDOC01-appb-I000022
［式（８）中、Ｙ1は炭素数１～４のフッ化アルカンジイル基を表す。］ [In the formula (8), Y 1 represents a fluoroalkanediyl group having 1 to 4 carbon atoms. ]
Figure JPOXMLDOC01-appb-I000023
Figure JPOXMLDOC01-appb-I000023
［式（９）中、Ｙ2は炭素数１～４のフッ化アルキル基を表す。］ [In the formula (9), Y 2 represents a fluorinated alkyl group having 1 to 4 carbon atoms. ]
　式（６）及び（７）においてＷ3～Ｗ7でそれぞれ表される炭素数１～４のフッ化アルキル基としては、ペルフルオロアルキル基が好ましく、例えば－ＣＦ3、－ＣＦ2ＣＦ3、－ＣＦ2ＣＦ2ＣＦ3、－ＣＦ（ＣＦ3）2、－ＣＦ2ＣＦ2ＣＦ2ＣＦ3、－ＣＦ2ＣＦ（ＣＦ3）2、－Ｃ（ＣＦ3）3等が挙げられる。 The fluoroalkyl group having 1 to 4 carbon atoms represented by W 3 to W 7 in the formulas (6) and (7) is preferably a perfluoroalkyl group, for example, —CF 3 , —CF 2 CF 3 , Examples thereof include CF 2 CF 2 CF 3 , —CF (CF 3 ) 2 , —CF 2 CF 2 CF 2 CF 3 , —CF 2 CF (CF 3 ) 2 and —C (CF 3 ) 3 .
　式（６）においてＷ3とＷ4とが結合して形成される炭素数２～４のフッ化アルカンジイル基としては、ペルフルオロアルカンジイル基が好ましく、例えば－ＣＦ2ＣＦ2－、－ＣＦ2ＣＦ2ＣＦ2－、－ＣＦ2ＣＦ2ＣＦ2ＣＦ2－等が挙げられる。 In the formula (6), the fluoroalkanediyl group having 2 to 4 carbon atoms formed by combining W 3 and W 4 is preferably a perfluoroalkanediyl group, for example, —CF 2 CF 2 —, —CF 2 CF 2 CF 2 —, —CF 2 CF 2 CF 2 CF 2 — and the like can be mentioned.
　式（８）においてＹ1で表される炭素数１～４のフッ化アルカンジイル基としては、ペルフルオロアルカンジイル基が好ましく、例えば、－ＣＦ2－、－ＣＦ2ＣＦ２－、－ＣＦ2ＣＦ2ＣＦ2－、－Ｃ（ＣＦ3）2－、－ＣＦ2ＣＦ2ＣＦ2ＣＦ2－等が挙げられる。 The fluorinated alkanediyl group having 1 to 4 carbon atoms represented by Y 1 in formula (8), perfluoro alkanediyl group is preferred, for example, -CF 2 -, - CF 2 CF2 -, - CF 2 CF 2 Examples thereof include CF 2 —, —C (CF 3 ) 2 —, —CF 2 CF 2 CF 2 CF 2 — and the like.
　式（９）においてＹ2で表される炭素数１～４のフッ化アルキル基としては、ペルフルオロアルキル基が好ましく、－ＣＦ3、－ＣＦ2ＣＦ3、－ＣＦ2ＣＦ2ＣＦ3、－ＣＦ（ＣＦ3）2、－ＣＦ2ＣＦ2ＣＦ2ＣＦ3、－ＣＦ2ＣＦ（ＣＦ3）2、－Ｃ（ＣＦ3）3等が挙げられる。 As the fluorinated alkyl group having 1 to 4 carbon atoms represented by Y 2 in the formula (9), a perfluoroalkyl group is preferable, and —CF 3 , —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —CF (CF 3 ) 2 , —CF 2 CF 2 CF 2 CF 3 , —CF 2 CF (CF 3 ) 2 , —C (CF 3 ) 3 and the like.
　式（６）で表されるアニオン（以下「アニオン（６）」という場合がある）としては、下記のアニオン（６－１）～（６－６）が挙げられる。 Examples of the anion represented by the formula (6) (hereinafter sometimes referred to as “anion (6)”) include the following anions (6-1) to (6-6).
Figure JPOXMLDOC01-appb-I000024
Figure JPOXMLDOC01-appb-I000024
　式（７）で表されるアニオン（以下「アニオン（７）」という場合がある）としては、例えば下記のアニオン（７－１）が挙げられる。 Examples of the anion represented by the formula (7) (hereinafter sometimes referred to as “anion (7)”) include the following anions (7-1).
Figure JPOXMLDOC01-appb-I000025
Figure JPOXMLDOC01-appb-I000025
　式（８）で表されるアニオン（以下「アニオン（８）」という場合がある）としては、例えば下記のアニオン（８－１）～（８－４）が挙げられる。 Examples of the anion represented by the formula (8) (hereinafter sometimes referred to as “anion (8)”) include the following anions (8-1) to (8-4).
Figure JPOXMLDOC01-appb-I000026
Figure JPOXMLDOC01-appb-I000026
　式（９）で表されるアニオン（以下「アニオン（９）」という場合がある）としては、例えば下記のアニオン（９－１）～（９－４）が挙げられる。 Examples of the anion represented by the formula (9) (hereinafter sometimes referred to as “anion (9)”) include the following anions (9-1) to (9-4).
Figure JPOXMLDOC01-appb-I000027
Figure JPOXMLDOC01-appb-I000027
　［Ｙ］m-として、タングステン、モリブデン、ケイ素及びリンからなる群から選ばれる少なくとも１つの元素と、酸素とを含有するアニオンが挙げられる。タングステンを含有する［Ｙ］m-としては、ヘテロポリ酸又はイソポリ酸のアニオンが好ましく、リンタングステン酸、ケイタングステン酸及びタングステン系イソポリ酸のアニオンがより好ましい。 [Y] m-includes an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and oxygen. As the [Y] m- containing tungsten, anions of heteropolyacid or isopolyacid are preferable, and anions of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid are more preferable.
　この様なタングステンを含有するヘテロポリ酸又はイソポリ酸のアニオンとしては、ケギン型リンタングステン酸イオンα－［ＰＷ12Ｏ40］3-、ドーソン型リンタングステン酸イオンα－［Ｐ2Ｗ18Ｏ62］6-、β－［Ｐ2Ｗ18Ｏ62］6-、ケギン型ケイタングステン酸イオンα－［ＳｉＷ12Ｏ40］4-、β－［ＳｉＷ12Ｏ40］4-、γ－［ＳｉＷ12Ｏ40］4-、さらにその他の例として［Ｐ2Ｗ17Ｏ61］10-、［Ｐ2Ｗ15Ｏ56］12-、［Ｈ2Ｐ2Ｗ12Ｏ48］12-、［ＮａＰ5Ｗ30Ｏ110］14-、α－［ＳｉＷ9Ｏ34］10-、γ－［ＳｉＷ10Ｏ36］8-、α－［ＳｉＷ11Ｏ39］8-、β－［ＳｉＷ11Ｏ39］8-、［Ｗ6Ｏ19］2-、［Ｗ10Ｏ32］4-、ＷＯ4 2-等が挙げられる。 The anions of such a heteropoly acid or isopoly acid containing tungsten include Keggin-type phosphotungstic acid ion α- [PW 12 O 40 ] 3- , Dawson-type phosphotungstic acid ion α- [P 2 W 18 O 62 ]. 6- , β- [P 2 W 18 O 62 ] 6- , Keggin-type silicotungstate ion α- [SiW 12 O 40 ] 4- , β- [SiW 12 O 40 ] 4- , γ- [SiW 12 O 40 ] 4- , and as other examples, [P 2 W 17 O 61 ] 10- , [P 2 W 15 O 56 ] 12- , [H 2 P 2 W 12 O 48 ] 12- , [NaP 5 W 30 O 110 ] 14- , α- [SiW 9 O 34 ] 10- , γ- [SiW 10 O 36 ] 8- , α- [SiW 11 O 39 ] 8- , β- [SiW 11 O 39 ] 8- , [W 6 O 19 ] 2− , [W 10 O 32 ] 4− , WO 4 2− and the like.
　ケイ素、及びリンからなる群から選ばれる少なくとも１つの元素と、酸素とからなるアニオンとしては、ＳｉＯ3 2－、ＰＯ4 3－が挙げられる。 Examples of anions composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus include SiO 3 2 — and PO 4 3 —.
　特に合成と後処理の容易さから、ケギン型リンタングステン酸イオン、ドーソン型リンタングステン酸イオン、ケギン型ケイタングステン酸イオン等のヘテロポリ酸アニオン、[Ｗ10Ｏ32]4-等のイソポリ酸アニオンが好ましい。 In particular, from the viewpoint of ease of synthesis and post-treatment, heteropoly acid anions such as Keggin-type phosphotungstate ion, Dawson-type phosphotungstate ion and Keggin-type silicotungstate ion, and isopoly acid anion such as [W 10 O 32 ] 4- preferable.
　式（Ａ－ＶＩ）で表される塩の具体例としては、下記式（Ａ－ＶＩ－１）～（Ａ－ＶＩ－２７）で表される塩が挙げられる。 Specific examples of the salt represented by the formula (A-VI) include salts represented by the following formulas (A-VI-1) to (A-VI-27).
Figure JPOXMLDOC01-appb-I000028
Figure JPOXMLDOC01-appb-I000028
Figure JPOXMLDOC01-appb-I000029
Figure JPOXMLDOC01-appb-I000029
Figure JPOXMLDOC01-appb-I000030
Figure JPOXMLDOC01-appb-I000030
Figure JPOXMLDOC01-appb-I000031
Figure JPOXMLDOC01-appb-I000031
Figure JPOXMLDOC01-appb-I000032
Figure JPOXMLDOC01-appb-I000032
　染料（Ａ１）は、好ましくは式（Ａ－ＶＩ－２７）で表される塩を含む。 The dye (A1) preferably contains a salt represented by the formula (A-VI-27).
　置換基としてスルホ基（－ＳＯ3Ｈ）を有する場合、ヒドロンと任意のカチオンとが交換されて塩を形成していてもよい。任意のカチオンとしては、アルカリ金属イオン、有機アンモニウムイオン、置換基を有していてもよいイミダゾリウムイオン等が挙げられる。
スルホ基を複数個有する場合、２価以上の金属イオンと塩を形成していてもよい。 When it has a sulfo group (—SO 3 H) as a substituent, the hydrone may be exchanged with an arbitrary cation to form a salt. Examples of the optional cation include an alkali metal ion, an organic ammonium ion, and an imidazolium ion which may have a substituent.
When it has a plurality of sulfo groups, it may form a salt with a divalent or higher valent metal ion.
　〔染料（Ａ２）〕
　染料（Ａ２）はキサンテン染料を含む。キサンテン染料としては、公知の物質を用いることができる。以下、染料（Ａ２）はキサンテン染料（Ａ２）ともいう。 [Dye (A2)]
The dye (A2) includes a xanthene dye. A known substance can be used as the xanthene dye. Hereinafter, the dye (A2) is also referred to as a xanthene dye (A2).
　キサンテン染料（Ａ２）は、分子内にキサンテン骨格を有する化合物を含む染料である。キサンテン染料（Ａ２）としては、例えば、Ｃ．Ｉ．アシッドレッド５１（以下、Ｃ．Ｉ．アシッドレッドの記載を省略し、番号のみの記載とする。他も同様である。）、５２、８７、９２、９４、２８９、３８８、Ｃ．Ｉ．アシッドバイオレット９、３０、１０２、Ｃ．Ｉ．ベーシックレッド１（ローダミン６Ｇ）、２、３、４、８、Ｃ．Ｉ．ベーシックレッド１０、１１、Ｃ．Ｉ．ベーシックバイオレット１０（ローダミンＢ）、１１、Ｃ．Ｉ．ソルベントレッド２１８、Ｃ．Ｉ．モーダントレッド２７、Ｃ．Ｉ．リアクティブレッド３６（ローズベンガルＢ）、スルホローダミンＧ、特開２０１０－３２９９９号公報に記載のキサンテン染料及び特許第４４９２７６０号公報に記載のキサンテン染料等が挙げられる。有機溶剤に溶解するものが好ましい。 The xanthene dye (A2) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (A2) include C.I. I. Acid Red 51 (hereinafter, CI Acid Red is omitted and only numbers are described. The same applies to the others.), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10, 11, C.I. I. Basic Violet 10 (Rhodamine B), 11, C.I. I. Solvent Red 218, C.I. I. Mordant Red 27, C.I. I. Examples thereof include Reactive Red 36 (Rose Bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999A and xanthene dyes described in Japanese Patent No. 4492760. Those that are soluble in organic solvents are preferred.
　これらの中でも、キサンテン染料（Ａ２）としては、式（１ａ）で表される化合物（以下、「化合物（１ａ）」という場合がある。）を含む染料が好ましい。化合物（１ａ）は、その互変異性体であってもよい。化合物（１ａ）を用いる場合、キサンテン染料（Ａ２）中の化合物（１ａ）の含有量は、好ましくは５０質量％以上、より好ましくは７０質量％以上、さらに好ましくは９０質量％以上である。特に、キサンテン染料（Ａ２）として、化合物（１ａ）のみを使用することが好ましい。 Among these, the xanthene dye (A2) is preferably a dye containing a compound represented by the formula (1a) (hereinafter, sometimes referred to as “compound (1a)”). The compound (1a) may be a tautomer thereof. When using the compound (1a), the content of the compound (1a) in the xanthene dye (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye (A2).
Figure JPOXMLDOC01-appb-I000033
Figure JPOXMLDOC01-appb-I000033
［式（１ａ）中、Ｒ1a～Ｒ4aは、互いに独立に、水素原子、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６～１０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ2－は、－Ｏ－、－ＣＯ－又は－ＮＲ11a－で置き換わっていてもよい。Ｒ1a及びＲ2aは、一緒になって窒素原子を含む環を形成してもよく、Ｒ3a及びＲ4aは、一緒になって窒素原子を含む環を形成してもよい。
　Ｒ5aは、－ＯＨ、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚａ+、－ＣＯ2Ｈ、－ＣＯ2 -Ｚａ+、－ＣＯ2Ｒ8a、－ＳＯ3Ｒ8a又は－ＳＯ2ＮＲ9aＲ10aを表す。
　Ｒ6a及びＲ7aは、互いに独立に、水素原子又は炭素数１～６のアルキル基を表す。
　ｍは、０～５の整数を表す。ｍが２以上のとき、複数のＲ5aは同一でも異なってもよい。
　ａは、０又は１の整数を表す。
　Ｘａは、ハロゲン原子を表す。
　Ｚａ+は、+Ｎ（Ｒ11a）4、Ｎａ+又はＫ+を表し、４つのＲ11aは同一でも異なってもよい。
　Ｒ8aは、炭素数１～２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
　Ｒ9a及びＲ10aは、互いに独立に、水素原子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し、該飽和炭化水素基に含まれる－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＮＨ－又は－ＮＲ8a－で置き換っていてもよく、Ｒ9a及びＲ10aは、互いに結合して窒素原子を含んだ３～１０員環の複素環を形成していてもよい。
　Ｒ11aは、水素原子、炭素数１～２０の１価の飽和炭化水素基又は炭素数７～１０のアラルキル基を表す。］ [In the formula (1a), R 1a to R 4a each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Optionally represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH 2 — contained in the saturated hydrocarbon group is replaced by —O—, —CO— or —NR 11a —. Good. R 1a and R 2a may together form a ring containing a nitrogen atom, and R 3a and R 4a may together form a ring containing a nitrogen atom.
R 5a is, -OH, -SO 3 -, -SO 3 H, -SO 3 - Za +, -CO 2 H, -CO 2 - Za +, -CO 2 R 8a, -SO 3 R 8a or -SO 2 NR 9a represents R 10a .
R 6a and R 7a each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, plural R 5a 's may be the same or different.
a represents an integer of 0 or 1.
Xa represents a halogen atom.
Za + represents + N (R 11a ) 4 , Na + or K + , and four R 11a 's may be the same or different.
R 8a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R 9a and R 10a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH 2 contained in the saturated hydrocarbon group. -May be replaced by -O-, -CO-, -NH- or -NR 8a- , and R 9a and R 10a are each a 3- to 10-membered ring containing a nitrogen atom bonded to each other. It may form a heterocycle.
R 11a represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]
　式（１ａ）において、－ＳＯ3 -が存在する場合、その数は１個である。 In formula (1a), when -SO 3 - is present, the number is 1.
　Ｒ1a～Ｒ4aにおける炭素数６～１０の１価の芳香族炭化水素基としては、例えば、フェニル基、トルイル基、キシリル基、メシチル基、プロピルフェニル基及びブチルフェニル基等が挙げられる。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1a to R 4a include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.
　該芳香族炭化水素基が有していてもよい置換基としては、ハロゲン原子、カルボキシ基、－Ｒ8a、－ＯＨ、－ＯＲ8a、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚａ+、－ＣＯ2Ｈ、－ＣＯ2Ｒ8a、－ＳＲ8a、－ＳＯ2Ｒ8a、－ＳＯ3Ｒ8a又は－ＳＯ2ＮＲ9aＲ10aが挙げられる。これらの中でも、置換基としては、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚａ+及び－ＳＯ2ＮＲ9aＲ10aが好ましく、－ＳＯ3 -Ｚａ+及び－ＳＯ2ＮＲ9aＲ10aがより好ましい。この場合の－ＳＯ3 -Ｚａ+としては、－ＳＯ3 -　+Ｎ（Ｒ11a）4が好ましい。Ｒ1a～Ｒ4aがこれらの基であると、化合物（１ａ）を含む本発明の着色硬化性樹脂組成物からは、異物の発生が少なく、且つ耐熱性に優れるカラーフィルタを形成できる。 The aromatic hydrocarbon group substituent which may have a halogen atom, a carboxyl group, -R 8a, -OH, -OR 8a , -SO 3 -, -SO 3 H, -SO 3 - Za + , -CO 2 H, -CO 2 R 8a , -SR 8a , -SO 2 R 8a , -SO 3 R 8a or -SO 2 NR 9a R 10a may be mentioned. Among them, as the substituent, -SO 3 -, -SO 3 H , -SO 3 - Za + and -SO 2 NR 9a R 10a is preferably, -SO 3 - Za + and -SO 2 NR 9a R 10a Is more preferable. In this case, as —SO 3 − Za + , —SO 3 − + N (R 11a ) 4 is preferable. When R 1a to R 4a are these groups, the color curable resin composition of the present invention containing the compound (1a) can form a color filter with less generation of foreign matter and excellent heat resistance.
　Ｒ1a～Ｒ4a及びＲ8a～Ｒ11a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、イコシル基等の直鎖状アルキル基；イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基、２－エチルヘキシル基等の分岐鎖状アルキル基；シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基等の炭素数３～２０の脂環式飽和炭化水素基が挙げられる。
　Ｒ1a～Ｒ4aにおける該飽和炭化水素基に含まれる水素原子は、例えば、カルボキシ基、炭素数６～１０の芳香族炭化水素基又はハロゲン原子で置換されていてもよい。
　Ｒ9a及びＲ10aにおける該飽和炭化水素基に含まれる水素原子は、例えば、ヒドロキシ基又はハロゲン原子で置換されていてもよい。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1a to R 4a and R 8a to R 11a include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group. , A linear alkyl group such as an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, and an icosyl group; a branched chain alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; Examples thereof include alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and cyclodecyl group.
The hydrogen atom contained in the saturated hydrocarbon group in R 1a to R 4a may be substituted with, for example, a carboxy group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom.
The hydrogen atom contained in the saturated hydrocarbon group for R 9a and R 10a may be substituted with, for example, a hydroxy group or a halogen atom.
　Ｒ1a及びＲ2aが一緒になって形成する環、並びにＲ3a及びＲ4aが一緒になって形成する環としては、例えば、以下のものが挙げられる。 Examples of the ring formed by R 1a and R 2a together and the ring formed by R 3a and R 4a together include the following.
Figure JPOXMLDOC01-appb-I000034
Figure JPOXMLDOC01-appb-I000034
　－ＯＲ8aとしては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、２－エチルヘキシルオキシ基及びイコシルオキシ基等が挙げられる。 Examples of —OR 8a include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an icosyloxy group.
　－ＣＯ2Ｒ8aとしては、例えば、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ｔｅｒｔ－ブトキシカルボニル基、ヘキシルオキシカルボニル基及びイコシルオキシカルボニル基等が挙げられる。 Examples of —CO 2 R 8a include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group.
　－ＳＲ8aとしては、例えば、メチルスルファニル基、エチルスルファニル基、ブチルスルファニル基、ヘキシルスルファニル基、デシルスルファニル基及びイコシルスルファニル基等が挙げられる。
　－ＳＯ2Ｒ8aとしては、例えば、メチルスルホニル基、エチルスルホニル基、ブチルスルホニル基、ヘキシルスルホニル基、デシルスルホニル基及びイコシルスルホニル基等が挙げられる。
　－ＳＯ3Ｒ8aとしては、例えば、メトキシスルホニル基、エトキシスルホニル基、プロポキシスルホニル基、ｔｅｒｔ－ブトキシスルホニル基、ヘキシルオキシスルホニル基及びイコシルオキシスルホニル基等が挙げられる。 Examples of —SR 8a include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO 2 R 8a include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO 3 R 8a include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.
　－ＳＯ2ＮＲ9aＲ10aとしては、例えば、スルファモイル基；
Ｎ－メチルスルファモイル基、Ｎ－エチルスルファモイル基、Ｎ－プロピルスルファモイル基、Ｎ－イソプロピルスルファモイル基、Ｎ－ブチルスルファモイル基、Ｎ－イソブチルスルファモイル基、Ｎ－ｓｅｃ－ブチルスルファモイル基、Ｎ－ｔｅｒｔ－ブチルスルファモイル基、Ｎ－ペンチルスルファモイル基、Ｎ－（１－エチルプロピル）スルファモイル基、Ｎ－（１，１－ジメチルプロピル）スルファモイル基、Ｎ－（１，２－ジメチルプロピル）スルファモイル基、Ｎ－（２，２－ジメチルプロピル）スルファモイル基、Ｎ－（１－メチルブチル）スルファモイル基、Ｎ－（２－メチルブチル）スルファモイル基、Ｎ－（３－メチルブチル）スルファモイル基、Ｎ－シクロペンチルスルファモイル基、Ｎ－ヘキシルスルファモイル基、Ｎ－（１，３－ジメチルブチル）スルファモイル基、Ｎ－（３，３－ジメチルブチル）スルファモイル基、Ｎ－ヘプチルスルファモイル基、Ｎ－（１－メチルヘキシル）スルファモイル基、Ｎ－（１，４－ジメチルペンチル）スルファモイル基、Ｎ－オクチルスルファモイル基、Ｎ－（２－エチルヘキシル）スルファモイル基、Ｎ－（１，５－ジメチル）ヘキシルスルファモイル基、Ｎ－（１，１，２，２－テトラメチルブチル）スルファモイル基等のＮ－１置換スルファモイル基；
Ｎ，Ｎ－ジメチルスルファモイル基、Ｎ，Ｎ－エチルメチルスルファモイル基、Ｎ，Ｎ－ジエチルスルファモイル基、Ｎ，Ｎ－プロピルメチルスルファモイル基、Ｎ，Ｎ－イソプロピルメチルスルファモイル基、Ｎ，Ｎ－ｔｅｒｔ－ブチルメチルスルファモイル基、Ｎ，Ｎ－ブチルエチルスルファモイル基、Ｎ，Ｎ－ビス（１－メチルプロピル）スルファモイル基、Ｎ，Ｎ－ヘプチルメチルスルファモイル基等のＮ，Ｎ－２置換スルファモイル基等が挙げられる。 —SO 2 NR 9a R 10a includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N- Heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- N-1, substituted sulfamoyl groups such as (1,5-dimethyl) hexylsulfamoyl group and N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group N, N-2 substituted sulfamoyl groups such as groups and the like.
　Ｒ5aは、－ＣＯ2Ｈ、－ＣＯ2 -Ｚａ+、－ＣＯ2Ｒ8a、－ＳＯ3 -、－ＳＯ3 -Ｚａ+、－ＳＯ3Ｈ又はＳＯ2ＮＨＲ9aが好ましく、ＳＯ3 -、－ＳＯ3 -Ｚａ+、－ＳＯ3Ｈ又はＳＯ2ＮＨＲ9aがより好ましい。
　ｍは、１～４が好ましく、１又は２がより好ましい。 R 5a is, -CO 2 H, -CO 2 - Za +, -CO 2 R 8a, -SO 3 -, -SO 3 - Za +, -SO 3 H or SO 2 NHR 9a are preferred, SO 3 -, -SO 3 - Za +, -SO 3 H or SO 2 NHR 9a is more preferable.
m is preferably 1 to 4, and more preferably 1 or 2.
　Ｒ6a及びＲ7aにおける炭素数１～６のアルキル基としては、上記で挙げたアルキル基のうち、炭素数１～６のものが挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms in R 6a and R 7a include the alkyl groups having 1 to 6 carbon atoms among the alkyl groups listed above.
　Ｒ11aにおける炭素数７～１０のアラルキル基としては、ベンジル基、フェニルエチル基、フェニルブチル基等が挙げられる。 Examples of the aralkyl group having 7 to 10 carbon atoms in R 11a include a benzyl group, a phenylethyl group and a phenylbutyl group.
　Ｚａ+は、+Ｎ（Ｒ11a）4、Ｎａ+又はＫ+であり、好ましくは+Ｎ（Ｒ11a）4である。
　前記+Ｎ（Ｒ11a）4としては、４つのＲ11aのうち、少なくとも２つが炭素数５～２０の１価の飽和炭化水素基であることが好ましい。また、４つのＲ11aの合計炭素数は２０～８０が好ましく、２０～６０がより好ましい。化合物（１ａ）中に+Ｎ（Ｒ11a）4が存在する場合、Ｒ11aがこれらの基であると、化合物（１ａ）を含む本発明の着色硬化性樹脂組成物から、異物が少ないカラーフィルタを形成できる。 Za + is + N (R 11a ) 4 , Na + or K + , and preferably + N (R 11a ) 4 .
As the + N (R 11a ) 4 , it is preferable that at least two of the four R 11a are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of the four R 11a is preferably 20 to 80, more preferably 20 to 60. When + N (R 11a ) 4 is present in the compound (1a), when R 11a is one of these groups, the colored filter containing the compound (1a) of the present invention can reduce the amount of foreign matters. Can be formed.
　化合物（１ａ）としては、式（２ａ）で表される化合物（以下「化合物（２ａ）」という場合がある。）が好ましい。化合物（２ａ）は、その互変異性体であってもよい。 The compound (1a) is preferably a compound represented by the formula (2a) (hereinafter sometimes referred to as “compound (2a)”). The compound (2a) may be a tautomer thereof.
Figure JPOXMLDOC01-appb-I000035
［式（２ａ）中、Ｒ21a～Ｒ24aは、互いに独立に、水素原子、－Ｒ26a又は置換基を有していてもよい炭素数６～１０の１価の芳香族炭化水素基を表す。Ｒ21a及びＲ22aは、一緒になって窒素原子を含む環を形成してもよく、Ｒ23a及びＲ24aは、一緒になって窒素原子を含む環を形成してもよい。
　Ｒ25aは、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ１+又は－ＳＯ2ＮＨＲ26aを表す。
　ｍ１は、０～５の整数を表す。ｍ１が２以上のとき、複数のＲ25aは同一でも異なってもよい。
　ａ１は、０又は１の整数を表す。
　Ｘ１は、ハロゲン原子を表す。
　Ｒ26aは、ハロゲン原子又はカルボキシ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。
　Ｚ１+は、+Ｎ（Ｒ27a）4、Ｎａ+又はＫ+を表し、４つのＲ27aは同一でも異なってもよい。
　Ｒ27aは、炭素数１～２０の１価の飽和炭化水素基又はベンジル基を表す。］
Figure JPOXMLDOC01-appb-I000035
[In the formula (2a), R 21a to R 24a each independently represents a hydrogen atom, —R 26a or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. .. R 21a and R 22a may together form a ring containing a nitrogen atom, and R 23a and R 24a may together form a ring containing a nitrogen atom.
R 25a represents —SO 3 − , —SO 3 H, —SO 3 — Z1 + or —SO 2 NHR 26a .
m1 represents an integer of 0 to 5. When m1 is 2 or more, a plurality of R 25a may be the same or different.
a1 represents an integer of 0 or 1.
X1 represents a halogen atom.
R 26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a halogen atom or a carboxy group.
Z1 + represents + N (R 27a ) 4 , Na + or K + , and four R 27a may be the same or different.
R 27a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. ]
　Ｒ21a～Ｒ24aにおける炭素数６～１０の１価の芳香族炭化水素基としては、前記Ｒ1a～Ｒ4aの芳香族炭化水素基として挙げたものと同様の基が挙げられる。該芳香族炭化水素基に含まれる水素原子は、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ１+、－ＳＯ3Ｒ26a又は－ＳＯ2ＮＨＲ26aで置換されていてもよい。
　Ｒ21a～Ｒ24aの組合せとしては、Ｒ21a及びＲ23aが、互いに独立に、水素原子又は炭素数１～１０の飽和炭化水素基（該飽和炭化水素基はハロゲン原子又はカルボキシ基を有していてもよい。）であり、Ｒ22a及びＲ24aが炭素数６～１０の１価の芳香族炭化水素基であって、該芳香族炭化水素基に含まれる水素原子が、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ１+、－ＳＯ3Ｒ26a又は－ＳＯ2ＮＨＲ26aで置換されているものが好ましい。さらに好ましい組合せは、Ｒ21a及びＲ23aが、互いに独立に、水素原子又は炭素数１～８のアルキル基（該アルキル基はハロゲン原子又はカルボキシ基を有していてもよい。）であり、Ｒ22a及びＲ24aが炭素数６～１０の１価の芳香族炭化水素基であって、該芳香族炭化水素基に含まれる水素原子が、－ＳＯ3 -Ｚ１+又は－ＳＯ2ＮＨＲ26aで置換されていているものである。Ｒ21a～Ｒ24aがこれらの基であると、化合物（２ａ）を含む本発明の着色硬化性樹脂組成物から、耐熱性に優れるカラーフィルタを形成できる。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 21a to R 24a include the same groups as those mentioned above as the aromatic hydrocarbon group of R 1a to R 4a . Hydrogen atoms contained in the aromatic hydrocarbon group, -SO 3 -, -SO 3 H , -SO 3 - Z1 +, it may be substituted by -SO 3 R 26a or -SO 2 NHR 26a.
As a combination of R 21a to R 24a , R 21a and R 23a are independently of each other a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms (the saturated hydrocarbon group has a halogen atom or a carboxy group). R 22a and R 24a are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is —SO 3 — , -SO 3 H, -SO 3 - Z1 +, which is substituted by -SO 3 R 26a or -SO 2 NHR 26a is preferable. A more preferable combination is that R 21a and R 23a are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (the alkyl group may have a halogen atom or a carboxy group), and R 22a and R 24a are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is replaced with —SO 3 — Z1 + or —SO 2 NHR 26a . It has been done. When R 21a to R 24a are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).
　Ｒ21a及びＲ22aが一緒になって形成する窒素原子を含む環、並びに、Ｒ23a及びＲ24aが一緒になって形成する窒素原子を含む環としては、Ｒ1a及びＲ2aが一緒になって形成する環と同様のものが挙げられる。中でも、脂肪族複素環が好ましい。該脂肪族複素環としては、例えば、下記のものが挙げられる。 The ring containing a nitrogen atom formed by R 21a and R 22a together, and the ring containing a nitrogen atom formed by R 23a and R 24a together are R 1a and R 2a together. The same as the ring to be formed is mentioned. Of these, an aliphatic heterocycle is preferable. Examples of the aliphatic heterocycle include the followings.
Figure JPOXMLDOC01-appb-I000036
Figure JPOXMLDOC01-appb-I000036
　Ｒ26a及びＲ27aにおける炭素数１～２０の１価の飽和炭化水素基としては、Ｒ8a～Ｒ11aで飽和炭化水素基として挙げたものと同様の基が挙げられる。
　Ｒ21a～Ｒ24aが－Ｒ26aである場合、－Ｒ26aは、それぞれ独立に、メチル基又はエチル基であることが好ましい。また、－ＳＯ3Ｒ26a及び－ＳＯ2ＮＨＲ26aにおけるＲ26aとしては、炭素数３～２０の分枝鎖状アルキル基が好ましく、炭素数６～１２の分枝鎖状アルキル基がより好ましく、２－エチルヘキシル基がさらに好ましい。Ｒ26aがこれらの基であると、化合物（２ａ）を含む本発明の着色硬化性樹脂組成物から、異物の発生が少ないカラーフィルタを形成できる。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 26a and R 27a include the same groups as those mentioned as the saturated hydrocarbon group in R 8a to R 11a .
When R 21a to R 24a are -R 26a , -R 26a is preferably each independently a methyl group or an ethyl group. As the R 26a in -SO 3 R 26a and -SO 2 NHR 26a, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6-12 carbon atoms, A 2-ethylhexyl group is more preferred. When R 26a is any of these groups, a color filter with less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).
　Ｚ１+は、+Ｎ（Ｒ27a）4、Ｎａ+又はＫ+であり、好ましくは+Ｎ（Ｒ27a）4である。
　前記+Ｎ（Ｒ27a）4としては、４つのＲ27aのうち、少なくとも２つが炭素数５～２０の１価の飽和炭化水素基であることが好ましい。また、４つのＲ27aの合計炭素数は２０～８０が好ましく、２０～６０がより好ましい。化合物（２ａ）中に+Ｎ（Ｒ27a）4が存在する場合、Ｒ27aがこれらの基であると、化合物（２ａ）を含む本発明の着色硬化性樹脂組成物から、異物の発生が少ないカラーフィルタを形成できる。 Z1 + is + N (R 27a ) 4 , Na + or K + , and preferably + N (R 27a ) 4 .
As + N (R 27a ) 4 , it is preferable that at least two of the four R 27a are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of the four R 27a is preferably 20 to 80, more preferably 20 to 60. When + N (R 27a ) 4 is present in the compound (2a), when R 27a is one of these groups, the colored curable resin composition of the present invention containing the compound (2a) hardly generates foreign matters. A color filter can be formed.
　ｍ１は、１～４が好ましく、１又は２がより好ましい。 M1 is preferably 1 to 4, and more preferably 1 or 2.
　また、化合物（１ａ）としては、式（３ａ）で表される化合物（以下「化合物（３ａ）」という場合がある。）も好ましい。化合物（３ａ）は、その互変異性体であってもよい。 Also, as the compound (1a), a compound represented by the formula (3a) (hereinafter sometimes referred to as “compound (3a)”) is also preferable. The compound (3a) may be a tautomer thereof.
Figure JPOXMLDOC01-appb-I000037
Figure JPOXMLDOC01-appb-I000037
［式（３ａ）中、Ｒ31a及びＲ32aは、互いに独立に、炭素数１～１０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、炭素数６～１０の芳香族炭化水素基、カルボキシ基又はハロゲン原子で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１～３のアルコキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる－ＣＨ2－は、－Ｏ－、－ＣＯ－又は－ＮＲ11a－で置き換わっていてもよい。
　Ｒ33a及びＲ34aは、互いに独立に、炭素数１～４のアルキル基、炭素数１～４のアルキルスルファニル基又は炭素数１～４のアルキルスルホニル基を表す。
　Ｒ31a及びＲ33aは、一緒になって窒素原子を含む環を形成してもよく、Ｒ32a及びＲ34aは、一緒になって窒素原子を含む環を形成してもよい。
　ｐ及びｑは、互いに独立に、０～５の整数を表す。ｐが２以上のとき、複数のＲ33aは同一でも異なってもよく、ｑが２以上のとき、複数のＲ34aは同一でも異なってもよい。
　Ｒ11aは、上記と同じ意味を表す。］ [In the formula (3a), R 31a and R 32a each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group has 6 to 10 carbon atoms. 10 aromatic hydrocarbon groups, a carboxy group or a halogen atom may be substituted, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, —CH 2 — contained in the saturated hydrocarbon group may be replaced by —O—, —CO— or —NR 11a —.
R 33a and R 34a each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R 31a and R 33a may together form a ring containing a nitrogen atom, and R 32a and R 34a may together form a ring containing a nitrogen atom.
p and q each independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R 33a may be the same or different, and when q is 2 or more, a plurality of R 34a may be the same or different.
R 11a has the same meaning as above. ]
　Ｒ31a及びＲ32aにおける炭素数１～１０の１価の飽和炭化水素基としては、Ｒ8aにおけるもののうち炭素数１～１０の基が挙げられる。
　置換基として有していてもよい炭素数６～１０の芳香族炭化水素基としては、Ｒ1aにおけるものと同じ基が挙げられる。
　炭素数１～３のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基等が挙げられる。
　Ｒ31a及びＲ32aは、互いに独立に、炭素数１～３の１価の飽和炭化水素基（該飽和炭化水素基はハロゲン原子又はカルボキシ基を有していてもよい）であることが好ましい。 Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R 31a and R 32a include groups having 1 to 10 carbon atoms among those in R 8a .
As the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted, the same groups as those for R 1a can be mentioned.
Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy group, ethoxy group and propoxy group.
It is preferable that R 31a and R 32a each independently represent a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (the saturated hydrocarbon group may have a halogen atom or a carboxy group).
　Ｒ33a及びＲ34aにおける炭素数１～４のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等が挙げられる。
　Ｒ33a及びＲ34aにおける炭素数１～４のアルキルスルファニル基としては、メチルスルファニル基、エチルスルファニル基、プロピルスルファニル基、ブチルスルファニル基及びイソプロピルスルファニル基等が挙げられる。
　Ｒ33a及びＲ34aにおける炭素数１～４のアルキルスルホニル基としては、メチルスルホニル基、エチルスルホニル基、プロピルスルホニル基、ブチルスルホニル基及びイソプロピルスルホニル基等が挙げられる。
　Ｒ33a及びＲ34aは、炭素数１～４のアルキル基が好ましく、メチル基がより好ましい。 Examples of the alkyl group having 1 to 4 carbon atoms in R 33a and R 34a include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R 33a and R 34a include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R 33a and R 34a include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.
R 33a and R 34a are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
　ｐ及びｑは、０～２の整数が好ましく、０又は１が好ましい。 The integers of 0 and 2 are preferable for p and q, and 0 or 1 is preferable.
　化合物（１ａ）としては、例えば、式（１－１）～式（１－４３）で表される化合物が挙げられる。なお、式中、Ｒ40aは、炭素数１～２０の１価の飽和炭化水素基を表し、好ましくは炭素数６～１２の分枝鎖状アルキル基、さらに好ましくは２－エチルヘキシル基である。Ｒ26aは、式（２ａ）におけるものと同じ意味を有する。 Examples of the compound (1a) include compounds represented by the formula (1-1) to the formula (1-43). In the formula, R 40a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. R 26a has the same meaning as in formula (2a).
Figure JPOXMLDOC01-appb-I000038
Figure JPOXMLDOC01-appb-I000038
Figure JPOXMLDOC01-appb-I000039
Figure JPOXMLDOC01-appb-I000039
Figure JPOXMLDOC01-appb-I000040
Figure JPOXMLDOC01-appb-I000040
Figure JPOXMLDOC01-appb-I000041
Figure JPOXMLDOC01-appb-I000041
Figure JPOXMLDOC01-appb-I000042
Figure JPOXMLDOC01-appb-I000042
Figure JPOXMLDOC01-appb-I000043
Figure JPOXMLDOC01-appb-I000043
Figure JPOXMLDOC01-appb-I000044
Figure JPOXMLDOC01-appb-I000044
Figure JPOXMLDOC01-appb-I000045
Figure JPOXMLDOC01-appb-I000045
Figure JPOXMLDOC01-appb-I000046
Figure JPOXMLDOC01-appb-I000046
Figure JPOXMLDOC01-appb-I000047
Figure JPOXMLDOC01-appb-I000047
Figure JPOXMLDOC01-appb-I000048
Figure JPOXMLDOC01-appb-I000048
Figure JPOXMLDOC01-appb-I000049
Figure JPOXMLDOC01-appb-I000049
Figure JPOXMLDOC01-appb-I000050
Figure JPOXMLDOC01-appb-I000050
Figure JPOXMLDOC01-appb-I000051
Figure JPOXMLDOC01-appb-I000051
Figure JPOXMLDOC01-appb-I000052
Figure JPOXMLDOC01-appb-I000052
Figure JPOXMLDOC01-appb-I000053
Figure JPOXMLDOC01-appb-I000053
Figure JPOXMLDOC01-appb-I000054
Figure JPOXMLDOC01-appb-I000054
Figure JPOXMLDOC01-appb-I000055
Figure JPOXMLDOC01-appb-I000055
Figure JPOXMLDOC01-appb-I000056
Figure JPOXMLDOC01-appb-I000056
　上記化合物のうち、式（１－１）～式（１－２３）、式（１－３７）～式（１－８５）及び式（１－１０２）～式（１－１０７）で表される化合物は化合物（２ａ）に相当し、式（１－２４）～式（１－３６）及び式（１－８６）～式（１－１０１）で表される化合物は化合物（３ａ）に相当する。
　これらの中でも、Ｃ．Ｉ．アシッドレッド２８９のスルホンアミド化物、Ｃ．Ｉ．アシッドレッド２８９の４級アンモニウム塩、Ｃ．Ｉ．アシッドバイオレット１０２のスルホンアミド化物又はＣ．Ｉ．アシッドバイオレット１０２の第四級アンモニウム塩が好ましい。このような化合物としては、例えば、式（１－１）～式（１－８）、式（１－１１）及び式（１－１２）で表される化合物等が挙げられる。
　また、有機溶媒への溶解性に優れる点で、式（１－２４）～式（１－３３）で表される化合物も好ましい。
　得られる塗膜の色度域及び透過率が良好となる観点から、式（１－３２）、式（１－４４）及び式（１－９７）で表される化合物もまた好ましい。 Of the above compounds, represented by formula (1-1) to formula (1-23), formula (1-37) to formula (1-85) and formula (1-102) to formula (1-107) The compound corresponds to the compound (2a), and the compounds represented by the formula (1-24) to the formula (1-36) and the formula (1-86) to the formula (1-101) correspond to the compound (3a). ..
Among these, C.I. I. Sulfonamide compound of Acid Red 289, C.I. I. Acid Red 289 quaternary ammonium salt, C.I. I. Acid violet 102 sulfonamide or C.I. I. The quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by Formula (1-1) to Formula (1-8), Formula (1-11), and Formula (1-12).
In addition, the compounds represented by the formula (1-24) to the formula (1-33) are also preferable in terms of excellent solubility in an organic solvent.
The compounds represented by Formula (1-32), Formula (1-44) and Formula (1-97) are also preferable from the viewpoint of improving the chromaticity range and the transmittance of the obtained coating film.
　キサンテン染料（Ａ２）は、市販されているキサンテン染料（例えば、中外化成（株）製の「Ｃｈｕｇａｉ　Ａｍｉｎｏｌ　Ｆａｓｔ　Ｐｉｎｋ　Ｒ－Ｈ／Ｃ」、田岡化学工業（株）製の「Ｒｈｏｄａｍｉｎ　６Ｇ」）を用いることができる。また、市販されているキサンテン染料を出発原料として、特開２０１０－３２９９９号公報を参考に合成することもできる。 As the xanthene dye (A2), a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Co., Ltd.) is used. be able to. Alternatively, a commercially available xanthene dye can be used as a starting material and can be synthesized with reference to JP 2010-32999 A.
　〔染料（Ａ３）〕
　染料（Ａ３）は、アントラキノン染料を含む。アントラキノン染料は、公知の物質を用いてもよい。アントラキノン染料としては、例えば、
　Ｃ．Ｉ．ソルベントイエロー１１７（以下、Ｃ．Ｉ．ソルベントイエロー等の記載を省略し、番号のみの記載とする。）、１６３、１６７、１８９、
　Ｃ．Ｉ．ソルベントオレンジ７７、８６、
　Ｃ．Ｉ．ソルベントレッド１１１、１４３、１４５、１４６、１５０、１５１、１５５、１６８、１６９、１７２、１７５、１８１、２０７、２２２、２２７、２３０、２４５、２４７、
　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１４、１８、３５、３６、４５、５８、５９、５９：１、６３、６８、６９、７８、７９、８３、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３、２８、２９、３２、３３、
　Ｃ．Ｉ．アシッドレッド８０、
　Ｃ．Ｉ．アシッドグリーン２５、２７、２８、４１、
　Ｃ．Ｉ．アシッドバイオレット３４、
　Ｃ．Ｉ．アシッドブルー２５、２７、４０、４５、７８、８０、１１２、
　Ｃ．Ｉ．ディスパースイエロー５１、
　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、
　Ｃ．Ｉ．ダイレクトブルー４０、
　Ｃ．Ｉ．モーダントレッド３、１１、
　Ｃ．Ｉ．モーダントブルー８
等が挙げられる。アントラキノン染料は、有機溶剤に溶解するものが好ましい。 [Dye (A3)]
The dye (A3) contains an anthraquinone dye. A known substance may be used as the anthraquinone dye. As the anthraquinone dye, for example,
C. I. Solvent Yellow 117 (hereinafter, CI Solvent Yellow and the like are omitted and only the numbers are described), 163, 167, 189,
C. I. Solvent Orange 77, 86,
C. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,
C. I. Solvent Green 3, 28, 29, 32, 33,
C. I. Acid Red 80,
C. I. Acid green 25, 27, 28, 41,
C. I. Acid Violet 34,
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112,
C. I. Disperse Yellow 51,
C. I. Disperse Violet 26, 27,
C. I. Disperse Blue 1, 14, 56, 60,
C. I. Direct blue 40,
C. I. Mordant Red 3, 11,
C. I. Modant blue 8
Etc. The anthraquinone dye is preferably one that dissolves in an organic solvent.
　〔染料（Ａ４）〕
　染料（Ａ４）は、テトラアザポルフィリン染料を含む。テトラアザポルフィリン染料は、分子内にテトラアザポルフィリン骨格を有する化合物である。また、テトラアザポルフィリン染料が酸性染料又は塩基性染料の場合、任意のカチオン又はアニオンと塩を形成していてもよい。 [Dye (A4)]
The dye (A4) includes a tetraazaporphyrin dye. The tetraazaporphyrin dye is a compound having a tetraazaporphyrin skeleton in the molecule. When the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.
　〔顔料〕
　顔料としては、有機顔料、無機顔料が挙げられ、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化合物が挙げられる。
顔料は、単独で、又は２種以上を組み合わせて用いることができる。 [Pigment]
Examples of the pigment include organic pigments and inorganic pigments, and compounds included in the pigments according to the color index (published by The Society of Dyers and Colorists).
The pigments may be used alone or in combination of two or more.
　顔料としては、Ｃ．Ｉ．ピグメントイエロー１、３、１２、１３、１４、１５、１６、１７、２０、２４、３１、５３、８３、８６、９３、９４、１０９、１１０、１１７、１２５、１２８、１３７、１３８、１３９、１４７、１４８、１５０、１５３、１５４、１６６、１７３、１８５、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、２０２、２０９、２１５、２１６、２２４、２４２、２５４、２５５、２６４、２６５、２６９などの赤色顔料；
　Ｃ．Ｉ．ピグメントブルー１５、１５：３、１５：４、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、５９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。 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, 185, 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, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 269, etc. Red pigment;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58, 59 and other green pigments;
C. I. Pigment Brown 23, 25 and other brown pigments;
C. I. Pigment Black 1 and 7 and other black pigments.
　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。顔料の粒径は、それぞれ均一であることが好ましい。 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 particle size of the pigment is preferably uniform.
　顔料は、顔料分散剤を含有させて分散処理を行うことで、顔料分散剤溶液の中で均一に分散した状態の顔料分散液とすることができる。顔料は、それぞれ単独で分散処理してもよいし、複数種を混合して分散処理してもよい。 The pigment can be made into a pigment dispersion liquid that is uniformly dispersed in the pigment dispersant solution by performing a dispersion treatment with the pigment dispersant included. Each of the pigments may be subjected to a dispersion treatment alone or a mixture of a plurality of pigments may be subjected to a dispersion treatment.
　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、アクリル系等の顔料分散剤が挙げられる。これらの顔料分散剤は、単独でも２種以上を組合せて用いてもよい。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（ＢＡＳＦ（株）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）等が挙げられる。 Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine and acrylic pigment dispersants. 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 BASF Co., Ltd.), and Azisper (trade names) Ajinomoto Fine Techno Co., Ltd., Disperbyk (manufactured by Big Chemie), and the like.
　顔料分散剤を用いる場合、その使用量は、顔料１００質量部に対して、好ましくは１００質量部以下であり、より好ましくは５質量部以上５０質量部以下である。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。 When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniform dispersion 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、着色硬化性樹脂組成物中の固形分の総量に対して、好ましくは５質量％以上７０質量％以下であり、より好ましくは５質量％以上６０質量％以下であり、さらに好ましくは５質量％以上５０質量％以下ある。
着色剤（Ａ）の含有率が前記の範囲内であると、所望とする分光や色濃度を得ることができる。 The content of the colorant (A) in the colored curable resin composition is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass based on the total amount of solids in the colored curable resin composition. It is from 60% by mass to 60% by mass, more preferably from 5% by mass to 50% by mass.
When the content of the colorant (A) is within the above range, desired spectrum and color density can be obtained.
　本明細書において「着色硬化性樹脂組成物中の固形分の総量」とは、着色硬化性樹脂組成物から溶剤（Ｅ）を除いた成分の合計量をいう。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。 In the present specification, the “total amount of solids in the colored curable resin composition” refers to the total amount of components excluding the solvent (E) from 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.
　着色剤（Ａ）は、好ましくは染料（Ａ１）～（Ａ４）からなる群から選択される少なくとも１種を含み、より好ましくは染料（Ａ１）及び（Ａ２）を含む。
　別の実施態様では、着色剤（Ａ）は、好ましくは上記式（Ａ－ＶＩ）で表される塩を含み、より好ましくは上記式（Ａ－ＶＩ－２７）で表される塩を含む。
　着色剤（Ａ）が染料（Ａ１）を含む場合、着色剤（Ａ）は、染料（Ａ１）を溶剤に分散させた分散液として含むことができる。
　さらに別の実施態様では、着色剤（Ａ）は、好ましくはキサンテン染料（Ａ２）を含み、より好ましくは上記式（１ａ）で表される化合物を含み、さらに好ましくは上記式（２ａ）で表される化合物を含み、特に好ましくは上記式（３ａ）で表される化合物を含み、より特に好ましくは上記式（１－３２）で表される化合物、式（１－４４）で表される化合物及び式（１－９７）で表される化合物からなる群から選択される少なくとも１種を含む。
　他の実施態様では、着色剤（Ａ）は、好ましくは上記式（Ａ－ＶＩ）で表される塩と、上記式（１ａ）で表される化合物とを含み、より好ましくは上記式（Ａ－ＶＩ－２７）で表される化合物と、上記式（１－３２）で表される化合物、式（１－４４）で表される化合物及び式（１－９７）で表される化合物からなる群から選択される少なくとも１種とを含む。
　さらに他の実施態様では、着色剤（Ａ）は、好ましくは染料（Ａ１）～（Ａ４）からなる群から選択される少なくとも１種と、少なくとも１種の顔料との組合せを含み、より好ましくは染料（Ａ１）又は染料（Ａ２）と、少なくとも１種の顔料との組合せを含み、さらに好ましくは上記式（１ａ）で表される化合物と、少なくとも１種の赤色顔料とを含み、特に好ましくは上記式（１－３２）で表される化合物、式（１－４４）で表される化合物及び式（１－９７）で表される化合物からなる群から選択される少なくとも１種と、Ｃ．Ｉ．ピグメントレッドとの組合せを含み、より特に好ましくは式（１－９７）で表される化合物と、Ｃ．Ｉ．ピグメントレッド２６９との組合せを含む。
　着色剤（Ａ）が顔料を含む場合、着色剤（Ａ）は、顔料を溶剤に分散させた分散液として含むことができる。 The colorant (A) preferably contains at least one selected from the group consisting of dyes (A1) to (A4), and more preferably contains dyes (A1) and (A2).
In another embodiment, the colorant (A) preferably comprises a salt represented by the above formula (A-VI), more preferably a salt represented by the above formula (A-VI-27).
When the colorant (A) contains the dye (A1), the colorant (A) can be contained as a dispersion liquid in which the dye (A1) is dispersed in a solvent.
In yet another embodiment, the colorant (A) preferably contains a xanthene dye (A2), more preferably a compound represented by the above formula (1a), and even more preferably a compound represented by the above formula (2a). Particularly preferably a compound represented by the above formula (3a), more preferably a compound represented by the above formula (1-32), a compound represented by the formula (1-44) And at least one selected from the group consisting of compounds represented by formula (1-97).
In another embodiment, the colorant (A) preferably contains a salt represented by the above formula (A-VI) and a compound represented by the above formula (1a), and more preferably the above formula (A). -VI-27), a compound represented by the formula (1-32), a compound represented by the formula (1-44) and a compound represented by the formula (1-97) And at least one selected from the group.
In yet another embodiment, the colorant (A) comprises a combination of at least one pigment, preferably selected from the group consisting of dyes (A1) to (A4), and more preferably at least one pigment. It contains a combination of the dye (A1) or the dye (A2) and at least one pigment, more preferably the compound represented by the formula (1a) and at least one red pigment, particularly preferably At least one selected from the group consisting of the compound represented by the formula (1-32), the compound represented by the formula (1-44), and the compound represented by the formula (1-97); I. Pigment Red, and more preferably a compound represented by the formula (1-97): C.I. I. Pigment Red 269 in combination.
When the colorant (A) contains a pigment, the colorant (A) can be contained as a dispersion liquid in which the pigment is dispersed in a solvent.
　着色剤（Ａ）が染料（Ａ１）を含む場合、着色剤（Ａ）における染料（Ａ１）の含有率は、好ましくは０．５質量％以上１００質量％以下であり、より好ましくは６１質量％以上９９．５質量％以下であり、さらに好ましくは８１質量％以上９９質量％以下である。 When the colorant (A) contains the dye (A1), the content of the dye (A1) in the colorant (A) is preferably 0.5% by mass or more and 100% by mass or less, more preferably 61% by mass. Or more and 99.5 mass% or less, and more preferably 81 mass% or more and 99 mass% or less.
　着色剤（Ａ）が染料（Ａ２）を含む場合、着色剤（Ａ）における染料（Ａ２）の含有率は、好ましくは０．１質量％以上８０質量％以下であり、より好ましくは０．３質量％以上４０質量％以下であり、さらに好ましくは０．５質量％以上２０質量％以下である。
　着色剤（Ａ）が染料（Ａ１）と（Ａ２）とを含む場合、着色剤（Ａ）における染料（Ａ１）と染料（Ａ２）との質量比［（Ａ１）：（Ａ２）］は、例えば０．０１：９９．９９～９９．９９：０．０１であってよく、好ましくは５０：５０～９９．９５：０．０５であり、より好ましくは９０：１０～９９．９：０．１である。
　着色剤（Ａ）が染料（Ａ２）と顔料とを含む場合、着色剤（Ａ）における染料（Ａ２）と顔料との質量比［（Ａ１）：顔料］は、例えば１：９９～９９：１であってよく、好ましくは５：９５～５０：５０であり、より好ましくは１０：９０～３０：７０である。 When the colorant (A) contains the dye (A2), the content of the dye (A2) in the colorant (A) is preferably 0.1% by mass or more and 80% by mass or less, more preferably 0.3% by mass or more. It is from 40% by mass to 40% by mass, more preferably from 0.5% by mass to 20% by mass.
When the colorant (A) contains the dyes (A1) and (A2), the mass ratio [(A1) :( A2)] of the dye (A1) and the dye (A2) in the colorant (A) is, for example, It may be 0.01: 99.99 to 99.99: 0.01, preferably 50:50 to 99.95: 0.05, and more preferably 90:10 to 99.9: 0.1. Is.
When the colorant (A) contains the dye (A2) and the pigment, the mass ratio [(A1): pigment] of the dye (A2) and the pigment in the colorant (A) is, for example, 1:99 to 99: 1. May be, preferably 5:95 to 50:50, more preferably 10:90 to 30:70.
　着色硬化性樹脂組成物が、溶剤（以下、溶剤（Ｅ）ともいう）を含む場合、予め着色剤（Ａ）と溶剤（Ｅ）とを含む着色剤含有液を調製した後、該着色剤含有液を使用して着色硬化性樹脂組成物を調製してもよい。着色剤（Ａ）が溶剤（Ｅ）に溶解しない場合、着色剤含有液は、着色剤（Ａ）を溶剤（Ｅ）に分散させて混合することにより分散液として調製することができる。着色剤含有液は、着色硬化性樹脂組成物に含有される溶剤（Ｅ）の一部又は全部を含んでいてもよい。 When the colored curable resin composition contains a solvent (hereinafter, also referred to as a solvent (E)), a colorant-containing solution containing a colorant (A) and a solvent (E) is prepared in advance, and then the colorant-containing solution is contained. A colored curable resin composition may be prepared using a liquid. When the colorant (A) is not dissolved in the solvent (E), the colorant-containing liquid can be prepared as a dispersion by dispersing the colorant (A) in the solvent (E) and mixing them. The colorant-containing liquid may contain a part or all of the solvent (E) contained in the colored curable resin composition.
　着色剤含有液中の固形分の含有率は、着色剤含有液の総量に対して、好ましくは０．１質量％以上９９．９質量％以下、より好ましくは１質量％以上９０質量％以下であり、さらに好ましくは１質量％以上６０％以下であり、特に好ましくは３質量％以上５０質量％以下である。 The content of the solid content in the colorant-containing liquid is preferably 0.1% by mass or more and 99.9% by mass or less, more preferably 1% by mass or more and 90% by mass or less, based on the total amount of the colorant-containing liquid. Yes, more preferably 1% by mass or more and 60% by mass or less, and particularly preferably 3% by mass or more and 50% by mass or less.
　着色剤含有液中の着色剤（Ａ）の含有率は、着色剤含有液中の固形分の総量中、好ましくは０．０１質量％以上１００質量％以下であり、より好ましくは０．１質量％以上９９．９質量％以下であり、さらに好ましくは１質量％以上９９質量％以下であり、特に好ましくは１０質量％以上９０質量％以下である。 The content of the colorant (A) in the colorant-containing liquid is preferably 0.01% by mass or more and 100% by mass or less, more preferably 0.1% by mass in the total amount of solids in the colorant-containing liquid. % Or more and 99.9 mass% or less, more preferably 1 mass% or more and 99 mass% or less, and particularly preferably 10 mass% or more and 90 mass% or less.
　本明細書において「着色剤含有液中の固形分の総量」とは、着色剤含有液から溶剤（Ｅ）を除いた成分の合計量をいう。固形分の総量及びこれに対する各成分の含有量は、液体クロマトグラフィー又はガスクロマトグラフィー等の公知の分析手段で測定することができる。 In the present specification, the “total amount of solids in the colorant-containing liquid” refers to the total amount of components excluding the solvent (E) from the colorant-containing liquid. 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.
　着色剤（Ａ）は、分散剤を含有させて分散処理を行うことで、着色剤（Ａ）が着色剤含有液の中で均一に分散した状態にすることができる。 The colorant (A) can be made to be in a state of being uniformly dispersed in the colorant-containing liquid by subjecting the colorant (A) to a dispersant and performing a dispersion treatment.
　分散剤としては、界面活性剤等が挙げられ、カチオン系、アニオン系、ノニオン系及び両性のいずれの界面活性剤であってもよい。具体的にはポリエステル系、ポリアミン系及びアクリル系等の界面活性剤等が挙げられる。これらの分散剤は、単独で又は二種以上を組合せて用いてもよい。分散剤としては、商品名で表すと、ＫＰ（信越化学工業（株）製）、フローレン（共栄社化学（株）製）、ソルスパース（登録商標）（ゼネカ（株）製）、ＥＦＫＡ（登録商標）（ＢＡＳＦ（株）製）、アジスパー（登録商標）（味の素ファインテクノ（株）製）及びＤｉｓｐｅｒｂｙｋ（登録商標）（ビックケミー（株）製）、ＢＹＫ（登録商標）（ビックケミー（株）製）等が挙げられる。 Examples of the dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples thereof include polyester-based, polyamine-based, and acrylic-based surfactants. You may use these dispersants individually or in combination of 2 or more types. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Sols Perth (registered trademark) (manufactured by Zeneca Corporation), and EFKA (registered trademark) are trade names. (Manufactured by BASF Co., Ltd.), Azisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and Disperbyk (registered trademark) (manufactured by Big Chemie), BYK (registered trademark) (manufactured by Big Chemie), and the like. Can be mentioned.
　前記着色剤含有液を調製するため、分散剤を用いる場合、該分散剤（固形分）の使用量は、着色剤（Ａ）１００質量部に対して、好ましくは５質量部以上１００質量部以下であり、より好ましくは５質量部以上５０質量部以下である。該分散剤の使用量が前記の範囲にあると、より均一な分散状態の着色剤含有液が得られる傾向がある。 When a dispersant is used to prepare the colorant-containing liquid, the amount of the dispersant (solid content) used is preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the colorant (A). And more preferably 5 parts by mass or more and 50 parts by mass or less. When the amount of the dispersant used is in the above range, a more uniformly dispersed colorant-containing liquid tends to be obtained.
　〔２〕樹脂（Ｂ）
　着色硬化性樹脂組成物は、前記樹脂（Ｂ）は下記式で表される樹脂〔以下、樹脂（Ｂ１）ともいう〕を含む。 [2] Resin (B)
In the colored curable resin composition, the resin (B) contains a resin represented by the following formula [hereinafter, also referred to as resin (B1)].
Figure JPOXMLDOC01-appb-I000057
Figure JPOXMLDOC01-appb-I000057
[式中、
　Ｚは、脂環式骨格を有するテトラカルボン酸の残基を表す。
　Ｇは、水素原子又は－ＣＯ－Ｘ－（ＣＯ2Ｈ）ｘを表し、Ｘは（ｘ＋１）価の多価カルボン酸の残基を表し、ｘは１以上３以下の整数を表す。
　Ｒ1は、水素原子又はメチル基を表し、複数のＲ1は、互いに同一であってよく、又は異なっていてもよい。
　Ｒ2は、炭素原子数１以上５以下のアルキル基又はハロゲン原子を表し、Ｒ2が複数存在する場合、該複数のＲ2は、互いに同一であってよく、又は異なっていてもよい。
　ｋは０以上１０以下の整数を表し、ｎは０以上４以下の整数を表し、ｍは１以上５０以下の整数を表す。］ [In the formula,
Z represents a residue of tetracarboxylic acid having an alicyclic skeleton.
G represents a hydrogen atom or -CO-X- (CO 2 H) x, X represents a residue of a (x + 1) -valent polycarboxylic acid, and x represents an integer of 1 or more and 3 or less.
R 1 represents a hydrogen atom or a methyl group, and a plurality of R 1 may be the same as or different from each other.
R 2 represents an alkyl group or a halogen atom having 1 to 5 carbon atoms, if R 2 there are a plurality, R 2 of the plurality of may well, or different and the same as each other.
k represents an integer of 0 or more and 10 or less, n represents an integer of 0 or more and 4 or less, and m represents an integer of 1 or more and 50 or less. ]
　Ｚにおける脂環式骨格を有するテトラカルボン酸としては、例えば炭素原子数４以上１２以下の脂環式骨格を少なくとも１つ有するテトラカルボン酸が挙げられる。その具体例としては、１，２，４，５－シクロヘキサンテトラカルボン酸、１，２，３，４－シクロブタンテトラカルボン酸、１，２，３，４－シクロペンタンテトラカルボン酸等のシクロアルカンテトラカルボン酸、ビシクロ［２．２．２］オクト－７－エン－２，３，５，６－テトラカルボン酸、ジシクロヘキシル３，３’－４，４’－テトラカルボン酸及びこれらの位置異性体等が挙げられる。 Examples of the tetracarboxylic acid having an alicyclic skeleton in Z include a tetracarboxylic acid having at least one alicyclic skeleton having 4 to 12 carbon atoms. Specific examples thereof include cycloalkanetetracarboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Carboxylic acid, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, dicyclohexyl 3,3′-4,4′-tetracarboxylic acid and their positional isomers, etc. Is mentioned.
　Ｚにおける脂環式骨格を有するテトラカルボン酸の残基としては、炭素数４～１０の脂環式骨格を有するテトラカルボン酸の残基が好ましく、炭素数４～６の脂環式骨格を有するテトラカルボン酸の残基がより好ましく、下記式（Ｚ－１）～（Ｚ－５）で表される構造がさらに好ましく、炭素数４～６の飽和脂環式骨格を有するテトラカルボン酸の残基がさらにより好ましく、式（Ｚ－１）で表される構造が特に好ましい。式中、＊は主鎖中の－ＣＯ（Ｏ）－との結合手を表し、＊＊はカルボキシ基との結合手を表す。 The tetracarboxylic acid residue having an alicyclic skeleton in Z is preferably a tetracarboxylic acid residue having an alicyclic skeleton having 4 to 10 carbon atoms, and having an alicyclic skeleton having 4 to 6 carbon atoms. The residue of tetracarboxylic acid is more preferable, the structure represented by the following formulas (Z-1) to (Z-5) is further preferable, and the residue of tetracarboxylic acid having a saturated alicyclic skeleton having 4 to 6 carbon atoms is preferable. A group is even more preferable, and a structure represented by formula (Z-1) is particularly preferable. In the formula, * represents a bond with —CO (O) — in the main chain, and ** represents a bond with a carboxy group.
Figure JPOXMLDOC01-appb-I000058
Figure JPOXMLDOC01-appb-I000058
　好ましい態様においては、Ｚは、式（Ｚ－１）で表される構造である。 In a preferred embodiment, Z is a structure represented by formula (Z-1).
　Ｇにおいて、Ｘにおける（ｘ＋１）価の多価カルボン酸としては、例えばマロン酸、コハク酸、グルタル酸、アジピン酸、トリカルバリル酸、ｔ－アコニット酸、トリメリット酸が挙げられる。ｘは１以上３以下の整数を表す。 In G, examples of the (x + 1) -valent polycarboxylic acid in X include malonic acid, succinic acid, glutaric acid, adipic acid, tricarballylic acid, t-aconitic acid, and trimellitic acid. x represents an integer of 1 or more and 3 or less.
　Ｘの例としては、例えば下記式で表される構造が挙げられる。式中、＊は－ＣＯ－の炭素原子との結合手を表し、＊＊はカルボキシ基との結合手を表す。 Examples of X include a structure represented by the following formula. In the formula, * represents a bond with a carbon atom of —CO—, and ** represents a bond with a carboxy group.
Figure JPOXMLDOC01-appb-I000059
Figure JPOXMLDOC01-appb-I000059
　Ｇにおける－ＣＯ－Ｘ－（ＣＯ2Ｈ）ｘの例としては、下記式（Ｇ－１）～（Ｇ－７）で表される構造である。式中、＊は酸素原子との結合手を表し、Ｒはカルボキシ基を表す。 Examples of —CO—X— (CO 2 H) x in G are structures represented by the following formulas (G-1) to (G-7). In the formula, * represents a bond with an oxygen atom, and R represents a carboxy group.
Figure JPOXMLDOC01-appb-I000060
Figure JPOXMLDOC01-appb-I000060
　Ｒ2における炭素原子数１以上５以下のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基等が挙げられる。 Examples of the alkyl group having 1 to 5 carbon atoms in R 2 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group and the like. ..
　Ｒ2におけるハロゲン原子としては、例えばフッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。 Examples of the halogen atom in R 2 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
　ｋは０以上１０以下の整数を表す。 Κ represents an integer from 0 to 10 inclusive.
　ｎは０以上４以下の整数を表し、好ましくは０以上２以下であり、より好ましくは０である。 N represents an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less, and more preferably 0.
　ｍは１以上５０以下の整数を表す。 ㆍ m represents an integer from 1 to 50.
　樹脂（Ｂ１）の具体例としては、例えば下記表に示す式（Ｂ１－１）～（Ｂ１－１９）で表される樹脂が挙げられる。 Specific examples of the resin (B1) include resins represented by the formulas (B1-1) to (B1-19) shown in the table below.
Figure JPOXMLDOC01-appb-T000061
Figure JPOXMLDOC01-appb-T000061
　樹脂（Ｂ１）としては、好ましくは式（Ｂ１－１）、式（Ｂ１－６）～式（Ｂ１－１９）で表される樹脂である。 The resin (B1) is preferably a resin represented by the formula (B1-1), the formula (B1-6) to the formula (B1-19).
　樹脂（Ｂ１）の固形分換算での酸価は、例えば８０ｍｇ－ＫＯＨ／ｇ以上１４０ｍｇ－ＫＯＨ／ｇ以下であってよく、１００ｍｇ－ＫＯＨ／ｇ以上１３０ｍｇ－ＫＯＨ／ｇ以下、１００ｍｇ－ＫＯＨ／ｇ以上１２０ｍｇ－ＫＯＨ／ｇ以下、又は１２０ｍｇ－ＫＯＨ／ｇ以上１３０ｍｇ－ＫＯＨ／ｇ以下でもよい。 The acid value of the resin (B1) in terms of solid content may be, for example, 80 mg-KOH / g or more and 140 mg-KOH / g or less, and 100 mg-KOH / g or more and 130 mg-KOH / g or less, 100 mg-KOH / g. It may be 120 mg-KOH / g or less, or 120 mg-KOH / g or more and 130 mg-KOH / g or less.
　樹脂（Ｂ１）の分子量は、ポリスチレン換算の重量平均分子量（Ｍｗ）は、例えば１０００以上１５０００以下であってよく、重量平均分子量（Ｍｗ）が５０００以上１３０００以下でもよく、重量平均分子量（Ｍｗ）が６０００以上８０００以下でもよく、重量平均分子量（Ｍｗ）が９０００以上１２０００以下でもよい。 As for the molecular weight of the resin (B1), the weight average molecular weight (Mw) in terms of polystyrene may be, for example, 1,000 or more and 15,000 or less, the weight average molecular weight (Mw) may be 5,000 or more and 13,000 or less, and the weight average molecular weight (Mw) is It may be 6000 or more and 8000 or less, and the weight average molecular weight (Mw) may be 9000 or more and 12000 or less.
　〔樹脂（Ｂ１）の製造方法〕
　樹脂（Ｂ１）は、ビスフェノールＡ型エポキシ（メタ）アクリレート又はその２～４価カルボン酸の変性物（α）〔以下、単に「（α）」ともいう。〕と、脂環式骨格を有するテトラカルボン酸二無水物（β）〔以下、単に「（β）」ともいう。〕とを反応させることにより得られる。本明細書において「（メタ）アクリレート」とは、アクリレート及びメタクリレートよりなる群から選ばれる少なくとも１種を表す。その他の「（メタ）」を付した用語においても同様である。 [Method for producing resin (B1)]
The resin (B1) is a bisphenol A type epoxy (meth) acrylate or a modified product (α) of a divalent to tetravalent carboxylic acid thereof [hereinafter, also simply referred to as “(α)”. ], And a tetracarboxylic dianhydride (β) having an alicyclic skeleton [hereinafter, also simply referred to as “(β)”. ] It is obtained by reacting with. In the present specification, the “(meth) acrylate” represents at least one selected from the group consisting of acrylate and methacrylate. The same applies to other terms with "(meta)".
　２～４価カルボン酸は、例えば上述の式（Ｂ１）におけるＧの説明において例示した（ｘ＋１）価の多価カルボン酸、例えばマロン酸、コハク酸、グルタル酸、アジピン酸、トリカルバリル酸、ｔ－アコニット酸、トリメリット酸等が挙げられる。 The divalent to tetravalent carboxylic acid is, for example, the (x + 1) -valent polyvalent carboxylic acid exemplified in the description of G in the above formula (B1), such as malonic acid, succinic acid, glutaric acid, adipic acid, tricarballylic acid, and t. -Aconitic acid, trimellitic acid and the like can be mentioned.
　（β）の具体例は、例えば上述の式（１）におけるＺについて例示した脂環式骨格を有するテトラカルボン酸の無水物が挙げられる。その具体例としては、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物、１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－シクロペンタンテトラカルボン酸二無水物等のシクロアルカンテトラカルボン酸二無水物、ビシクロ［２．２．２］オクト－７－エン－２，３，５，６－テトラカルボン酸二無水物、ジシクロヘキシル３，３’，４，４’－テトラカルボン酸二無水物及びこれらの位置異性体等が挙げられる。 Specific examples of (β) include anhydrides of tetracarboxylic acids having an alicyclic skeleton exemplified for Z in the above formula (1). Specific examples thereof include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. Cycloalkanetetracarboxylic acid dianhydrides such as acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, dicyclohexyl 3,3 ′, 4,4′-tetracarboxylic dianhydride and positional isomers thereof are included.
　樹脂（Ｂ１）の製造方法としては、例えば（α）及び（β）の所定量、及び溶剤等を反応容器中に仕込んで、脱酸素雰囲気下で、攪拌、加熱、保温する方法等が挙げられる。溶剤としては、（α）及び（β）を溶解するものであればよく、例えばプロピレングリコールモノメチルエーテル等が挙げられる。 Examples of the method for producing the resin (B1) include a method in which a predetermined amount of (α) and (β), a solvent and the like are charged into a reaction vessel, and stirring, heating, and heat retaining are performed in a deoxygenated atmosphere. .. As the solvent, any solvent capable of dissolving (α) and (β) may be used, and examples thereof include propylene glycol monomethyl ether.
　得られた樹脂（Ｂ１）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、後述する溶剤（Ｅ）を使用することにより、反応後の溶液をそのまま使用することができ、製造工程を簡略化することができる。 The obtained resin (B1) may be used as the solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. May be used. In particular, when the solvent (E) described below is used as a solvent in this polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.
　反応は、（α）１００質量部に対して、例えば（β）１質量部～５０質量部添加して行うことができる。 The reaction can be carried out, for example, by adding 1 to 50 parts by mass of (β) to 100 parts by mass of (α).
　樹脂（Ｂ１）のポリスチレン換算の重量平均分子量（Ｍｗ）は、好ましくは１，０００以上１００，０００以下であり、より好ましくは２，０００以上５０，０００以下であり、さらに好ましくは３，０００以上３０，０００以下であり、特に好ましくは５，０００以上１５，０００以下である。重量平均分子量（Ｍｗ）が上記範囲にあると、未露光部の現像液に対する溶解性が高く、得られるパターンの残膜率や硬度も高い傾向にある。 The polystyrene equivalent weight average molecular weight (Mw) of the resin (B1) is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 50,000 or less, and further preferably 3,000 or more. It is 30,000 or less, and particularly preferably 5,000 or more and 15,000 or less. When the weight average molecular weight (Mw) is in the above range, the unexposed portion has high solubility in a developing solution, and the residual film rate and hardness of the obtained pattern tend to be high.
　樹脂（Ｂ１）の固形分換算での酸価は、好ましくは５ｍｇ－ＫＯＨ／ｇ以上２００ｍｇ－ＫＯＨ／ｇ以下であり、より好ましくは５０ｍｇ－ＫＯＨ／ｇ以上１８０ｍｇ－ＫＯＨ／ｇ以下であり、さらに好ましくは８０ｍｇ－ＫＯＨ／ｇ以上１５０ｍｇ－ＫＯＨ／ｇ以下である。酸価は、樹脂１ｇを中和するの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 (B1) in terms of solid content is preferably 5 mg-KOH / g or more and 200 mg-KOH / g or less, more preferably 50 mg-KOH / g or more and 180 mg-KOH / g or less. It is preferably 80 mg-KOH / g or more and 150 mg-KOH / g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by, for example, titration with an aqueous potassium hydroxide solution.
　樹脂（Ｂ１）の含有量は、着色硬化性樹脂組成物の固形分１００質量％中、好ましくは５質量％以上５０質量％以下であり、より好ましくは１０質量％以上４５質量％以下であり、さらに好ましく１５質量％以上４０質量％以下である。樹脂（Ｂ１）の含有量が、上記範囲にあると、未露光部の現像液に対する溶解性が高い傾向がある。 The content of the resin (B1) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less in 100% by mass of the solid content of the colored curable resin composition. It is more preferably 15% by mass or more and 40% by mass or less. When the content of the resin (B1) is in the above range, the solubility of the unexposed portion in the developing solution tends to be high.
　樹脂（Ｂ）は、樹脂（Ｂ１）とは異なった樹脂（以下、樹脂（Ｂ２）ともいう）を１種又は２種以上さらに含むことができる。 The resin (B) may further contain one kind or two or more kinds of resin different from the resin (B1) (hereinafter, also referred to as resin (B2)).
　樹脂（Ｂ２）は、アルカリ可溶性樹脂であることが好ましい。アルカリ可溶性とは、アルカリ化合物の水溶液である現像液に溶解する性質のことをいう。樹脂（Ｂ２）としては、以下の樹脂［Ｋ１］～［Ｋ６］等が挙げられる。 The resin (B2) is preferably an alkali-soluble resin. Alkali-soluble refers to the property of being dissolved in a developer which is an aqueous solution of an alkali compound. Examples of the resin (B2) 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より選択される少なくとも１種〔以下、「単量体（ａ）」ということがある。〕と、炭素数２～４の環状エーテル構造及びエチレン性不飽和結合を有する単量体〔以下、「単量体（ｂ）」ということがある。）との共重合体。
　樹脂［Ｋ２］：単量体（ａ）と単量体（ｂ）と、単量体（ａ）と共重合可能な単量体（ただし、単量体（ａ）及び単量体（ｂ）とは異なる。）〔以下「単量体（ｃ）」ということがある。〕との共重合体。
　樹脂［Ｋ３］：単量体（ａ）と単量体（ｃ）との共重合体。
　樹脂［Ｋ４］：単量体（ａ）と単量体（ｃ）との共重合体に単量体（ｂ）を反応させて得られる樹脂。
　樹脂［Ｋ５］：単量体（ｂ）と単量体（ｃ）との共重合体に単量体（ａ）を反応させて得られる樹脂。
　樹脂［Ｋ６］：単量体（ｂ）と単量体（ｃ）との共重合体に単量体（ａ）を反応させ、さらにカルボン酸無水物を反応させて得られる樹脂。 Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides [hereinafter, sometimes referred to as "monomer (a)". ] And a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "monomer (b)". ) With a copolymer.
Resin [K2]: a monomer (a), a monomer (b), and a monomer copolymerizable with the monomer (a) (however, the monomer (a) and the monomer (b)) The following may be referred to as "monomer (c)". ] The copolymer with.
Resin [K3]: Copolymer of monomer (a) and monomer (c).
Resin [K4]: A resin obtained by reacting the copolymer of the monomer (a) and the monomer (c) with the monomer (b).
Resin [K5]: A resin obtained by reacting the copolymer of the monomer (b) and the monomer (c) with the monomer (a).
Resin [K6]: A resin obtained by reacting the copolymer of the monomer (b) and the monomer (c) with the monomer (a) and further reacting with a carboxylic acid anhydride.
　単量体（ａ）としては、具体的には、
　（メタ）アクリル酸、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；
　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；
　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；
　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（ハイミック酸無水物）等の不飽和ジカルボン酸類無水物；
　コハク酸モノ〔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；
　α－（ヒドロキシメチル）（メタ）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（メタ）アクリル酸等が挙げられる。
　中でも、共重合反応性の観点やアルカリ水溶液への溶解性の観点から、（ａ）は、（メタ）アクリル酸、無水マレイン酸等であることが好ましい。 As the monomer (a), specifically,
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-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 A bicyclo unsaturated compound containing a carboxy group such as [2.2.1] hept-2-ene, 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, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent polycarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate. ;
Examples thereof include unsaturated (meth) acrylic acid containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) (meth) acrylic acid.
Among them, (a) is preferably (meth) acrylic acid, maleic anhydride or the like, from the viewpoint of copolymerization reactivity and the solubility in an alkaline aqueous solution.
　なお、本明細書において、「（メタ）アクリル」とは、アクリル及びメタクリルからなる群より選択される少なくとも１種を表す。「（メタ）アクリロイル」及び「（メタ）アクリレート」等の表記についても同様である。 In the present specification, “(meth) acrylic” means at least one selected from the group consisting of acrylic and methacrylic. The same applies to expressions such as "(meth) acryloyl" and "(meth) acrylate".
　単量体（ｂ）は、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（オキソラン環）からなる群より選択される少なくとも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。単量体（ｂ）は、好ましくは炭素数２～４の環状エーテル構造と（メタ）アクリロイルオキシ基とを有する単量体である。
　単量体（ｂ）としては、オキシラニル基とエチレン性不飽和結合とを有する単量体〔以下、「単量体（ｂ１）」ということがある。〕、オキセタニル基とエチレン性不飽和結合とを有する（ｂ２）〔以下、単量体「（ｂ２）」ということがある。〕、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〔以下、「単量体（ｂ３）」ということがある。〕等が挙げられる。 The monomer (b) includes 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 (oxolane ring)) and an ethylenically unsaturated bond. A polymerizable compound having The monomer (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
The monomer (b) may be a monomer having an oxiranyl group and an ethylenically unsaturated bond [hereinafter, referred to as "monomer (b1)". ] (B2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as a monomer "(b2)". ], A monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as “monomer (b3)”]. ] Etc. are mentioned.
　（ｂ１）としては、不飽和脂肪族炭化水素をエポキシ化した構造を有する単量体〔以下、「単量体（ｂ１－１）」ということがある。〕、不飽和脂環式炭化水素をエポキシ化した構造を有する単量体〔以下、「単量体（ｂ１－２）」ということがある。〕が挙げられる。 (B1) may be a monomer having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter, referred to as “monomer (b1-1)”. ], A monomer having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon [hereinafter, sometimes referred to as "monomer (b1-2)". ] Is mentioned.
　単量体（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 the monomer (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, and m-vinylbenzylglycidyl. Ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxy) Methyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxy) Methyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4 Examples thereof include 6-tris (glycidyloxymethyl) styrene.
　単量体（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；ダイセル化学工業（株）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；ダイセル化学工業（株）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；ダイセル化学工業（株）製）、式（Ｉ）で表される化合物、式（ＩＩ）で表される化合物等が挙げられる。 Examples of the monomer (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth). Acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) And a compound represented by the formula (II).
Figure JPOXMLDOC01-appb-I000062
Figure JPOXMLDOC01-appb-I000062
［式（Ｉ）及び式（ＩＩ）中、Ｒaa及びＲabは、互いに独立に、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。Ｘa1及びＸa2は、互いに独立に、単結合、＊－Ｒac－、＊－Ｒac－Ｏ－、＊－Ｒac－Ｓ－、又は＊－Ｒac－ＮＨ－を表す。Ｒac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 (I) and (II), R aa and R ab independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. May be replaced with. X a1 and X a2 are each independently a single bond, * - R ac -, * - R ac -O -, * - R ac -S-, or * -R represents the ac -NH-. R ac 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。
　Ｒaa及びＲab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であり、より好ましくは水素原子、メチル基である。
　Ｒacを構成する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。 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.
R aa and R ab are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.
The alkanediyl group constituting R ac is a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-group. Examples thereof include a diyl group and a hexane-1,6-diyl group.
　Ｘa1及びＸa2は、好ましくは単結合、メチレン基、エチレン基、＊－ＣＨ2－Ｏ－（＊はＯとの結合手を表す）基、＊－ＣＨ2ＣＨ2－Ｏ－基であり、より好ましくは単結合、＊－ＣＨ2ＣＨ2－Ｏ－基である。
　式（Ｉ）で表される化合物の具体例として、式（Ｉ－１）～式（Ｉ－１５）で表される化合物が挙げられ、好ましくは式（Ｉ－１）、式（Ｉ－３）、式（Ｉ－５）、式（Ｉ－７）、式（Ｉ－９）、式（Ｉ－１１）～式（Ｉ－１５）で表される化合物が挙げられ、より好ましくは式（Ｉ－１）、式（Ｉ－７）、式（Ｉ－９）、式（Ｉ－１５）で表される化合物が挙げられる。 X a1 and X a2 are preferably a single bond, a methylene group, an ethylene group, a * —CH 2 —O— (* represents a bond with O) group, or a * —CH 2 CH 2 —O— group. , And more preferably a single bond or a * —CH 2 CH 2 —O— group.
Specific examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15), preferably the formula (I-1) and the formula (I-3). ), The formula (I-5), the formula (I-7), the formula (I-9), the formula (I-11) to the formula (I-15), and more preferably the formula (I-15). Examples thereof include compounds represented by I-1), formula (I-7), formula (I-9) and formula (I-15).
Figure JPOXMLDOC01-appb-I000063
Figure JPOXMLDOC01-appb-I000063
Figure JPOXMLDOC01-appb-I000064
Figure JPOXMLDOC01-appb-I000064
　式（ＩＩ）で表される化合物の具体例としては、式（ＩＩ－１）～式（ＩＩ－１５）で表される化合物が挙げられ、好ましくは式（ＩＩ－１）、式（ＩＩ－３）、式（ＩＩ－５）、式（ＩＩ－７）、式（ＩＩ－９）、式（ＩＩ－１１）～式（ＩＩ－１５）で表される化合物が挙げられ、より好ましくは式（ＩＩ－１）、式（ＩＩ－７）、式（ＩＩ－９）、式（ＩＩ－１５）で表される化合物が挙げられる。 Specific examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15), preferably the formula (II-1) and the formula (II- 3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15), and more preferably Formula Examples thereof include compounds represented by (II-1), formula (II-7), formula (II-9) and formula (II-15).
Figure JPOXMLDOC01-appb-I000065
Figure JPOXMLDOC01-appb-I000065
Figure JPOXMLDOC01-appb-I000066
Figure JPOXMLDOC01-appb-I000066
　式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物は、それぞれ単独で用いることができる。それらは、任意の比率で混合することができる。混合する場合、その混合比率は、式（Ｉ）：式（ＩＩ）〔モル比〕で、好ましくは５：９５～９５：５、より好ましくは１０：９０～９０：１０、さらに好ましくは２０：８０～８０：２０である。
　単量体（ｂ２）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であることが好ましい。
　単量体（ｂ２）の好ましい例として、３－メチル－３－（メタ）アクリロイルオキシメチルオキセタン、３－エチル－３－（メタ）アクリロイルオキシメチルオキセタン、３－メチル－３－（メタ）アクリロイルオキシエチルオキセタン、３－エチル－３－（メタ）アクリロイルオキシエチルオキセタンが挙げられる。
　単量体（ｂ３）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であることが好ましい。単量体（ｂ３）の好ましい例として、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。 The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can be mixed in any ratio. When mixing, the mixing ratio is represented by the formula (I): formula (II) [molar ratio], preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and further preferably 20 :. 80 to 80:20.
The monomer (b2) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.
Preferred examples of the monomer (b2) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxy. Examples thereof include ethyl oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.
The monomer (b3) is preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Preferred examples of the monomer (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.
　単量体（ｃ）の具体例として、
　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」と呼ばれている。また、「トリシクロデシル（メタ）アクリレート」と呼ばれることもある。
〕、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」と呼ばれている。〕、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；
　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；
　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；　Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド、Ｎ－スクシンイミジル－３－マレイミドベンゾエート、Ｎ－スクシンイミジル－４－マレイミドブチレート、Ｎ－スクシンイミジル－６－マレイミドカプロエート、Ｎ－スクシンイミジル－３－マレイミドプロピオネート、Ｎ－（９－アクリジニル）マレイミド等のジカルボニルイミド誘導体；
　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。
　中でも、共重合反応性及び耐熱性の観点から、（ｃ）としては、ベンジル（メタ）アクリレート、トリシクロデシル（メタ）アクリレート、スチレン、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、ビシクロ［２．２．１］ヘプト－２－エン等が好ましい。また、パターン形成時の現像性に優れることから、（ｃ）としては、ベンジル（メタ）アクリレート、トリシクロデシル（メタ）アクリレートがより好ましい。 As a specific example of the monomer (c),
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- Iyl (meth) acrylate [In the art, it is referred to by its trivial name as "dicyclopentanyl (meth) acrylate". It may also be called "tricyclodecyl (meth) acrylate".
], Tricyclo [5.2.1.0 2,6 ] decen-8-yl (meth) acrylate [in the art, commonly known as "dicyclopentenyl (meth) acrylate". ], Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (Meth) acrylic acid ester such as (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid ester 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; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl Dicarbonylimide derivatives such as 4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide;
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.
Among them, from the viewpoint of copolymerization reactivity and heat resistance, examples of (c) include benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, Bicyclo [2.2.1] hept-2-ene and the like are preferable. Further, benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferable as (c) because they are excellent in developability during pattern formation.
　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、以下の範囲にあることが好ましい。
単量体（ａ）に由来する構造単位；２モル％以上５０モル％以下（より好ましくは１０モル％以上４５モル％以下）、
単量体（ｂ）に由来する構造単位、特に単量体（ｂ１）に由来する構造単位；５０モル％以上９８モル％以下（より好ましくは５５モル％以上９０モル％以下）。
　樹脂［Ｋ１］の構造単位の比率が、上記範囲にあると、保存安定性、現像性、得られるパターンの耐溶剤性に優れる傾向がある。
　樹脂［Ｋ１］は、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。
　具体的には、単量体（ａ）及び単量体（ｂ）（特に単量体（ｂ１））の所定量、重合開始剤及び溶剤等を反応容器中に仕込んで、脱酸素雰囲気下で、攪拌、加熱、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のいずれをも使用することができる。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）が挙げられる。溶剤としては、各モノマーを溶解するものであればよく、着色硬化性樹脂組成物の溶剤として後述する溶剤（Ｅ）等を用いることができる。
　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、後述する溶剤（Ｅ）を使用することにより、反応後の溶液をそのまま使用することができ、製造工程を簡略化することができる。 In the resin [K1], the ratio of the structural units derived from each is preferably in the following range in all the structural units constituting the resin [K1].
Structural unit derived from monomer (a); 2 mol% or more and 50 mol% or less (more preferably 10 mol% or more and 45 mol% or less),
Structural units derived from the monomer (b), particularly structural units derived from the monomer (b1); 50 mol% or more and 98 mol% or less (more preferably 55 mol% or more and 90 mol% or less).
When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability, the developability and the solvent resistance of the obtained pattern tend to be excellent.
The resin [K1] is described in the literature “Experimental method for polymer synthesis” (Takayuki Otsu, Kagaku Dojin, 1st edition, 1st edition, published on March 1, 1972) and the literature. It can be manufactured by referring to the cited references.
Specifically, a predetermined amount of the monomer (a) and the monomer (b) (particularly the monomer (b1)), a polymerization initiator, a solvent and the like are charged into a reaction vessel, and the reaction is performed under a deoxygenated atmosphere. , Stirring, heating, and heat retention. The polymerization initiator, solvent and the like used here are not particularly limited, and any of those commonly used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Be done. As the solvent, any solvent capable of dissolving each monomer may be used, and the solvent (E) described later or the like can be used as the solvent of the colored curable resin composition.
The obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. May be used. In particular, when the solvent (E) described below is used as a solvent in this polymerization, the solution after the reaction can be used as it is, and the manufacturing process 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、以下の範囲にあることが好ましい。
単量体（ａ）に由来する構造単位；４モル％以上４５モル％以下（より好ましくは１０モル％以上３０モル％以下）、
単量体（ｂ）に由来する構造単位、特に単量体（ｂ１）に由来する構造単位；２モル％以上９５モル％（より好ましくは５モル％以上８０モル％）、
単量体（ｃ）に由来する構造単位；１モル％以上６５モル％以下（より好ましくは５モル％以上６０モル％以下）。
　樹脂［Ｋ２］の構造単位の比率が、上記範囲にあると、保存安定性、現像性、得られるパターンの耐溶剤性、耐熱性及び機械強度に優れる傾向がある。
　樹脂［Ｋ２］は、樹脂［Ｋ１］の製造方法として記載した方法と同様にして製造することができる。具体的には、単量体（ａ）、単量体（ｂ）（特に単量体（ｂ１））及び単量体（ｃ）の所定量、重合開始剤及び溶剤を反応容器中に仕込んで、脱酸素雰囲気下で、攪拌、加熱、保温する方法が挙げられる。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。 In the resin [K2], the ratio of the structural units derived from each is preferably in the following range in all the structural units constituting the resin [K2].
Structural unit derived from monomer (a); 4 mol% or more and 45 mol% or less (more preferably 10 mol% or more and 30 mol% or less),
Structural units derived from the monomer (b), particularly structural units derived from the monomer (b1); 2 mol% or more and 95 mol% (more preferably 5 mol% or more and 80 mol%),
Structural unit derived from monomer (c); 1 mol% or more and 65 mol% or less (more preferably 5 mol% or more and 60 mol% or less).
When the ratio of the structural unit of the resin [K2] is in the above range, storage stability, developability, solvent resistance of the obtained pattern, heat resistance and mechanical strength tend to be excellent.
The resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1]. Specifically, the reaction vessel is charged with a predetermined amount of the monomer (a), the monomer (b) (particularly the monomer (b1)) and the monomer (c), a polymerization initiator and a solvent. A method of stirring, heating, and keeping heat under a deoxygenated atmosphere can be mentioned. The obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. May be used.
　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、以下の範囲にあることが好ましい。
単量体（ａ）に由来する構造単位；２モル％以上５５モル％以下（より好ましくは１０モル％以上５０モル％以下）、
単量体（ｃ）に由来する構造単位；４５モル％以上９８モル％以下（より好ましくは５０モル％以上９０モル％以下）。
　樹脂［Ｋ３］は、樹脂［Ｋ１］の製造方法として記載した方法と同様にして製造することができる。 In the resin [K3], the ratio of the structural units derived from each is preferably in the following range in all the structural units constituting the resin [K3].
Structural unit derived from the monomer (a); 2 mol% or more and 55 mol% or less (more preferably 10 mol% or more and 50 mol% or less),
Structural unit derived from monomer (c); 45 mol% or more and 98 mol% or less (more preferably 50 mol% or more and 90 mol% or less).
The resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1].
　樹脂［Ｋ４］は、単量体（ａ）と単量体（ｃ）との共重合体を得て、単量体（ｂ）が有する炭素数２～４の環状エーテル構造、特に単量体（ｂ１）が有するオキシラン環を単量体（ａ）が有するカルボン酸及び／又はカルボン酸無水物に付加させることにより製造することができる。具体的には、まず単量体（ａ）と単量体（ｃ）との共重合体を、樹脂［Ｋ１］の製造方法として記載した方法と同様にして製造する。この場合、それぞれに由来する構造単位の比率は、単量体（ａ）と単量体（ｃ）との共重合体を構成する全構造単位中、以下の範囲にあることが好ましい。
単量体（ａ）に由来する構造単位；５モル％以上５０モル％以下（より好ましくは１０モル％以上４５モル％以下）、
単量体（ｃ）に由来する構造単位；５０モル％以上９５モル％以下（より好ましくは５５モル％以上９０モル％以下）。 The resin [K4] is a cyclic ether structure having 2 to 4 carbon atoms contained in the monomer (b) obtained by obtaining a copolymer of the monomer (a) and the monomer (c), particularly a monomer. It can be produced by adding the oxirane ring of (b1) to the carboxylic acid and / or carboxylic acid anhydride of the monomer (a). Specifically, first, a copolymer of the monomer (a) and the monomer (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range in all structural units constituting the copolymer of the monomer (a) and the monomer (c).
Structural unit derived from monomer (a); 5 mol% or more and 50 mol% or less (more preferably 10 mol% or more and 45 mol% or less),
Structural unit derived from monomer (c); 50 mol% or more and 95 mol% or less (more preferably 55 mol% or more and 90 mol% or less).
　次に、上記共重合体中の単量体（ａ）に由来するカルボン酸及び／又はカルボン酸無水物の一部に、単量体（ｂ）が有する炭素数２～４の環状エーテル構造、特に単量体（ｂ１）が有するオキシラン環を反応させる。具体的には、単量体（ａ）と単量体（ｃ）との共重合体の製造に引き続き、フラスコ内雰囲気を窒素から空気に置換し、単量体（ｂ）（特に単量体（ｂ１））、カルボン酸又はカルボン酸無水物と環状エーテル構造との反応触媒（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、６０～１３０℃で、１～１０時間反応することにより、樹脂［Ｋ４］を得ることができる。
　単量体（ｂ）の使用量、特に単量体（ｂ１）の使用量は、単量体（ａ）１００モルに対して、好ましくは５モル以上８０モル以下、より好ましくは１０モル以上７５モル以下である。この範囲とすることにより、保存安定性、現像性、耐溶剤性、耐熱性、機械強度及び感度のバランスが良好になる傾向がある。環状エーテル構造の反応性が高く、未反応の単量体（ｂ）が残存しにくいことから、樹脂［Ｋ４］に用いる単量体（ｂ）としては単量体（ｂ１）が好ましく、単量体（ｂ１－１）がより好ましい。
　上記反応触媒の使用量は、単量体（ａ）、単量体（ｂ）（特に単量体（ｂ１））及び単量体（ｃ）の合計量に対して０．００１質量％以上５質量％以下であることが好ましい。
上記重合禁止剤の使用量は、単量体（ａ）、単量体（ｂ）及び単量体（ｃ）の合計量に対して０．００１質量％以上５質量％以下であることが好ましい。
　仕込方法、反応温度及び時間等の反応条件は、製造設備や重合による発熱量等を考慮して適宜調整することができる。なお、重合条件と同様に、製造設備や重合による発熱量等を考慮し、仕込方法や反応温度を適宜調整することができる。 Next, a part of the carboxylic acid and / or carboxylic acid anhydride derived from the monomer (a) in the above copolymer has a cyclic ether structure having 2 to 4 carbon atoms, which the monomer (b) has. Particularly, the oxirane ring of the monomer (b1) is reacted. Specifically, following the production of the copolymer of the monomer (a) and the monomer (c), the atmosphere in the flask is replaced with nitrogen from air to obtain the monomer (b) (particularly, the monomer). (B1)), a reaction catalyst of carboxylic acid or carboxylic acid anhydride with a cyclic ether structure (eg, tris (dimethylaminomethyl) phenol, etc.), a polymerization inhibitor (eg, hydroquinone, etc.) and the like are put in a flask, and the mixture is added to The resin [K4] can be obtained by reacting at 130 ° C. for 1 to 10 hours.
The amount of the monomer (b) used, particularly the amount of the monomer (b1) used, is preferably 5 mol or more and 80 mol or less, more preferably 10 mol or more 75 with respect to 100 mol of the monomer (a). It is less than or equal to mol. Within this range, the storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tend to be well balanced. The monomer (b1) is preferable as the monomer (b) used in the resin [K4] because the reactivity of the cyclic ether structure is high and the unreacted monomer (b) is unlikely to remain. The body (b1-1) is more preferable.
The reaction catalyst is used in an amount of 0.001% by mass or more and 5 with respect to the total amount of the monomer (a), the monomer (b) (particularly the monomer (b1)) and the monomer (c). It is preferably not more than mass%.
The amount of the polymerization inhibitor used is preferably 0.001% by mass or more and 5% by mass or less based on the total amount of the monomers (a), (b) and (c). ..
Reaction conditions such as a charging method, a reaction temperature and a time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the 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［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、単量体（ｂ）（特に単量体（ｂ１））と単量体（ｃ）との共重合体を得る。上記と同様に、得られた共重合体は、反応後の溶液をそのまま使用してもよいし、濃縮あるいは希釈した溶液を使用してもよいし、再沈殿等の方法で固体（粉体）として取り出したものを使用してもよい。
　単量体（ｂ）（特に単量体（ｂ１））及び単量体（ｃ）に由来する構造単位の比率は、上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、以下の範囲にあることが好ましい。
　単量体（ｂ）に由来する構造単位、特に単量体（ｂ１）に由来する構造単位；５モル％以上９５モル％以下（より好ましくは１０モル％以上９０モル％以下）、
　単量体（ｃ）に由来する構造単位；５モル％以上９５モル％以下（より好ましくは１０モル％以上９０モル％以下）。 In the first step, the resin [K5] is a copolymer of the monomer (b) (particularly the monomer (b1)) and the monomer (c) in the same manner as in the above-mentioned method for producing the resin [K1]. A polymer is obtained. Similarly to the 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 ratio of the structural units derived from the monomer (b) (particularly the monomer (b1)) and the monomer (c) is based on the total number of moles of all structural units constituting the above copolymer. It is preferably within the following range.
Structural units derived from the monomer (b), particularly structural units derived from the monomer (b1); 5 mol% or more and 95 mol% or less (more preferably 10 mol% or more and 90 mol% or less),
Structural unit derived from monomer (c); 5 mol% or more and 95 mol% or less (more preferably 10 mol% or more and 90 mol% or less).
　さらに、樹脂［Ｋ４］の製造方法と同様の条件で、単量体（ｂ）（特に単量体（ｂ１））と単量体（ｃ）との共重合体が有する単量体（ｂ）に由来する環状エーテル構造に、単量体（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。上記の共重合体に反応させる単量体（ａ）の使用量は、単量体（ｂ）（特に単量体（ｂ１））１００モルに対して、５モル以上８０モル以下であることが好ましい。環状エーテル構造の反応性が高く、未反応の単量体（ｂ）が残存しにくいことから、樹脂［Ｋ５］に用いる単量体（ｂ）としては単量体（ｂ１）が好ましく、単量体（ｂ１－１）がより好ましい。 Further, under the same conditions as in the method for producing the resin [K4], the monomer (b) contained in the copolymer of the monomer (b) (particularly the monomer (b1)) and the monomer (c). The resin [K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in the monomer (a) with the cyclic ether structure derived from The amount of the monomer (a) to be reacted with the above copolymer is 5 mol or more and 80 mol or less with respect to 100 mol of the monomer (b) (particularly the monomer (b1)). preferable. The monomer (b1) is preferably used as the monomer (b) used in the resin [K5] because the cyclic ether structure has high reactivity and the unreacted monomer (b) is unlikely to remain. The body (b1-1) is more preferable.
　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。
環状エーテル構造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。 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 structure and the carboxylic acid or the carboxylic acid anhydride.
　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（ハイミック酸無水物）等が挙げられる。 Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride) and the like. Be done.
　樹脂［Ｋ１］～［Ｋ６］のうち、樹脂（Ｂ）として好ましい樹脂は、［Ｋ１］又は［Ｋ２］である。樹脂（Ｂ２）は、１種の樹脂からなっていてもよく、２種以上の樹脂を含んでいてもよい。 Among the resins [K1] to [K6], the resin preferable as the resin (B) is [K1] or [K2]. The resin (B2) may be composed of one kind of resin or may contain two or more kinds of resins.
　樹脂（Ｂ２）のポリスチレン換算の重量平均分子量（Ｍｗ）は、好ましくは３，０００以上１００，０００以下であり、より好ましくは５，０００以上５０，０００以下であり、さらに好ましくは５，０００以上３０，０００以下である。重量平均分子量（Ｍｗ）が上記範囲にあると、未露光部の現像液に対する溶解性が高く、得られるパターンの残膜率や硬度も高い傾向にある。樹脂（Ｂ２）の分子量分布［重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）］は、好ましくは１．１～６であり、より好ましくは１．２～４である。 The polystyrene equivalent weight average molecular weight (Mw) of the resin (B2) is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, and further preferably 5,000 or more. It is 30,000 or less. When the weight average molecular weight (Mw) is in the above range, the unexposed portion has high solubility in a developing solution, and the residual film rate and hardness of the obtained pattern tend to be high. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B2) is preferably 1.1 to 6, and more preferably 1.2 to 4.
　樹脂（Ｂ２）の固形分換算での酸価は、好ましくは５ｍｇ－ＫＯＨ／ｇ以上２００ｍｇ－ＫＯＨ／ｇ以下であり、より好ましくは５０ｍｇ－ＫＯＨ／ｇ以上１８０ｍｇ－ＫＯＨ／ｇ以下であり、さらに好ましくは６０ｍｇ－ＫＯＨ／ｇ以上１４０ｍｇ－ＫＯＨ／ｇ以下である。酸価は、樹脂１ｇを中和するの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 (B2) in terms of solid content is preferably 5 mg-KOH / g or more and 200 mg-KOH / g or less, more preferably 50 mg-KOH / g or more and 180 mg-KOH / g or less. It is preferably 60 mg-KOH / g or more and 140 mg-KOH / g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by, for example, titration with an aqueous potassium hydroxide solution.
　着色硬化性樹脂組成物が樹脂（Ｂ２）を含む場合、樹脂（Ｂ２）の含有量は、着色硬化性樹脂組成物の固形分中、好ましくは１質量％以上５０質量％以下であり、３質量％以上４０質量％以下である。樹脂（Ｂ２）の含有量が、上記範囲にあると、未露光部の現像液に対する溶解性が高い傾向がある。 When the colored curable resin composition contains the resin (B2), the content of the resin (B2) in the solid content of the colored curable resin composition is preferably 1% by mass or more and 50% by mass or less, and 3% by mass. % To 40% by mass. When the content of the resin (B2) is in the above range, the solubility of the unexposed area in the developing solution tends to be high.
　樹脂（Ｂ）の含有率は、着色硬化性樹脂組成物の固形分中、好ましくは７質量％以上６５質量％以下であり、より好ましくは１３質量％以上６０質量％以下であり、さらに好ましくは１７質量％以上５５質量％以下である。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) in the solid content of the colored curable resin composition is preferably 7% by mass or more and 65% by mass or less, more preferably 13% by mass or more and 60% by mass or less, and further preferably It is 17% by mass or more and 55% by mass or less. 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.
　予め着色剤含有液を調製した後、該着色剤含有液を使用して着色硬化性樹脂組成物を調製する場合、着色剤含有液は、着色硬化性樹脂組成物に含有される後述の樹脂（Ｂ）の一部又は全部、好ましくは一部を予め含んでいてもよい。樹脂（Ｂ）を予め含ませておくことで着色剤含有液の分散安定性をさらに改善することができる。好ましくは、着色剤含有液は樹脂（Ｂ２）を予め含む。 When a colored curable resin composition is prepared using the colorant-containing liquid after preparing the colorant-containing liquid in advance, the colorant-containing liquid is a resin (described below) contained in the colored curable resin composition ( Part or all of B), preferably part, may be contained in advance. By including the resin (B) in advance, the dispersion stability of the colorant-containing liquid can be further improved. Preferably, the colorant-containing liquid contains the resin (B2) in advance.
　着色剤含有液中の樹脂（Ｂ）の含有量は、着色剤（Ａ）１００質量部に対して、例えば１００００質量部以下であってよく、好ましくは５０００質量部以下であり、より好ましくは１０００質量部以下であり、さらに好ましくは１質量部以上５００質量部以下であり、特に好ましくは５質量部以上２００質量部以下であり、とりわけ好ましくは１０質量部以上１００質量部以下である。 The content of the resin (B) in the colorant-containing liquid may be, for example, 10000 parts by mass or less, preferably 5000 parts by mass or less, and more preferably 1000 parts by mass with respect to 100 parts by mass of the coloring agent (A). The amount is not more than 1 part by mass, more preferably not less than 1 part by mass and not more than 500 parts by mass, particularly preferably not less than 5 parts by mass and not more than 200 parts by mass, particularly preferably not less than 10 parts by mass and not more than 100 parts by mass.
　〔３〕重合性化合物（Ｃ）
　重合性化合物（Ｃ）は、光照射等より重合開始剤（Ｄ）から発生する活性ラジカル等によって重合し得る化合物であれば、特に限定されず、重合性のエチレン性不飽和結合を有する化合物等が挙げられる。重合性化合物（Ｃ）の重量平均分子量は、３，０００以下であることが好ましく、１，５００以下であることがより好ましい。 [3] Polymerizable compound (C)
The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical or the like generated from the polymerization initiator (D) by light irradiation or the like, and a compound having a polymerizable ethylenically unsaturated bond and the like. Is mentioned. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less, and more preferably 1,500 or less.
　中でも、重合性化合物（Ｃ）としては、エチレン性不飽和結合を３つ以上有する光重合性化合物であることが好ましく、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（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）アクリレート等が挙げられる。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、ジペンタエリスリトールヘキサ（メタ）アクリレート等が好ましい。 Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and 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 Examples thereof include pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.
　本発明の着色硬化性樹脂組成物は、１種又は２種以上の重合性化合物（Ｃ）を含有することができる。重合性化合物（Ｃ）の含有量は、着色硬化性樹脂組成物中の樹脂（Ｂ）１００質量部に対して、好ましくは２０質量部以上１５０質量部以下であり、より好ましくは４０質量部以上１１０質量部以下である。 The colored curable resin composition of the present invention may contain one or more polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 parts by mass or more and 150 parts by mass or less, more preferably 40 parts by mass or more, with respect to 100 parts by mass of the resin (B) in the colored curable resin composition. It is 110 parts by mass or less.
　重合性化合物（Ｃ）の含有率は、固形分の総量に対して、７質量％以上６５質量％以下であることが好ましく、より好ましくは１３質量％以上６０質量％以下であり、さらに好ましくは１７質量％以上５５質量％以下である。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 7% by mass or more and 65% by mass or less, more preferably 13% by mass or more and 60% by mass or less, and further preferably, based on the total amount of the solid content. It is 17% by mass or more and 55% by mass or less. 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.
　〔４〕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、重合を開始し得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。 [4] Polymerization initiator (D)
The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate an active radical, an acid or the like by the action of light or heat and initiates polymerization, and a known polymerization initiator can be used.
　重合開始剤（Ｄ）としては、Ｏ－アシルオキシム化合物等のオキシム系化合物、アルキルフェノン化合物、ビイミダゾール化合物、トリアジン化合物、アシルホスフィンオキサイド化合物等が挙げられる。 Examples of the polymerization initiator (D) include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.
　重合開始剤（Ｄ）は、感度や、精密なパターン形状の形成性等を考慮して、２種以上を併用してもよい。重合開始剤（Ｄ）は、感度及び所望の線幅を有するパターン形状を精密に作り込むうえで有利であることから、Ｏ－アシルオキシム化合物等のオキシム系化合物を含むことが好ましい。 The polymerization initiator (D) may be used in combination of two or more in consideration of sensitivity, formability of precise pattern shape, and the like. The polymerization initiator (D) preferably contains an oxime compound such as an O-acyl oxime compound because it is advantageous in precisely forming a pattern shape having sensitivity and a desired line width.
　Ｏ－アシルオキシム化合物は、式（ｄ）で表される構造を有する化合物である。以下、＊は結合手を表す。 The O-acyl oxime compound is a compound having a structure represented by the formula (d). Hereinafter, * represents a bond.
Figure JPOXMLDOC01-appb-I000067
Figure JPOXMLDOC01-appb-I000067
　このようなＯ－アシルオキシム化合物としては、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）ブタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロペンチルプロパン－１－オン－２－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－｛２－メチル－４－（３，３－ジメチル－２，４－ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－イミン、Ｎ－ベンゾイルオキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－オン－２－イミン等が挙げられ、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）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－イミン及びＮ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロペンチルプロパン－１－オン－２－イミンからなる群から選ばれる少なくとも１種が好ましい。イルガキュアＯＸＥ０１、ＯＸＥ０２、ＯＸＥ０３（以上、ＢＡＳＦ（株）製）、Ｎ－１９１９（（株）ＡＤＥＫＡ製）等の市販品を用いてもよい。これらのＯ－アシルオキシム化合物であると、フォトリソグラフ性能に優れたカラーフィルタが得られる傾向にある。 Examples of such 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-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane- 1-one-2-imine and the like. Among them, the O-acyl oxime compound is N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- From the group consisting of 1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine At least one selected is preferable. Commercially available products such as Irgacure OXE01, OXE02, OXE03 (all manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may be used. When these O-acyl oxime compounds are used, a color filter having excellent photolithographic performance tends to be obtained.
　アルキルフェノン化合物は、式（ｄ４）で表される構造又は式（ｄ５）で表される構造を有する化合物である。＊は、結合手を表す。これらの構造中、ベンゼン環は置換基を有していてもよい。 The alkylphenone compound is a compound having a structure represented by the formula (d4) or a structure represented by the formula (d5). * Represents a bond. In these structures, the benzene ring may have a substituent.
Figure JPOXMLDOC01-appb-I000068
Figure JPOXMLDOC01-appb-I000068
　式（ｄ４）で表される構造を有する化合物としては、２－メチル－２－モルホリノ－１－（４－メチルスルファニルフェニル）プロパン－１－オン、２－ジメチルアミノ－１－（４－モルホリノフェニル）－２－ベンジルブタン－１－オン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］ブタン－１－オン等が挙げられる。イルガキュア３６９、９０７、３７９（以上、ＢＡＳＦ（株）製）等の市販品を用いてもよい。
　式（ｄ５）で表される構造を有する化合物としては、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－〔４－（２－ヒドロキシエトキシ）フェニル〕プロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－（４－イソプロペニルフェニル）プロパン－１－オンのオリゴマー、α，α－ジエトキシアセトフェノン、ベンジルジメチルケタール等が挙げられる。
　感度の点で、アルキルフェノン化合物としては、式（ｄ４）で表される構造を有する化合物が好ましい。 Examples of the compound having the structure represented by the formula (d4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl ) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one and the like. Be done. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF Corp.) may be used.
Examples of the compound having the structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy). ) Phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal.
From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d4).
　ビイミダゾール化合物としては、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。中でも、下記式で表される化合物又はこれらの混合物が好ましい。 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 (trialkoxyphenyl) Biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), and a biphenyl in which the phenyl group at the 4,4 ', 5,5'-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (see, for example, JP-A-7-10913). Of these, compounds represented by the following formulas or mixtures thereof are preferable.
Figure JPOXMLDOC01-appb-I000069
Figure JPOXMLDOC01-appb-I000069
　トリアジン化合物としては、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-methoxystyryl)- 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-methyl) Phenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like can be mentioned. ..
　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。
　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－ブチルペルオキシカルボニル）ベンゾフェノン、２，４，６－トリメチルベンゾフェノン等のベンゾフェノン化合物；９，１０－フェナンスレンキノン、２－エチルアントラキノン、カンファーキノン等のキノン化合物；１０－ブチル－２－クロロアクリドン、ベンジル、フェニルグリオキシル酸メチル、チタノセン化合物等が挙げられる。これらは、後述の重合開始助剤（Ｄ１）（特にアミン）と組合せて用いることが好ましい。 Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
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, 2 -Quinone compounds such as ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with the below-mentioned polymerization initiation aid (D1) (particularly amine).
　重合開始剤（Ｄ）の含有量は、樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、好ましくは０．１質量部以上３０質量部以下であり、より好ましくは２質量部以上２０質量部以下である。重合開始剤（Ｄ）の含有量が上記範囲内にあると、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傾向にある。 The content of the polymerization initiator (D) is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 2 parts by mass or more and 20 parts by mass or less. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time is shortened, so that the productivity of the color filter tends to be improved.
　〔５〕重合開始助剤（Ｄ１）
　重合開始助剤（Ｄ１）は、重合開始剤によって重合が開始された重合性化合物の重合を促進するために用いられる化合物、もしくは増感剤である。重合開始助剤（Ｄ１）を含む場合、重合開始剤（Ｄ）と組合せて用いられる。
　重合開始助剤（Ｄ１）としては、アミン化合物、アルコキシアントラセン化合物、チオキサントン化合物及びカルボン酸化合物等が挙げられる。中でも、チオキサントン化合物が好ましい。重合開始助剤（Ｄ１）を２種以上併用してもよい。 [5] Polymerization initiation aid (D1)
The polymerization initiation aid (D1) is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator. When the polymerization initiator auxiliary agent (D1) is contained, it is used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds. Of these, thioxanthone compounds are preferable. You may use together 2 or more types of polymerization initiation assistants (D1).
　アミン化合物としては、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、４－ジメチルアミノ安息香酸メチル、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸イソアミル、安息香酸２－ジメチルアミノエチル、４－ジメチルアミノ安息香酸２－エチルヘキシル、Ｎ，Ｎ－ジメチルパラトルイジン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン（通称ミヒラーズケトン）、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、４，４’－ビス（エチルメチルアミノ）ベンゾフェノン等が挙げられ、中でも、４，４’－ビス（ジエチルアミノ）ベンゾフェノンが好ましい。ＥＡＢ－Ｆ（保土谷化学工業（株）製）等の市販品を用いてもよい。 As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly called Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Examples include ethylmethylamino) benzophenone, and among them, 4,4′-bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.
　アルコキシアントラセン化合物としては、９，１０－ジメトキシアントラセン、２－エチル－９，１０－ジメトキシアントラセン、９，１０－ジエトキシアントラセン、２－エチル－９，１０－ジエトキシアントラセン、９，１０－ジブトキシアントラセン、２－エチル－９，１０－ジブトキシアントラセン等が挙げられる。 Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and 9,10-dibutoxy. Examples thereof include anthracene and 2-ethyl-9,10-dibutoxyanthracene.
　チオキサントン化合物としては、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン、１－クロロ－４－プロポキシチオキサントン等が挙げられる。 Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.
　カルボン酸化合物としては、フェニルスルファニル酢酸、メチルフェニルスルファニル酢酸、エチルフェニルスルファニル酢酸、メチルエチルフェニルスルファニル酢酸、ジメチルフェニルスルファニル酢酸、メトキシフェニルスルファニル酢酸、ジメトキシフェニルスルファニル酢酸、クロロフェニルスルファニル酢酸、ジクロロフェニルスルファニル酢酸、Ｎ－フェニルグリシン、フェノキシ酢酸、ナフチルチオ酢酸、Ｎ－ナフチルグリシン、ナフトキシ酢酸等が挙げられる。 As the carboxylic acid compound, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.
　重合開始助剤（Ｄ１）の含有量は、樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、好ましくは０．１質量部以上３０質量部以下、より好ましくは１質量部以上２０質量部以下である。重合開始助剤（Ｄ１）の含有量が上記範囲内にあると、さらに高感度で青色パターンを形成することができ、カラーフィルタの生産性が向上する傾向にある。 The content of the polymerization initiation aid (D1) is preferably 0.1 part by mass or more and 30 parts by mass or less, and more preferably 1 part by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is from 20 parts by mass to 20 parts by mass. When the content of the polymerization initiation aid (D1) is within the above range, a blue pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.
　〔６〕溶剤（Ｅ）
　本発明の着色硬化性樹脂組成物は、１種又は２種以上の溶剤（Ｅ）を含むことが好ましい。溶剤（Ｅ）としては、エステル溶剤（－ＣＯＯ－を含む溶剤）、エステル溶剤以外のエーテル溶剤（－Ｏ－を含む溶剤）、エーテルエステル溶剤（－ＣＯＯ－と－Ｏ－とを含む溶剤）、エステル溶剤以外のケトン溶剤（－ＣＯ－を含む溶剤）、アルコール溶剤、芳香族炭化水素溶剤、アミド溶剤及びジメチルスルホキシド等が挙げられる。 [6] Solvent (E)
The colored curable resin composition of the present invention preferably contains one or more solvents (E). As the solvent (E), an ester solvent (a solvent containing —COO—), an ether solvent other than the ester solvent (a solvent containing —O—), an ether ester solvent (a solvent containing —COO— and —O—), Examples thereof include ketone solvents (solvents containing —CO—) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.
　エステル溶剤としては、乳酸メチル、乳酸エチル、乳酸ブチル、２－ヒドロキシイソブタン酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル、ギ酸ペンチル、酢酸イソペンチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、シクロヘキサノールアセテート及びγ－ブチロラクトン等が挙げられる。
　エーテル溶剤としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、３－メトキシ－１－ブタノール、３－メトキシ－３－メチルブタノール、テトラヒドロフラン、テトラヒドロピラン、１，４－ジオキサン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、アニソール、フェネトール及びメチルアニソール等が挙げられる。 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.
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、ジエチレングリコールモノブチルエーテルアセテート及びジプロピレングリコールメチルエーテルアセテート等が挙げられる。 Examples of ether ester solvents 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, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.
　ケトン溶剤としては、４－ヒドロキシ－４－メチル－２－ペンタノン、アセトン、２－ブタノン、２－ヘプタノン、３－ヘプタノン、４－ヘプタノン、４－メチル－２－ペンタノン、シクロペンタノン、シクロヘキサノン及びイソホロン等が挙げられる。 Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Etc.
　アルコール溶剤としては、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール及びグリセリン等が挙げられる。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等が挙げられる。アミド溶剤としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド及びＮ－メチルピロリドン等が挙げられる。 Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene. Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
　溶剤（Ｅ）は、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を含むことが好ましい。中でも、溶剤（Ｅ）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、３－メトキシブチルアセテート、３－メトキシ－１－ブタノール、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からなる群より選択される少なくとも１種を含むことが好ましく、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、ジプロピレングリコールメチルエーテルアセテート、乳酸エチル、３－メトキシブチルアセテート、３－メトキシ－１－ブタノール及び３－エトキシプロピオン酸エチルからなる群より選択される少なくとも１種を含むことがより好ましい。 The solvent (E) preferably contains an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm from the viewpoint of coating property and drying property. Among them, the solvent (E) is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3 -Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferably contained, and at least one selected from the group consisting of propylene glycol monomethyl ether acetate and propylene glycol monomethyl is preferred. More preferably, at least one selected from the group consisting of ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate is included.
　溶剤（Ｅ）の含有量は、着色硬化性樹脂組成物中、好ましくは７０質量％以上９５質量％以下であり、より好ましくは７５質量％以上９２質量％以下である。言い換えると、着色硬化性樹脂組成物の固形分は、好ましくは５質量％以上３０質量％以下、より好ましくは８質量％以上２５質量％以下である。溶剤（Ｅ）の含有量が上記範囲にあると、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) in the colored curable resin composition is preferably 70% by mass or more and 95% by mass or less, more preferably 75% by mass or more and 92% by mass or less. In other words, the solid content of the colored curable resin composition is preferably 5% by mass or more and 30% by mass or less, more preferably 8% by mass or more and 25% by mass or less. When the content of the solvent (E) is in the above range, the flatness at the time of application becomes good, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good.
　〔７〕レベリング剤（Ｆ）
　本発明の着色硬化性樹脂組成物は、１種又は２種以上のレベリング剤（Ｆ）を含むことができる。レベリング剤（Ｆ）としては、（フッ素原子を有しない）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。 [7] Leveling agent (F)
The colored curable resin composition of the present invention may contain one kind or two or more kinds of leveling agents (F). Examples of the leveling agent (F) include silicone-based surfactants (having no fluorine atom), fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
　シリコーン系界面活性剤としては、分子内にシロキサン結合を有する界面活性剤等が挙げられる。具体的には、トーレシリコーンＤＣ３ＰＡ、同ＳＨ７ＰＡ、同ＤＣ１１ＰＡ、同ＳＨ２１ＰＡ、同ＳＨ２８ＰＡ、同ＳＨ２９ＰＡ、同ＳＨ３０ＰＡ、同ＳＨ８４００（商品名：東レ・ダウコーニング（株）製）、ＫＰ３２１、ＫＰ３２２、ＫＰ３２３、ＫＰ３２４、ＫＰ３２６、ＫＰ３４０、ＫＰ３４１（信越化学工業（株）製）、ＴＳＦ４００、ＴＳＦ４０１、ＴＳＦ４１０、ＴＳＦ４３００、ＴＳＦ４４４０、ＴＳＦ４４４５、ＴＳＦ－４４４６、ＴＳＦ４４５２及びＴＳＦ４４６０（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）等が挙げられる。 Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324. , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 (manufactured by Momentive Performance Materials Japan LLC), etc. Can be mentioned.
　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 fluorinated surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florade (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.).
　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 silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).
　レベリング剤（Ｆ）の含有量は、着色硬化性樹脂組成物中、通常０．００１質量％以上０．６質量％以下であり、好ましくは０．００２質量％以上０．４質量％以下、より好ましくは０．００５質量％以上０．３質量％以下である。なお、この含有量に、上記顔料分散剤の含有量は含まれない。 The content of the leveling agent (F) is usually 0.001% by mass or more and 0.6% by mass or less, preferably 0.002% by mass or more and 0.4% by mass or less, in the colored curable resin composition. Preferably it is 0.005 mass% or more and 0.3 mass% or less. The content of the pigment dispersant is not included in this content.
　〔８〕その他の成分
　本発明の着色硬化性樹脂組成物には、必要に応じて、充填剤、樹脂（Ｂ）以外の高分子化合物、密着促進剤、紫外線吸収剤、酸化防止剤、凝集防止剤、有機酸、有機アミン化合物、硬化剤等の添加剤を１種又は２種以上含有することができる。 [8] Other components In the colored curable resin composition of the present invention, if necessary, a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an antioxidant, an aggregation preventive agent. One or more kinds of additives such as an agent, an organic acid, an organic amine compound, and a curing agent can be contained.
　＜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、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、溶剤（Ｅ）、レベリング剤（Ｆ）、重合開始助剤（Ｄ１）、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 comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and optionally a solvent (E) and a leveling agent ( It can be prepared by mixing F), the polymerization initiation aid (D1) and other components.
　＜カラーフィルタ及びその製造方法、カラーフィルタ並びに表示素子＞
　本発明の着色硬化性樹脂組成物は、カラーフィルタの材料として有用である。本発明の着色硬化性樹脂組成物から形成されたカラーフィルタもまた、本願発明の範疇に入る。カラーフィルタは、着色パターンを形成していてもよい。
　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、好ましくはフォトリソグラフ法が挙げられる。フォトリソグラフ法は、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。本発明の着色硬化性樹脂組成物から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。本発明に係るカラーフィルタは、典型的には着色画素として用いられる。 <Color filter and its manufacturing method, color filter and display element>
The colored curable resin composition of the present invention is useful as a material for a color filter. A color filter formed from the colored curable resin composition of the present invention also falls within the scope of the present invention. The color filter may form a colored pattern.
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, and a photolithographic method is preferable. The photolithographic method is a method in which a colored curable resin composition is applied to a substrate and 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 that is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and / or not developing. A colored pattern or a colored coating film formed from the colored curable resin composition of the present invention is the color filter of the present invention. The color filter according to the present invention is typically used as a colored pixel.
　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等のガラス板や、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等の樹脂板、シリコン、上記基板上にアルミニウム、銀、銀／銅／パラジウム合金薄膜等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 silica coated, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, the above substrate Aluminum, silver, silver / copper / palladium alloy thin film, etc. are used. Other color filter layers, resin layers, transistors, circuits and the like may be formed on these substrates.
　フォトリソグラフ法による各着色画素の形成は、公知又は慣用の装置や条件で行うことができ、例えば次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。 The formation of each colored pixel by the photolithography method can be performed by a known or commonly used apparatus and conditions, and can be produced, for example, as follows. First, a 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.
　加熱乾燥を行う場合の温度としては、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～５分間が好ましく、３０秒間～３分間がより好ましい。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 temperature for heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. 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、光源としては、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。 Next, the colored composition layer is exposed through a photomask for forming a desired 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, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
　露光には、露光面全体に均一に平行光線を照射することや、フォトマスクと着色組成物層が形成された基板との正確な位置合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。 For the exposure, since it is possible to uniformly illuminate the entire exposed surface with parallel light rays and perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed, exposure of the mask aligner and stepper, etc. Preference is given to using the device.
　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であることが好ましい。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。 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 developer.
The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide. 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. Furthermore, the developing solution may contain a surfactant.
　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。
　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。ポストベーク温度としては、１５０℃以上２５０℃以下が好ましく、１６０℃以上２３５℃以下がより好ましい。ポストベーク時間としては、１分間以上１２０分間以下が好ましく、１０分間以上６０分間以下がより好ましい。 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.
Furthermore, it is preferable to perform post-baking on the obtained colored pattern. The post-baking temperature is preferably 150 ° C or higher and 250 ° C or lower, more preferably 160 ° C or higher and 235 ° C or lower. The post-baking time is preferably 1 minute or more and 120 minutes or less, more preferably 10 minutes or more and 60 minutes or less.
　得られた着色パターンの膜厚は隣接画素に影響することから、できる限り薄いことが好ましい。特に厚膜になった場合には、液晶パネルを作製した際に、光源の光が２色以上の画素を通過して漏れ出てくることがあり、斜めからパネルを見た場合、色の鮮やかさが失われてしまうおそれがある。ポストベーク後の着色パターンの膜厚は、一般的に３μｍ以下であることが好ましく、２．８μｍ以下であることがより好ましい。着色パターンの膜厚の下限は特に限定されないが、通常０．２μｍ以上であり、０．５μｍ以上であってもよい。本発明の着色硬化性樹脂組成物は、着色パターン製造時に優れた現像性を示すため、カラーフィルタの材料として優れている。 The thickness of the obtained colored pattern affects adjacent pixels, so it is preferable that the thickness is as thin as possible. Especially when a thick film is used, light from a light source may leak through pixels of two or more colors when a liquid crystal panel is manufactured. May be lost. Generally, the film thickness of the colored pattern after post-baking is preferably 3 μm or less, and more preferably 2.8 μm or less. The lower limit of the thickness of the colored pattern is not particularly limited, but is usually 0.2 μm or more, and may be 0.5 μm or more. The colored curable resin composition of the present invention is excellent as a material for a color filter because it exhibits excellent developability during the production of a colored pattern.
　本発明の着色硬化性樹脂組成物から形成された着色塗膜は、耐光性に優れ、好ましくは耐熱性にも優れる。本発明の着色硬化性樹脂組成物から形成された着色塗膜は、耐光性（ΔＥａｂ*）が例えば５．０未満であってよく、好ましくは４．９以下、より好ましくは４．８以下である。本発明によれば、特定の着色剤を含む着色硬化性樹脂組成物から形成された着色塗膜において、同一の着色剤を含む本発明によらない着色硬化性樹脂組成物から形成された着色塗膜と比べて、着色塗膜の耐光性（ΔＥａｂ*）を例えば０．５以上小さくすることが可能であり、好ましくは１．０以上、より好ましくは２．０以上小さくすることができる。耐光性（ΔＥａｂ*）は後述の実施例欄において説明する方法に従って測定することができる。 The colored coating film formed from the colored curable resin composition of the present invention has excellent light resistance and preferably also heat resistance. The colored coating film formed from the colored curable resin composition of the present invention may have a light resistance (ΔEab * ) of, for example, less than 5.0, preferably 4.9 or less, more preferably 4.8 or less. is there. According to the present invention, in a colored coating film formed from a colored curable resin composition containing a specific colorant, a colored coating formed from a colored curable resin composition not containing the same colorant according to the present invention. The light resistance (ΔEab * ) of the colored coating film can be reduced by, for example, 0.5 or more, preferably 1.0 or more, and more preferably 2.0 or more, as compared with the film. The light resistance (ΔEab * ) can be measured according to the method described in the Examples section below.
　本発明に係るカラーフィルタは、耐光性に優れ、好ましくは耐熱性及び現像性にも優れることから、表示素子、例えば液晶表示素子、有機ＥＬ素子、電子ペーパー等、及び固体撮像素子に用いられるカラーフィルタとして有用である。 The color filter according to the present invention has excellent light resistance, preferably heat resistance and developability, and thus is used for display devices such as liquid crystal display devices, organic EL devices, electronic papers, and solid-state imaging devices. It is useful as a filter.
　以下、本発明の硬化性樹脂組成物について、具体的な実施例を挙げて説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。特に断りのない限り、「部」は「質量部」を、「％」は「質量％」をそれぞれ意味する。また特に断らない限り反応は窒素雰囲気下にて行った。 Hereinafter, the curable resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass". Unless otherwise specified, the reaction was carried out in a nitrogen atmosphere.
　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).
　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℃
　　　溶媒　　　　　　；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.
Device: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by 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.
　樹脂の固形分換算での酸価は、樹脂を含む溶液について水酸化カリウム水溶液を用いて滴定することにより、樹脂１ｇを中和するのに必要な水酸化カリウムの量（ｍｇ）を求めた値とした。 The acid value in terms of solid content of the resin is a value obtained by titrating a solution containing the resin with an aqueous solution of potassium hydroxide to obtain the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin. And
〔合成例１〕
　特開２０１５－３８２０１号公報記載の方法に従って、式（Ａ－ＩＶ－２７）で表される塩を合成した。 [Synthesis Example 1]
The salt represented by the formula (A-IV-27) was synthesized according to the method described in JP-A-2015-38201.
Figure JPOXMLDOC01-appb-I000070
Figure JPOXMLDOC01-appb-I000070
〔合成例２〕
　式（ａ２）で表される化合物４０．５部と２，６－キシリジン（東京化成（株）製）６０．５部とを遮光条件下混合し、Ｎ－メチルピリドン２００部中、１５０℃で８時間攪拌した。得られた混合物を室温まで冷却後、水１２００部、及び３５％塩酸７５部の混合液中に添加し室温で１時間攪拌したところ、結晶が析出した。析出した結晶を吸引濾過により取得しメタノール１００部にて洗浄後、１晩６０℃減圧乾燥し、式（ａ３）で表される化合物４９部を得た。収率は８５％であった。 [Synthesis example 2]
40.5 parts of the compound represented by the formula (a2) and 60.5 parts of 2,6-xylidine (manufactured by Tokyo Kasei Co., Ltd.) were mixed under light-shielding conditions, and 200 parts of N-methylpyridone at 150 ° C. Stir for 8 hours. The obtained mixture was cooled to room temperature, added to a mixed solution of 1200 parts of water and 75 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour, and crystals were precipitated. The precipitated crystals were collected by suction filtration, washed with 100 parts of methanol and dried under reduced pressure at 60 ° C. overnight to obtain 49 parts of the compound represented by the formula (a3). The yield was 85%.
Figure JPOXMLDOC01-appb-I000071
Figure JPOXMLDOC01-appb-I000071
　次いで、式（ａ３）で表される化合物２８．８部と、１－ブロモプロパン２１．６部及び炭酸カリウム２４．２部をＮ－メチルピリドン１４４部中に加え、９０℃で４時間攪拌した。得られた反応混合物を室温まで冷却後に濃縮し、水５６０部中に添加し１０～１５℃で１時間攪拌したところ、結晶が析出した。生じた結晶を吸引濾過により取得後乾燥し、イオン交換水１０００部で洗浄後、１晩６０℃減圧乾燥し、式（１－３２）で表される化合物（以下、化合物（Ａ－２）と記載する）３０．０部を得た。収率は９１％であった。 Then, 28.8 parts of the compound represented by the formula (a3), 21.6 parts of 1-bromopropane and 24.2 parts of potassium carbonate were added to 144 parts of N-methylpyridone, and the mixture was stirred at 90 ° C. for 4 hours. .. The obtained reaction mixture was cooled to room temperature, concentrated, added to 560 parts of water and stirred at 10 to 15 ° C. for 1 hour, and crystals were precipitated. The resulting crystals are collected by suction filtration, dried, washed with 1000 parts of ion-exchanged water, and dried under reduced pressure at 60 ° C. overnight to give a compound represented by the formula (1-32) (hereinafter referred to as compound (A-2)). 30.0 parts are obtained. The yield was 91%.
Figure JPOXMLDOC01-appb-I000072
Figure JPOXMLDOC01-appb-I000072
　化合物（Ａ－２）の同定
（質量分析）イオン化モード＝ＥＳＩ＋：　ｍ／ｚ＝[Ｍ＋Ｈ]+６５９．３
　　　　　　　　　　　　　　Ｅｘａｃｔ　Ｍａｓｓ：　６５８．３ Identification of compound (A-2) (mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 659.3
Exact Mass: 658.3
〔合成例３〕
　特開２０１７－２２６８１４号の実施例２に記載の方法に従い、式（１－９７）で表される化合物（以下、化合物（Ａ－４）と記載する）１．０部を得た。 [Synthesis Example 3]
According to the method described in Example 2 of JP-A-2017-226814, 1.0 part of the compound represented by the formula (1-97) (hereinafter referred to as compound (A-4)) was obtained.
Figure JPOXMLDOC01-appb-I000073
Figure JPOXMLDOC01-appb-I000073
　式（１－１９９）で表される化合物の同定
（質量分析）イオン化モード＝ＥＳＩ＋：　ｍ／ｚ＝［Ｍ＋Ｈ］+　７４７．５
　　　　　　　　　　　　　　Ｅｘａｃｔ　Ｍａｓｓ：　７４６．３ Identification of Compound Represented by Formula (1-199) (Mass Spectrometry) Ionization Mode = ESI +: m / z = [M + H] + 747.5
Exact Mass: 746.3
〔合成例４〕
　特開２０１６－２７０７５号の実施例１に記載の方法に従い、式（１－４４）で表される化合物（以下、化合物（Ａ－５）と記載する）５２部を得た。 [Synthesis Example 4]
According to the method described in Example 1 of JP-A-2016-27075, 52 parts of a compound represented by the formula (1-44) (hereinafter referred to as compound (A-5)) was obtained.
Figure JPOXMLDOC01-appb-I000074
Figure JPOXMLDOC01-appb-I000074
　式（１－３４）で表される化合物の同定
（質量分析）イオン化モード＝ＥＳＩ＋：　ｍ／ｚ＝［Ｍ＋Ｈ］+　５９９．２
　　　　　　　　　　　　　　Ｅｘａｃｔ　Ｍａｓｓ：　５９８．２ Identification of Compound Represented by Formula (1-34) (Mass Spectrometry) Ionization Mode = ESI +: m / z = [M + H] + 599.2
Exact Mass: 598.2
〔合成例５－１〕
（樹脂（Ｂ１－１ａ）の合成）
　セパラブルフラスコ中に、ビスフェノールＡ型エポキシアクリレートのプロピレングリコールモノメチルエーテルアセテート溶液を固形分換算で６６．６部、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物１７.４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３２．７部を混合し、徐々に昇温して１００～１０５℃で１４時間反応させた。その後、プロピレングリコールモノメチルエーテルアセテート７.２部を加えて希釈し、下記式（Ｂ１－１）で表される構造を有する共重合体（樹脂（Ｂ１－１ａ）溶液；固形分５６．９％）を得た。得られた共重合体の酸価は固形分換算で１１３.７ｍｇ－ＫＯＨ/ｇ、重量平均分子量Ｍｗは６４００であった。 [Synthesis Example 5-1]
(Synthesis of resin (B1-1a))
In a separable flask, 66.6 parts of propylene glycol monomethyl ether acetate solution of bisphenol A type epoxy acrylate in terms of solid content, 17.4 parts of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and propylene glycol. 32.7 parts of monomethyl ether acetate were mixed and gradually heated to react at 100 to 105 ° C. for 14 hours. Then, 7.2 parts of propylene glycol monomethyl ether acetate was added and diluted to obtain a copolymer having a structure represented by the following formula (B1-1) (resin (B1-1a) solution; solid content 56.9%). Got The acid value of the obtained copolymer was 113.7 mg-KOH / g in terms of solid content, and the weight average molecular weight Mw was 6400.
Figure JPOXMLDOC01-appb-I000075
Figure JPOXMLDOC01-appb-I000075
　［式（Ｂ１－１）中、ｋは０以上１０以下の整数を表し、ｍは１以上５０以下の整数を表す。］ [In the formula (B1-1), k represents an integer of 0 or more and 10 or less, and m represents an integer of 1 or more and 50 or less. ]
〔合成例５－２〕
（樹脂（Ｂ１－１ｂ）の合成）
　セパラブルフラスコ中に、ビスフェノールＡ型エポキシアクリレートのプロピレングリコールモノメチルエーテルアセテート溶液を固形分換算で６６．６部、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物２０．２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３２．７部を混合し、徐々に昇温して１００～１０５℃で１４時間反応させた。その後、プロピレングリコールモノメチルエーテルアセテート９.６部を加えて希釈し、式（Ｂ１－１）で表される構造を有する共重合体（樹脂（Ｂ１－１ｂ）溶液；固形分５８．５％）を得た。得られた共重合体の酸価は固形分換算で１２６.０ｍｇ－ＫＯＨ/ｇ、重量平均分子量Ｍｗは１０２００であった。 [Synthesis Example 5-2]
(Synthesis of resin (B1-1b))
In a separable flask, 66.6 parts of propylene glycol monomethyl ether acetate solution of bisphenol A type epoxy acrylate, 20.2 parts of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and propylene glycol in terms of solid content. 32.7 parts of monomethyl ether acetate were mixed and gradually heated to react at 100 to 105 ° C. for 14 hours. Then, 9.6 parts of propylene glycol monomethyl ether acetate was added and diluted to obtain a copolymer (resin (B1-1b) solution; solid content 58.5%) having a structure represented by the formula (B1-1). Obtained. The acid value of the obtained copolymer was 126.0 mg-KOH / g in terms of solid content, and the weight average molecular weight Mw was 10200.
〔合成例６〕
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流し窒素雰囲気に置換し、乳酸エチル１４１部、プロピレングリコールモノメチルエーテルアセテート１７８部を入れ、攪拌しながら８５℃まで加熱した。次いで、アクリル酸３８部、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－９－イルアクリレートの混合物（含有比はモル比で１：１）２５部、Ｎ－シクロヘキシルマレイミド１３７部、２－ヒドロキシエチルメタクリレート５０部、プロピレングリコールモノメチルエーテルアセテート３３８部の混合溶液を５時間かけて滴下した。一方、２，２－アゾビスイソブチロニトリル５部をプロピレングリコールモノメチルエーテルアセテート８８部に溶解した溶液を６時間かけて滴下した。滴下終了後、８５℃で４時間保持した後、室温まで冷却して、Ｂ型粘度計（２３℃）で測定した粘度２３ｍＰａｓ、固形分２５．６％の共重合体（樹脂（Ｂ－２））溶液を得た。生成した共重合体の重量平均分子量Ｍｗは８．０×１０3、分散度２．１、固形分換算の酸価は１１０ｍｇ－ＫＯＨ／ｇであった。樹脂（Ｂ２－１）は、以下の構造単位を有する。 [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, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 85 ° C. with stirring. Then, 38 parts of acrylic acid, 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 25 parts of a mixture of decan-9-yl acrylate (content ratio is 1: 1 by molar ratio), 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate is added. It dripped over 5 hours. On the other hand, a solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was kept at 85 ° C. for 4 hours, then cooled to room temperature, and had a viscosity of 23 mPas measured by a B-type viscometer (23 ° C.) and a solid content of 25.6% (resin (B-2)). ) A solution was obtained. The weight average molecular weight Mw of the produced copolymer was 8.0 × 10 3 , the dispersity was 2.1, and the acid value in terms of solid content was 110 mg-KOH / g. The resin (B2-1) has the following structural units.
Figure JPOXMLDOC01-appb-I000076
Figure JPOXMLDOC01-appb-I000076
〔合成例７〕
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流し窒素雰囲気に置換し、プロピレングリコールモノメチルエーテルアセテート２８０部を入れ、攪拌しながら８０℃まで加熱した。次いで、アクリル酸３８部、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－９－イルアクリレートの混合物（含有比はモル比で１：１）２８９部、プロピレングリコールモノメチルエーテルアセテート１２５部の混合溶液を５時間かけて滴下した。一方、２，２－アゾビス（２，４－ジメチルバレロニトリル）３３部をプロピレングリコールモノメチルエーテルアセテート２３５部に溶解させた溶液を６時間かけて滴下した。滴下終了後、８０℃で４時間保持した後、室温まで冷却して、固形分３５．１％、Ｂ型粘度計（２３℃）で測定した粘度１２５ｍＰａｓの共重合体（樹脂（Ｂ－３））溶液を得た。生成した共重合体の重量平均分子量Ｍｗは９．２×１０3、分散度２．０８、固形分換算の酸価は７７ｍｇ－ＫＯＨ／ｇであった。樹脂（Ｂ２－２）は以下の構造単位を有する。 [Synthesis example 7]
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, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then, 38 parts of acrylic acid, 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 289 parts of a mixture of decan-9-yl acrylate (content ratio is 1: 1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution of 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was kept at 80 ° C. for 4 hours, then cooled to room temperature, and solidified at 35.1% and had a viscosity of 125 mPas measured by a B type viscometer (23 ° C.) (resin (B-3)). ) A solution was obtained. The weight average molecular weight Mw of the produced copolymer was 9.2 × 10 3 , the dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. The resin (B2-2) has the following structural units.
Figure JPOXMLDOC01-appb-I000077
Figure JPOXMLDOC01-appb-I000077
〔分散液１の作製〕
　合成例１で得られた式（Ａ－ＩＶ－２７）で表される塩を５１．２部、分散剤（ＢＹＫ社製　ＢＹＫＬＰＮ－６９１９；プロピレングリコールモノメチルエーテルアセテート６０％溶液）を２１．４部、樹脂（Ｂ２－２）（固形分換算）を２０．５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３３４部を混合し、０．４μｍのジルコニアビーズ６００部を加え、ペイントコンディショナー（ＬＡＵ社製）を使用して１時間振盪した。その後、ジルコニアビーズをろ過により除去して分散液（Ａ－１）を得た。 [Preparation of dispersion 1]
51.2 parts of the salt represented by the formula (A-IV-27) obtained in Synthesis Example 1 and 21.4 parts of a dispersant (BYKLPN-6919 manufactured by BYK; propylene glycol monomethyl ether acetate 60% solution). , 20.5 parts of resin (B2-2) (as solid content) and 334 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and a paint conditioner (manufactured by LAU) was used. And shaken for 1 hour. Then, the zirconia beads were removed by filtration to obtain a dispersion liquid (A-1).
〔分散液２の作製〕
　Ｃ．Ｉ．ピグメントレッド２６９を４６．５部、分散剤（固形分換算）を２３．２部、樹脂（Ｂ２－２）（固形分換算）を１３．９部、プロピレングリコールモノメチルエーテル５７．７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２４６部を混合し、０．４μｍのジルコニアビーズ６００部を加え、ペイントコンディショナー（ＬＡＵ社製）を使用して１時間振盪した。その後、ジルコニアビーズをろ過により除去して分散液（Ａ－３）を得た。 [Preparation of dispersion 2]
C. I. Pigment Red 269 46.5 parts, dispersant (solid content) 23.2 parts, Resin (B2-2) (solid content) 13.9 parts, propylene glycol monomethyl ether 57.7 parts and propylene glycol. 246 parts of monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid (A-3).
〔実施例１～５、比較例１～４〕
〔着色硬化性樹脂組成物の調製〕
　表３～表６に示す各成分を混合して、各々の着色硬化性樹脂組成物を得た。
・着色剤（Ａ）：
　分散液（Ａ－１）：〔分散液１の作製〕で得られた分散液（Ａ－１），
　分散液（Ａ－３）：〔分散液２の作製〕で得られた分散液（Ａ－３），
　着色剤（Ａ－２）：〔合成例２〕で得られた化合物（Ａ－２），
　着色剤（Ａ－４）：〔合成例３〕で得られた化合物（Ａ－４），
着色剤（Ａ－５）：〔合成例４〕で得られた化合物（Ａ－５），
・樹脂（Ｂ）：
　（Ｂ１－１ａ）：〔合成例５－１〕で得られた樹脂（Ｂ１－１ａ）（固形分換算）,
　（Ｂ１－１ｂ）：〔合成例５－２〕で得られた樹脂（Ｂ１－１ｂ）（固形分換算），
　（Ｂ２－１）：〔６〕で得られた樹脂（Ｂ２－１）（固形分換算）,
・重合性化合物（Ｃ）
　（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）：
　（Ｄ－１）：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；オキシム化合物）
・溶剤（Ｅ）：
　（Ｅ－１）：乳酸エチル
　（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
　（Ｅ－３）：ジアセトンアルコール
・レベリング剤（Ｆ）：
　（Ｆ－１）：ポリエーテル変性シリコーンオイル（固形分換算）
（トーレシリコーンＳＨ８４００；東レダウコーニング（株）製） [Examples 1 to 5, Comparative Examples 1 to 4]
[Preparation of colored curable resin composition]
The components shown in Tables 3 to 6 were mixed to obtain respective colored curable resin compositions.
・ Colorant (A):
Dispersion (A-1): Dispersion (A-1) obtained in [Preparation of Dispersion 1],
Dispersion (A-3): Dispersion (A-3) obtained in [Preparation of Dispersion 2],
Colorant (A-2): Compound (A-2) obtained in [Synthesis Example 2],
Colorant (A-4): Compound (A-4) obtained in [Synthesis Example 3],
Colorant (A-5): Compound (A-5) obtained in [Synthesis Example 4],
・ Resin (B):
(B1-1a): Resin (B1-1a) obtained in [Synthesis example 5-1] (as solid content),
(B1-1b): Resin (B1-1b) obtained in [Synthesis Example 5-2] (as solid content),
(B2-1): Resin (B2-1) obtained in [6] (solid content conversion),
-Polymerizable compound (C)
(C-1): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
-Polymerization initiator (D):
(D-1): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Corporation; oxime compound)
・ Solvent (E):
(E-1): Ethyl lactate (E-2): Propylene glycol monomethyl ether acetate (E-3): Diacetone alcohol / leveling agent (F):
(F-1): Polyether-modified silicone oil (solid content conversion)
(Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)
　得られた着色硬化性樹脂組成物について、下記の方法により、その評価を行った。結果を表３に示す。 The obtained colored curable resin composition was evaluated by the following method. The results are shown in Table 3.
＜カラーフィルタ（着色塗膜）の形成＞
　２インチ角のガラス基板（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スピンコート法で塗布した後、１００℃で３分間プリベークして、着色組成物層を形成した。冷却後、露光機（ＴＭＥ－１５０ＲＳＫ；トプコン（株）製）を用いて、大気雰囲気下、６０ｍＪ／ｃｍ2の露光量（３６５ｎｍ基準）で着色組成物層に光照射した。光照射後、オーブン中、２３０℃で２０分間ポストベークを行うことにより、着色塗膜を得た。放冷後、得られた着色塗膜の膜厚を、膜厚測定装置（ＤＥＫＴＡＫ３；日本真空技術（株）製））を用いて測定したところ、３．０μｍであった。 <Formation of color filter (colored coating film)>
A colored curable resin composition was applied onto a 2-inch square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, an exposure device (TME-150RSK; manufactured by Topcon Corp.) was used to irradiate the colored composition layer with light at an exposure amount of 60 mJ / cm 2 (365 nm standard) in an air atmosphere. After light irradiation, post-baking was performed in an oven at 230 ° C. for 20 minutes to obtain a colored coating film. After allowing to cool, the film thickness of the obtained colored coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 3.0 μm.
＜耐光性評価＞
　得られたガラス基板上の薄膜について、測色機（ＯＳＰ－ＳＰ－２００；オリンパス（株）製）を用いて分光を測定し、Ｃ光源の等色関数を用いてＣＩＥのＸＹＺ表色系におけるｘｙ色度座標（ｘ、ｙ）及びＹを測定した。上記パターンをキセノンランプで４８時間照射した。照射後、再度ｘｙ色度座標及びＹを測定し、該測定値からＪＩＳ　Ｚ　８７３０：２００９（７．色差の計算方法）に記載される方法で、照射前後での色差ΔＥａｂ*を計算した。結果を表３に示す。 <Light resistance evaluation>
The thin film on the glass substrate thus obtained was subjected to spectroscopic measurement using a colorimeter (OSP-SP-200; manufactured by Olympus Corp.), and the CIE XYZ color system was used using the color matching function of the C light source. The xy chromaticity coordinates (x, y) and Y were measured. The above pattern was irradiated with a xenon lamp for 48 hours. After irradiation, the xy chromaticity coordinates and Y were measured again, and the color difference ΔEab * before and after irradiation was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000078
単位：質量部
Figure JPOXMLDOC01-appb-T000078
Unit: parts by mass
　実施例１～２の着色硬化性樹脂組成物を用いて形成されたパターンにおいて、ΔＥａｂ*は比較例１より小さい値を示し、高い耐光性が確認された。
　実施例３の着色硬化性樹脂組成物を用いて形成されたパターンにおいて、ΔＥａｂ*は比較例２より小さい値を示し、高い耐光性が確認された。
　実施例４の着色硬化性樹脂組成物を用いて形成されたパターンにおいて、ΔＥａｂ*は比較例３より小さい値を示し、高い耐光性が確認された。
　実施例５の着色硬化性樹脂組成物を用いて形成されたパターンにおいて、ΔＥａｂ*は比較例４より小さい値を示し、高い耐光性が確認された。
　本願発明に従う実施例１～５はいずれも、比較例１～４に比べΔＥａｂ*が小さく、高い耐光性が確認された。本願発明の着色硬化性樹脂組成物によれば、優れた着色塗膜を形成することができることが理解される。 In the patterns formed using the colored curable resin compositions of Examples 1 and 2, ΔEab * showed a value smaller than that of Comparative Example 1, and high light resistance was confirmed.
In the pattern formed using the colored curable resin composition of Example 3, ΔEab * showed a value smaller than that of Comparative Example 2, and high light resistance was confirmed.
In the pattern formed using the colored curable resin composition of Example 4, ΔEab * showed a value smaller than that of Comparative Example 3, and high light resistance was confirmed.
In the pattern formed using the colored curable resin composition of Example 5, ΔEab * showed a value smaller than that of Comparative Example 4, and high light resistance was confirmed.
In each of Examples 1 to 5 according to the present invention, ΔEab * was smaller than that of Comparative Examples 1 to 4, and high light resistance was confirmed. It is understood that the colored curable resin composition of the present invention can form an excellent colored coating film.
　本発明の着色硬化性樹脂組成物によると、耐光性に優れた着色塗膜を形成することができ、産業上極めて有用である。 According to the colored curable resin composition of the present invention, a colored coating film having excellent light resistance can be formed, which is extremely useful industrially.

Claims (6)

  1. 　着色剤（Ａ）と、樹脂（Ｂ）と、重合性化合物（Ｃ）と、重合開始剤（Ｄ）と、を含有し、前記樹脂（Ｂ）は下記式（Ｂ１）で表される樹脂を含む、着色硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-I000001
    ［式中、
    　Ｚは、脂環式骨格を有するテトラカルボン酸の残基を表す。
    　Ｇは、水素原子又は－ＣＯ－Ｘ－（ＣＯ2Ｈ）ｘを表し、Ｘは（ｘ＋１）価の多価カルボン酸の残基を表し、ｘは１以上３以下の整数を表す。
    　Ｒ1は、水素原子又はメチル基を表し、複数のＲ1は、互いに同一であってよく、又は異なっていてもよい。
    　Ｒ2は、炭素原子数１以上５以下のアルキル基又はハロゲン原子を表し、Ｒ2が複数存在する場合、該複数のＲ2は、互いに同一であってよく、又は異なっていてもよい。
    　ｋは０以上１０以下の整数を表し、ｎは０以上４以下の整数を表し、ｍは１以上５０以下の整数を表す。］     A colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D) are contained, and the resin (B) is a resin represented by the following formula (B1). A colored curable resin composition containing.
    Figure JPOXMLDOC01-appb-I000001
    [In the formula,
    Z represents a residue of tetracarboxylic acid having an alicyclic skeleton.
    G represents a hydrogen atom or -CO-X- (CO 2 H) x, X represents a residue of a (x + 1) -valent polycarboxylic acid, and x represents an integer of 1 or more and 3 or less.
    R 1 represents a hydrogen atom or a methyl group, and a plurality of R 1 may be the same as or different from each other.
    R 2 represents an alkyl group or a halogen atom having 1 to 5 carbon atoms, if R 2 there are a plurality, R 2 of the plurality of may well, or different and the same as each other.
    k represents an integer of 0 or more and 10 or less, n represents an integer of 0 or more and 4 or less, and m represents an integer of 1 or more and 50 or less. ]
  2. 　前記式（Ｂ１）において、Ｚは炭素数４～１０の脂環式骨格を有するテトラカルボン酸の残基である、請求項１に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to claim 1, wherein in the formula (B1), Z is a residue of a tetracarboxylic acid having an alicyclic skeleton having 4 to 10 carbon atoms.
  3. 　前記式（Ｂ１）において、Ｚは炭素数４～６の飽和脂環式骨格を有するテトラカルボン酸の残基である、請求項１又は２に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to claim 1 or 2, wherein in the formula (B1), Z is a residue of a tetracarboxylic acid having a saturated alicyclic skeleton having 4 to 6 carbon atoms.
  4. 　請求項１～３のいずれか一項に記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。 A color filter formed from the colored curable resin composition according to any one of claims 1 to 3.
  5. 　請求項４に記載のカラーフィルタを含む表示素子。 A display device including the color filter according to claim 4.
  6. 　請求項５に記載のカラーフィルタを含む固体撮像素子。 A solid-state image sensor including the color filter according to claim 5.
PCT/JP2019/043190 2018-11-14 2019-11-05 Colored curable resin composition WO2020100646A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020217012920A KR20210090620A (en) 2018-11-14 2019-11-05 Colored curable resin composition
CN201980075082.7A CN113166338B (en) 2018-11-14 2019-11-05 Colored curable resin composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018213509 2018-11-14
JP2018-213509 2018-11-14
JP2019088862A JP7292963B2 (en) 2018-11-14 2019-05-09 Colored curable resin composition
JP2019-088862 2019-05-09

Publications (1)

Publication Number Publication Date
WO2020100646A1 true WO2020100646A1 (en) 2020-05-22

Family

ID=70731558

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/043190 WO2020100646A1 (en) 2018-11-14 2019-11-05 Colored curable resin composition

Country Status (1)

Country Link
WO (1) WO2020100646A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005316449A (en) * 2004-03-30 2005-11-10 Nippon Steel Chem Co Ltd Photosensitive resin composition and color filter using the same
JP2006003860A (en) * 2003-11-26 2006-01-05 Nippon Steel Chem Co Ltd Photosensitive resin composition and color filter using the same
JP2006276421A (en) * 2005-03-29 2006-10-12 Nippon Steel Chem Co Ltd Photosensitive resin composition and color filter using same
WO2018211890A1 (en) * 2017-05-19 2018-11-22 ナガセケムテックス株式会社 Alkali soluble resin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006003860A (en) * 2003-11-26 2006-01-05 Nippon Steel Chem Co Ltd Photosensitive resin composition and color filter using the same
JP2005316449A (en) * 2004-03-30 2005-11-10 Nippon Steel Chem Co Ltd Photosensitive resin composition and color filter using the same
JP2006276421A (en) * 2005-03-29 2006-10-12 Nippon Steel Chem Co Ltd Photosensitive resin composition and color filter using same
WO2018211890A1 (en) * 2017-05-19 2018-11-22 ナガセケムテックス株式会社 Alkali soluble resin

Similar Documents

Publication Publication Date Title
JP6713517B2 (en) Red colored curable resin composition
JP6028326B2 (en) Colored curable resin composition
JP6098113B2 (en) Colored photosensitive resin composition
JP6019596B2 (en) Colored photosensitive resin composition
JP6019597B2 (en) Colored photosensitive resin composition
JP5962388B2 (en) Colored curable resin composition
JP2017128708A (en) Colored curable resin composition
JP2018035345A (en) Colored curable resin composition
JP6912237B2 (en) Color curable resin composition, color filter and display device containing it
KR101980262B1 (en) Colored photosensitive resin composition
JP6238516B2 (en) Colored curable resin composition
KR101972963B1 (en) Colored photosensitive resin composition
JP6047885B2 (en) Colored photosensitive resin composition
JP6115005B2 (en) Colored photosensitive resin composition
JP6931575B2 (en) Coloring composition, coloring curable resin composition, color filter and liquid crystal display device
WO2020170944A1 (en) Colored curable resin composition, color filter, and display device
JP7292963B2 (en) Colored curable resin composition
WO2021020265A1 (en) Colored curable resin composition
JP7457577B2 (en) Phenothiazine compound and curable resin composition containing the same
WO2020100646A1 (en) Colored curable resin composition
JP7324045B2 (en) Colored curable resin composition
JP2013050505A (en) Colored photosensitive 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: 19884900

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19884900

Country of ref document: EP

Kind code of ref document: A1