WO2020170944A1 - Colored curable resin composition, color filter, and display device - Google Patents
Colored curable resin composition, color filter, and display device Download PDFInfo
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- WO2020170944A1 WO2020170944A1 PCT/JP2020/005613 JP2020005613W WO2020170944A1 WO 2020170944 A1 WO2020170944 A1 WO 2020170944A1 JP 2020005613 W JP2020005613 W JP 2020005613W WO 2020170944 A1 WO2020170944 A1 WO 2020170944A1
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- 0 CCN(CC)c(cc1O2)ccc1C(c1c(*)cccc1)=C(C=C1)C2=CC1=*(C)CCC*(C)* Chemical compound CCN(CC)c(cc1O2)ccc1C(c1c(*)cccc1)=C(C=C1)C2=CC1=*(C)CCC*(C)* 0.000 description 2
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
Definitions
- the present invention relates to a colored curable resin composition, a color filter and a display device.
- Patent Document 1 JP-A-2018-101015 (Patent Document 1) describes a colored resin composition for a color filter, which contains a coloring material represented by the following formula, a binder component, and a solvent.
- the line width of the pattern of the color filter obtained after post-baking tends to be thick. It is in.
- An object of the present invention is to have a high film thickness retention rate (hereinafter, may be abbreviated as “film thickness retention rate”) in a color filter before and after post-baking, and the line width of the color filter obtained after post-baking does not become thick.
- film thickness retention rate a high film thickness retention rate
- a colored curable resin composition is provided.
- a colored curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (E), The colored curable resin composition, wherein the colorant (A) contains a xanthene dye, and the thiol compound (E) contains an ether bond-containing thiol compound.
- the ether bond-containing thiol compound is a compound represented by the formula (I).
- A-(R 1 -SH) n (I) [In the formula, A represents a residue of a polyhydric alcohol having m hydroxy groups, The plurality of R 1 bonded to oxygen atoms derived from the m hydroxy groups each independently represents an alkylene group having 1 to 10 carbon atoms, m is an integer of 2 or more, n is an integer of 2 or more, and m ⁇ n. ] [3] The colored curable resin composition according to [2], wherein m is 2 to 10. [4] The colored curable resin composition according to [2] or [3], wherein the polyhydric alcohol is pentaerythritol or trimethylolpropane. [5] The colored curable resin composition according to any one of [1] to [4], wherein the xanthene dye contains a compound represented by 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.
- 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 a halogen atom, —OH, —SO 3 ⁇ , —SO 3 H, —SO 3 ⁇ Za + , —CO 2 H, —CO 2 — Za + , —CO 2 R 8a , —SO 3 R 8a. , —NR 9a R 10a or —SO 2 NR 9a 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, a plurality of R 5a 's may be the same or different.
- a represents an integer of 0 or 1.
- Xa ⁇ represents a counter ion.
- Za + represents + N(R 11a ) 4 , Na + or K + , and four R 11a 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.
- R 21a to R 24a are each independently a hydrogen atom, —R 26a , an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituted group. It represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a group. 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 a halogen atom, —SO 3 ⁇ , —SO 3 H, —SO 3 ⁇ Za1 + , —NR 28a R 29a 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. Xa1 ⁇ represents a counter ion.
- R 28a and R 29a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and —CH 2 contained in the saturated hydrocarbon group. - May be replaced by -O- or -CO-, and R 28a and R 29a may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. Good.
- R 26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a halogen atom or a carboxy group.
- Za1 + 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.
- the present invention it is possible to provide a colored curable resin composition that has a high film thickness retention rate in the color filter before and after post-baking and does not increase the line width of the color filter obtained after post-baking.
- the xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule.
- xanthene dyes include C.I. I. Acid Red 51 (hereinafter, CI Acid Red is omitted and only the 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.
- the xanthene dye a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable.
- the compound (1a) may be a tautomer thereof.
- the content of the compound (1a) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more.
- the compound represented by the formula (1a) also includes compatible isomers thereof.
- 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 a halogen atom, —OH, —SO 3 ⁇ , —SO 3 H, —SO 3 ⁇ Za + , —CO 2 H, —CO 2 — Za + , —CO 2 R 8a , —SO 3 R 8a. , —NR 9a R 10a or —SO 2 NR 9a 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, a plurality of R 5a 's may be the same or different.
- a represents an integer of 0 or 1.
- Xa ⁇ represents a counter ion.
- Za + represents + N(R 11a ) 4 , Na + or K + , and four R 11a 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 which is bonded. 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 a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group and a butylphenyl group.
- Examples of the substituent that the aromatic hydrocarbon group may have include a halogen atom, a carboxy group, a silicon atom-containing 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, and -SO 2 NR 9a R 10a thereof.
- the substituent is preferably a silicon atom-containing group, —SO 3 ⁇ , —SO 3 H, —SO 3 ⁇ Za + , —SO 2 NR 9a R 10a , and a silicon atom containing group, —SO 3 — Za + and -SO 2 NR 9a R 10a are more preferred.
- —SO 3 ⁇ Za + —SO 3 ⁇ + N(R 11a ) 4 is preferable.
- R 1a to R 4a are these groups, the colored 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.
- the silicon atom-containing group represents a group containing a silicon atom and may be, for example, a group represented by the formula (ii). -Si(R 50a ) 3 (ii) [In the formula, R 50a represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. A plurality of R 50a may be the same or different. ] R 50a is preferably an alkoxy group having 1 to 4 carbon atoms. Specific examples of the silicon atom-containing group include a silyloxy group such as a trimethylsilyloxy group, a triethylsilyloxy group, a trimethoxysilyl group, and triethoxysilyl.
- 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.
- Examples of the substituent which the saturated hydrocarbon group in R 1a to R 4a may have include a carboxy group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a silicon atom-containing group, and a halogen atom.
- Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms are the same as the aromatic hydrocarbon group for R 1a to R 4a .
- Examples and preferred ranges of the silicon atom-containing group are the same as those described as the substituents that the aromatic hydrocarbon group for R 1a to R 4a may have.
- the substituent that the saturated hydrocarbon group in R 1a to R 4a may have is preferably a carboxy group and a silicon atom-containing group.
- Examples of the substituent that the saturated hydrocarbon group for R 9a and R 10a may have include a hydroxy group, a silicon atom-containing group, and a halogen atom.
- Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms are the same as above.
- Examples and preferred ranges of the silicon atom-containing group are the same as above.
- 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-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group Group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-heptylsulf
- R 5a is preferably a halogen atom, —CO 2 H, —CO 2 ⁇ Za + , —CO 2 R 8a , —SO 3 ⁇ , —SO 3 — Za + , —SO 3 H or SO 2 NHR 9a , and SO 3 ⁇ , —SO 3 ⁇ Za + , —SO 3 H, —NR 9a R 10a or SO 2 NHR 9a is more preferable.
- R 9a and R 10a are preferably each independently a saturated hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.
- Examples of the alkyl group having 1 to 6 carbon atoms in R 6a and R 7a include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.
- 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 at least two of the four R 11a are preferably 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.
- + N(R 11a ) 4 is present in the compound (1a)
- R 11a is one of these groups, the colored filter containing the compound (1a) of the colored curable resin composition of the present invention contains less foreign matter. Can be formed.
- the counter ion represented by Xa ⁇ include halide ions and counter ions represented by formula (y1) and formula (y2).
- R B1 represents a fluorinated alkyl group having 1 to 12 carbon atoms.
- R B2 and R B3 each independently represent a halogen atom or a fluorinated alkyl group having 1 to 12 carbon atoms.
- Examples of the halide ion include fluoride ion, chloride ion, bromide ion and iodide ion.
- fluorinated alkyl group having 1 to 12 carbon atoms represented by R B1 include fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1,1,2,2,2-pentafluoroethyl group.
- Examples thereof include a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, and a perfluorohexyl group, preferably a group in which all hydrogen atoms are replaced by fluorine atoms (that is, a perfluoroalkyl group), and more preferably carbon.
- Examples of the halogen atom represented by R B2 and R B3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
- Examples of the fluorinated alkyl group having 1 to 12 carbon atoms represented by R B2 and R B3 include the same as the fluorinated alkyl group represented by R B1 , and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Is mentioned.
- R B2 and R B3 may combine with each other to form a ring containing —SO 2 —N — —SO 2 —.
- 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 have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. And optionally represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
- 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 a halogen atom, —SO 3 ⁇ , —SO 3 H, —SO 3 ⁇ Za1 + , —NR 28a R 29a or —SO 2 NHR 26a .
- m1 represents an integer of 0 to 5.
- R 25a 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.
- Xa1 ⁇ represents a counter ion.
- R 28a and R 29a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and —CH 2 contained in the saturated hydrocarbon group. - May be replaced by -O- or -CO-, and R 28a and R 29a may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. Good.
- R 26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a halogen atom or a carboxy group.
- Za1 + 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 .
- the hydrogen atom contained in the aromatic hydrocarbon group is a carboxy group, a silicon atom-containing group, —SO 3 ⁇ , —SO 3 H, —SO 3 ⁇ Za1 + , —SO 3 R 26a or —SO 2 NHR 26a . It may be substituted.
- R 21a to R 24a , R 21a and R 23a each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms (the saturated hydrocarbon group is a halogen atom, a silicon atom-containing group or a carboxy group).
- R 22a and R 24a each independently represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (a hydrogen atom contained in the aromatic hydrocarbon group).
- R 21a and R 23a each independently have a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (the alkyl group may have a halogen atom, a silicon atom-containing group or a carboxy group).
- R 22a and R 24a each represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group is a carboxy group, a silicon atom-containing group, —SO 3 — Za1 + or -SO 2 NHR 26a may be substituted).
- 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 exemplary and preferred ranges of the silicon atom-containing group are the same as the exemplary and preferred ranges in the description of the above formula (1a).
- Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R 21a to R 24a are the same as those listed as the aromatic hydrocarbon group for R 1a to R 4a .
- the hydrogen atom contained in the aromatic hydrocarbon group is substituted with a silicon atom-containing group, —SO 3 ⁇ , —SO 3 H, —SO 3 ⁇ Za1 + , —SO 3 R 26a or —SO 2 NHR 26a. May be.
- the exemplary and preferred ranges of the silicon atom-containing group are the same as the exemplary and preferred ranges in the description of the above formula (1a).
- Examples of R 28a and R 29a include the same as R 9a and R 10a in formula (1a).
- R 1a and R 2a are formed together.
- R 1a and R 2a are formed together.
- 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 21a to R 24a are monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent
- R 21a to R 24a are each independently a methyl group or an ethyl group. It is preferable.
- 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 one 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).
- Za1 + is + N(R 27a ) 4 , Na + or K + , and preferably + N(R 27a ) 4 .
- the + N(R 27a ) 4 at least two of the four R 27a are preferably 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.
- the counter ion represented by Xa1 ⁇ is the same as the exemplified and preferred ranges in the above description of Xa ⁇ .
- 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.
- the aromatic hydrocarbon group of 10 may be substituted with a carboxy group, a silicon atom-containing group or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be a silicon atom-containing group or a group having 1 to 3 carbon atoms. It may be substituted with an alkoxy group, and —CH 2 — contained in the saturated hydrocarbon group may be replaced with —O—, —CO— or —NR 11a —.
- R 33a and R 34a each independently represent a silicon atom-containing group, 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 described above. ]
- Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R 31a and R 32a include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Groups and the like.
- Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be contained as a substituent include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.
- alkoxy group having 1 to 3 carbon atoms examples include methoxy group, ethoxy group, propoxy group and the like. 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).
- the exemplary and preferred ranges of the silicon atom-containing group are the same as the exemplary and preferred ranges in the description of the above formula (1a).
- Examples of the alkyl group having 1 to 4 carbon atoms for 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 for 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 each independently preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. Examples and preferable ranges of the silicon atom-containing group for R 33a and R 34a are the same as the examples and preferable ranges in the above description of the formula (1a).
- integers of 0 and 2 are preferable for p and q, and 0 or 1 is preferable.
- Examples of compound (1a) include compounds represented by formula (1-1) to formula (1-97).
- 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).
- xanthene dye As the xanthene dye, 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.) can be used. .. Alternatively, a commercially available xanthene dye can be used as a starting material, and can also be synthesized with reference to JP-A-2010-32999.
- xanthene dye for example, “Chugai Aminol Fast Pink RH/C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Co., Ltd.
- a commercially available xanthene dye can be used as a starting material, and can also be synthesized with reference to JP-A-2010-32999.
- the content of the xanthene dye in the colorant (A) may be, for example, 0.1% by mass or more and 100% by mass or less, and more preferably 0.1% by mass or less, based on the total amount of solids in the colorant (A). 1 mass% or more and 99.0 mass% or less, more preferably 0.5 mass% or more and 90.0 mass% or less, particularly preferably 1.0 mass% or more and 50.0 mass% or less, and particularly It is preferably 1.5% by mass or more and 30.0% by mass or less.
- the “total amount of solids in the colorant (A)” means the total amount of components excluding the solvent (F) from the colorant (A).
- 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.
- Colorant (A) The content of the colorant (A) in the colored curable resin composition is preferably 5% by mass or more and 80% 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 70% by mass to 70% by mass, and more preferably from 5% by mass to 60% 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” means the total amount of components excluding the solvent (F) from the colored curable resin composition.
- the colored curable resin composition contains a solvent (hereinafter, also referred to as a solvent (F))
- a colorant-containing liquid containing a colorant (A) and a solvent (F) 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 (F) and mixing them.
- the colorant-containing liquid may contain a part or all of the solvent (F) contained in the colored curable resin composition.
- the content of solids 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 with respect to the total amount of the colorant-containing liquid. It is 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, and more preferably 0.1% by mass in the total amount of solids in the colorant-containing liquid. % To 99.9% by mass, more preferably 1% to 99% by mass, and particularly preferably 10% to 90% by mass.
- total amount of solids in the colorant-containing liquid refers to the total amount of components excluding the solvent (F) from the colorant-containing liquid.
- the colorant (A) can be made to be in a state of being uniformly dispersed in the colorant-containing liquid by including a dispersant in the 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. When the amount of the dispersant used is within the above range, a more uniformly dispersed colorant-containing liquid tends to be obtained.
- the colorant (A) may further contain a colorant other than the above-mentioned xanthene dye [hereinafter, also referred to as a colorant (A1)].
- the colorant (A1) may include at least one selected from the group consisting of dyes and pigments other than the xanthene dyes described above.
- the dye contained in the colorant (A1) known 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)
- compounds classified as dyes such as solvent, acid, basic, reactive, direct, disperse, mordant, and vat, and known dyes described in Dyeing Note (Shikiso Co., Ltd.).
- the dye may be appropriately selected according to the desired spectral spectrum of the color filter. These dyes may be used alone or in combination of two or more kinds.
- the dye is preferably an organic solvent-soluble dye.
- the dye examples include C.I. I. Solvent Yellow 4 (hereinafter, CI Solvent Yellow and the like are omitted and only numbers are described), 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.
- Acid Green 1 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, C. 104, 105, 106, 109, etc.
- Acid dyes C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; C. I.
- 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.
- the dye according to the chemical structure, triarylmethane dye, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, Examples thereof include acridine dye, styryl dye, coumarin dye, quinoline dye, nitro dye and tetraazaporphyrin dye.
- the colorant (A) preferably contains a triarylmethane dye as a dye. It is preferable that the colorant (A) contains a triarylmethane-based dye since the brightness of the obtained color filter tends to be improved.
- pigments contained in the colorant (A1) include organic pigments and inorganic pigments, and compounds that are classified as pigments by 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 Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, 291, C.
- the pigment may be rosin-treated, surface-treated with a pigment derivative having an acidic group or 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 subjecting the pigment dispersant to a dispersion treatment.
- Each of the pigments may be subjected to a dispersion treatment alone, or a plurality of kinds of pigments may be mixed and subjected to a dispersion treatment.
- pigment dispersants 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 with respect to 100 parts by mass of the pigment.
- the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniform dispersed state tends to be obtained.
- the content of the colorant (A1) in the colorant (A) is, for example, 0.1 based on the total solid content of the colorant (A).
- the content may be from 9 to 99.9% by mass, more preferably from 0.1 to 99% by mass, still more preferably from 0.5 to 97% by mass.
- the colorant (A) contains a triarylmethane dye
- the content of the triarylmethane dye in the colorant (A) may be in the range of the content of the colorant (A1).
- the colorant (A) contains a triarylmethane dye
- the colorant (A) may contain only a xanthene dye and a triarylmethane dye, or in addition to these, another colorant (A1). May be included.
- the colored curable resin composition of the present invention contains one type or two or more types of resin (B).
- the resin (B) 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 (B) include the following resins [K1] to [K6].
- Resin [K1] at least one kind (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides [hereinafter sometimes referred to as "(a)”. ] And a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter, sometimes referred to as “(b)”. ) And a copolymer.
- Resin [K2] (a) and (b), and a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) [hereinafter "(c)”. There is a thing. ] The copolymer with.
- Resin [K3] A copolymer of (a) and (c).
- Resin [K4] A resin obtained by reacting (b) with the copolymer of (a) and (c).
- Resin [K5] Resin obtained by reacting (a) with the copolymer of (b) and (c).
- Resin [K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.
- 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-ethylbic
- (a) is preferably (meth)acrylic acid, maleic anhydride or the like, more preferably acrylic acid and maleic anhydride, from the viewpoints of copolymerization reactivity and 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 the notations such as “(meth)acryloyl” and “(meth)acrylate”.
- (B) is a polymerization having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond.
- a sex compound Refers to a sex compound.
- (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
- Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter, referred to as "(b1)”. ], a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as “(b2)”. ], a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "(b3)”. ] Etc. are mentioned.
- (B1) may be a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter referred to as "(b1-1)”. ], and a monomer (b1-2) having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon [hereinafter, sometimes referred to as "(b1-2)”. ] Is mentioned.
- Examples of (b1-1) include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, ⁇ -ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p.
- Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel 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 (BI) And compounds represented by formula (B-II).
- R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group. May be substituted with a hydroxy group.
- X 1 and X 2 are each independently a single bond, * - R c -, * - R c -O -, * - R c -S-, or * represents a -R c -NH-.
- R c represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O.
- alkyl group having 1 to 4 carbon atoms examples include 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 a and R b 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 c 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 1 and X 2 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.
- the compound represented by the formula (BI) include compounds represented by the formulas (BI-1) to (BI-15), and preferably the formula (BI- 1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9), formula (BI-11) to formula (BI-11) And a compound represented by the formula (BI-15), more preferably the formula (BI-1), the formula (BI-7), the formula (BI-9) and the formula (BI). Examples of the compound include -15).
- Specific examples of the compound represented by the formula (B-II) include compounds represented by the formula (B-II-1) to the formula (B-II-15), preferably the formula (B-II). -1), formula (B-II-3), formula (B-II-5), formula (B-II-7), formula (B-II-9), formula (B-II-11) to formula Examples thereof include compounds represented by (B-II-15), more preferably, formula (B-II-1), formula (B-II-7), formula (B-II-9) and formula (B- II-15) and the like.
- the compound represented by the formula (BI) and the compound represented by the formula (B-II) can be used alone. They can be mixed in any ratio.
- the mixing ratio is represented by formula (BI): formula (B-II) [molar ratio], preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and further It is preferably 20:80 to 80:20.
- the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group.
- (b2) 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyl oxetane may be mentioned.
- the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group.
- (b3) examples 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 is also sometimes referred to as “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, diethyl itaconic acid; 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-
- 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.
- benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable as (c) since 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 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, March 1, 1972) and the literature. It can be manufactured with reference to the cited references. Specifically, a method of charging a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent and the like into a reaction vessel and stirring, heating, and keeping the temperature in a deoxygenated atmosphere is a method. Can be mentioned.
- 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.).
- azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.
- organic peroxides benzoyl peroxide, etc.
- 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 (F) 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 (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. There is a method of doing.
- 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].
- a copolymer of (a) and (c) is obtained, and the cyclic ether structure having 2 to 4 carbon atoms contained in (b), particularly the oxirane ring contained in (b1) is It can be produced by addition to the carboxylic acid and/or carboxylic acid anhydride.
- the copolymer of (a) and (c) is produced in the same manner as the method described as the method of producing 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 copolymer of (a) and (c).
- a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the above copolymer has a cyclic ether structure having 2 to 4 carbon atoms, which is contained in (b), particularly (b1). React the oxirane ring.
- the atmosphere in the flask is replaced with nitrogen from air to produce (b) (particularly (b1)), a carboxylic acid or a carboxylic acid anhydride.
- a reaction catalyst eg, tris(dimethylaminomethyl)phenol etc.
- a polymerization inhibitor eg hydroquinone etc.
- Resin [K4] can be obtained.
- the amount of (b) used, particularly (b1), is preferably 5 to 80 mol, and more preferably 10 to 75 mol, per 100 mol of (a). Within this range, the storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tend to be well balanced.
- the (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).
- the amount of the reaction catalyst used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) (particularly (b1)) and (c).
- the amount of the polymerization inhibitor used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) and (c).
- Reaction conditions such as charging method, reaction temperature and 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.
- a copolymer of (b) (particularly (b1)) and (c) is obtained in the same manner as in the above-mentioned method for producing the resin [K1].
- the obtained copolymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
- the ratio of the structural units derived from (b) (particularly (b1)) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the above copolymer.
- (a) is added to the cyclic ether structure derived from (b) in the copolymer of (b) (particularly (b1)) and (c).
- the resin [K5] can be obtained by reacting the carboxylic acid or carboxylic acid anhydride that it has.
- the amount of (a) used to react with the above-mentioned copolymer is preferably 5 to 80 mol per 100 mol of (b) (particularly (b1)). Since the cyclic ether structure has high reactivity and the unreacted (b) hardly remains, (b1) is preferable as (b) used in the resin [K5], and (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.
- the resin preferable as the resin (B) is [K1] or [K2].
- the resin (B) 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 (B) 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, and particularly preferably 10,000 or more and 30,000 or less.
- Mw weight average molecular weight
- the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 or more and 6 or less, more preferably 1.2 or more and 4 or less.
- the acid value of the resin (B) 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 mg-KOH/g. Yes, more preferably 80 mg-KOH/g or more and 150 mg-KOH/g or less, and particularly preferably 95 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 using an aqueous potassium hydroxide solution.
- the content of the resin (B) is preferably 1% by mass or more and 50% by mass or less, and 5% by mass or more and 45% by mass or less in 100% by mass of the solid content of the colored curable resin composition.
- the content of the resin (B) is in the above range, the unexposed portion tends to have high solubility in the developing solution.
- the polymerizable compound (C) is not particularly limited as long as it is a compound 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.
- 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, dipentaerythritol poly(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate , Tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol Hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipenta
- the colored curable resin composition of the present invention may contain one kind or two or more kinds of 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, and more preferably 10% by mass or more and 60% by mass, based on the total amount of solids in the colored curable resin composition. % Or less, and more preferably 10% by mass or more and 50% by mass or less.
- the content of the polymerizable compound (C) is within the above range, the film thickness retention rate when forming a colored pattern and the chemical resistance of the color filter tend to be improved.
- Polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids and the like by the action of light or heat and initiating polymerization, and known polymerization initiators can be used.
- polymerization initiators that generate active radicals include O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.
- the O-acyl oxime compound is a compound having a partial structure represented by the formula (d1).
- * represents a bond.
- O-acyl oxime compound examples include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, 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-methyl
- O-acyl oxime compounds are N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1.
- the alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3).
- the benzene ring may have a substituent.
- Examples of the compound having the partial structure represented by the formula (d2) 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 Etc.
- Commercially available products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
- Examples of the compound having the partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4-(2 -Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomer, ⁇ , ⁇ -diethoxy Acetophenone, benzyl dimethyl ketal, etc. are mentioned.
- the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).
- triazine compound examples include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-(4- Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy Styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4 -Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-Methylpheny
- acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- a commercially available product such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.
- biimidazole compound examples include 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole and 2,2′-bis(2,3-dichlorophenyl)- 4,4',5,5'-Tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4 ,4',5,5'-Tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis (2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole,2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trime
- benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 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, Examples thereof include quinone compounds such as 2-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
- Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl.
- Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate, Examples thereof include benzoin tosylate.
- the polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds, and O-acyloxy A polymerization initiator containing a vinyl compound is more preferable.
- the content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and 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 included, 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 thereof 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 parts by mass or more and 30 parts by mass or less, 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, the pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.
- the thiol compound (E) contains an ether bond-containing thiol compound.
- the film thickness retention tends to increase.
- the colored curable resin composition of the present invention may contain one or more ether bond-containing thiol compounds.
- the ether bond-containing thiol compound may contain, for example, a sulfanyl group (—SH) in an amount of 2 or more and 6 or less, and preferably 3 or more and 5 or less.
- the ether bond-containing thiol compound may have an ether bond, for example, 2 or more and 6 or less, preferably 3 or more and 5 or less.
- the ether bond-containing thiol compound is preferably a compound represented by the formula (I).
- A-(R 1 -SH) n (I) [In the formula, A represents a residue of a polyhydric alcohol having m hydroxy groups, The plurality of R 1 bonded to oxygen atoms derived from the m hydroxy groups each independently represents an alkylene group having 1 to 10 carbon atoms, m is an integer of 2 or more, n is an integer of 2 or more, and m ⁇ n. ]
- A represents a residue of a polyhydric alcohol having m hydroxy groups.
- the polyhydric alcohol residue has a structure in which a hydrogen atom (H) constituting at least one hydroxy group (OH) is removed from the polyhydric alcohol.
- the oxygen atom (O) bonded to the removed hydrogen atom that is, the oxygen atom derived from the hydroxy group is bonded to n R 1 . All the oxygen atom may be bonded to R 1 derived from a hydroxy group in the polyhydric alcohol, part thereof may be bonded to R 1.
- the polyhydric alcohol is not particularly limited as long as it is a compound having two or more hydroxy groups in one molecule.
- examples thereof include aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, aromatic ring-containing polyhydric alcohols, sugars and their derivatives.
- aliphatic polyhydric alcohols, alicyclic polyhydric alcohols and/or aromatic ring-containing polyhydric alcohols are preferable. More preferably, it is an aliphatic polyhydric alcohol.
- the aliphatic polyhydric alcohol preferably has 2 to 30 carbon atoms.
- alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol and 1,12-dodecamethylene glycol;
- Polyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol; trihydric or higher polyhydric alcohols such as (poly)glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, sorbitan; And the like, and may be an alkylene oxide adduct thereof (for example, the number of added moles is 1 to 50).
- the alicyclic polyhydric alcohol is preferably one having 3 to 30 carbon atoms, for example. Specific examples thereof include alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
- the aromatic ring-containing polyhydric alcohol preferably has 6 to 30 carbon atoms.
- Specific examples include alkylene oxide adducts of bisphenols such as bisphenol A, bisphenol F and bisphenol S (for example, the number of added moles is 2 to 30).
- M may be 2 or more, but it is preferably 2 to 10, more preferably 2 to 8, still more preferably 2 to 6, and particularly preferably 3 to 6.
- the polyhydric alcohol in A is preferably a polyhydric alcohol having 3 to 6 hydroxy groups, more preferably pentaerythritol, trimethylolpropane and dipentaerythritol.
- R 1 is the same or different and represents an alkylene group having 1 to 10 carbon atoms.
- the alkylene group may be linear or branched.
- the carbon atom bonded to the mercapto group may be a primary carbon atom, a secondary carbon atom or a tertiary carbon atom. From the viewpoint of reactivity, it is preferably a primary carbon atom or a secondary carbon atom.
- R 1 may have one or more substituents, but it is preferable that R 1 does not contain a substituent.
- substituents which R 1 may have include a halogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group and a phosphoric acid group.
- the molecular weight of the ether bond-containing thiol compound may be, for example, 50 or more and 700 or less, and is preferably 100 or more and 500 or less, more preferably 150 or more and 380 or less from the viewpoint of viscosity reduction.
- ether bond-containing thiol compounds examples include pentaerythritol trispropanethiol, trimethylolpropane dipropanethiol, and the like.
- the ether bond-containing thiol compound can be produced by a known production method. For example, it can be manufactured according to the method described in WO2016/171072.
- the thiol compound (E) may contain one or more thiol compounds (E1) other than the above-mentioned ether bond-containing thiol compound.
- the thiol compound (E1) is particularly preferably used when the polymerization initiator (D) is an oxime compound such as an O-acyl oxime compound and/or a biimidazole compound.
- the thiol compound (E1) is a compound having at least one sulfanyl group (-SH) in the molecule.
- the thiol compound (E1) is preferably a compound having one sulfanyl group in the molecule.
- Examples of compounds having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanyl Pyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridin-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino- 2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6 -Sulfanylpyrimidine, 4,6
- Examples of the compound having two or more sulfanyl groups in the molecule include hexanedithiol, decandithiol, 1,4-bis(methylsulfanyl)benzene, butanediol bis(3-sulfanylpropionate), butanediol bis(3-sulfanyl).
- the content of the thiol compound (E) is preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 45 parts by mass or less, further preferably 100 parts by mass of the polymerization initiator (D). Is 5 parts by mass or more and 40 parts by mass or less.
- the colored curable resin composition of the present invention preferably contains one or more solvents (F).
- 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—
- a ketone solvent a solvent containing —CO—
- an alcohol solvent an aromatic hydrocarbon solvent, an amide solvent, 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 methyl anisole.
- 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 (F) 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 (F) 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.
- it contains 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.
- the content of the solvent (F) 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 (G) examples 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 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC), etc. Can be mentioned.
- fluorinated surfactant examples include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F543.
- R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).
- silicone-based surfactant having a fluorine atom examples include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megafac (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).
- the content of the leveling agent (G) is usually 0.0001% by mass or more and 0.6% by mass or less, preferably 0.0001% by mass or more and 0.4% by mass or less, in the colored curable resin composition. Preferably it is 0.0001 mass% or more and 0.2 mass% or less.
- the content of the pigment dispersant is not included in this content.
- a filler a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an anticoagulant, an organic acid may be added, if necessary.
- One or two or more kinds of additives such as 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, if necessary, a thiol compound (E), a solvent ( It can be prepared by mixing F), the leveling agent (G), the polymerization initiation aid (D1), the antioxidant (H), 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 the photolithographic method is preferable.
- the photolithography method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed.
- a colored coating film 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.
- the substrate examples include quartz glass, borosilicate glass, alumina silicate glass, glass plate such as silica-coated soda lime glass, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and the above substrate.
- resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and the above substrate.
- Aluminum, silver, silver/copper/palladium alloy thin film, etc. are used.
- Other color filter layers, resin layers, transistors, circuits, transparent electrodes and the like may be formed on these substrates.
- the formation of colored pixels by the photolithographic 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 heating and drying is preferably 30°C or higher and 120°C or lower, more preferably 50°C or higher and 110°C or lower.
- 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 depending on the intended thickness of the color filter.
- the colored composition layer is exposed through a photomask for forming an intended colored pattern.
- the pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
- a light source used for exposure a light source that emits light having a wavelength of 250 nm or more and 450 nm or less is preferable. 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.
- 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 coloring 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 developing solution 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% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less.
- the developing solution may contain a surfactant.
- Development method may be paddle method, dipping method, 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.
- the colored curable resin composition of the present invention has a small amount of residue on the base material, where the unexposed portion of the colored composition layer is dissolved in the developer and removed.
- 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 to 120 minutes, more preferably 10 to 60 minutes.
- the colored curable resin composition of the present invention has a film thickness of a colored composition layer after exposure, development and post-baking with respect to a film thickness of the colored composition layer before exposure [after heating (pre-baking) and/or drying under reduced pressure]. Is high, and may be, for example, 50% or more.
- the thickness of the colored coating film or colored pattern formed from the colored curable resin composition is preferably as thin as possible because it affects adjacent pixels. Especially when a thick film is used, light from a light source may leak out through pixels of two or more colors when a liquid crystal panel is manufactured. May be lost.
- the film thickness of the colored coating film or 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 coating film or the colored pattern is not particularly limited, but is usually 1 ⁇ m or more, and may be 1.5 ⁇ m or more.
- the colored coating film or the colored pattern can exhibit excellent developability and is therefore excellent as a color filter.
- the colored curable resin composition of the present invention has a high film thickness retention ratio of the colored coating film or the colored pattern before and after post-baking, so that a predetermined film thickness is obtained even with a relatively small amount of the curable resin composition. be able to.
- the colored curable resin composition of the present invention has a higher film thickness retention rate than the conventional film thickness retention rate of the colored curable resin composition.
- the difference from the colored curable resin composition of 2 may be, for example, 2% or more.
- the color filter according to the present invention is useful as a color filter used for a display device (liquid crystal display device, organic EL device, electronic paper, etc.) and a solid-state image sensor.
- the colored 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.
- “part” means “part by mass”
- “%” means “% by mass”.
- the reaction was carried out in a nitrogen atmosphere.
- 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 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 necessary to neutralize 1 g of the resin.
- the mixture was kept at 0° C. and stirred for 5 hours to complete the reaction, and then the solid content was filtered.
- the solid content was repeatedly washed with methanol and water alternately until the filtrate was no longer colored and no salt was deposited. After that, the solid content was dried in a vacuum dryer at 80° C. for 18 hours to obtain 10.7 parts of the target red pigment 1.
- N-ethyl-o-toluidine manufactured by Tokyo Kasei Co., Ltd.
- 30.6 parts of N-ethyl-o-toluidine manufactured by Tokyo Kasei Co., Ltd.
- An aqueous solution prepared by dissolving 79.2 parts of sodium monochloroacetate in 120 parts of ion-exchanged water was added to the flask, 60.4 parts of a 30% sodium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 18 hours. After further adding 600 parts of ion-exchanged water to the flask, the mixture was stirred for 1 hour, and the precipitated yellowish white solid was collected by filtration.
- the obtained yellowish white solid was washed with 120 parts of acetonitrile and then with 560 parts of ion-exchanged water.
- a yellow white solid after washing 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 156 parts of toluene were charged into a flask equipped with a stirrer, and the mixture was allowed to stand at room temperature for 2 hours. Stir for hours. 80.8 parts of a 30% sodium hydroxide aqueous solution was added dropwise thereto over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by liquid separation operation.
- the solvent was removed from the obtained organic layer by an evaporator, and then the organic layer was dried at 60° C. under reduced pressure to obtain a compound represented by the formula (t-3) as a blue-violet solid.
- the yield of blue-violet solid was 39.4 parts.
- 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 the dropping, the mixture was kept at 85° C. for 4 hours, then cooled to room temperature to obtain a copolymer (resin B1) solution having a viscosity of 23 mPas measured by a B-type viscometer (23° C.) and a solid content of 25.4%. It was The weight average molecular weight Mw of the produced copolymer was 8.0 ⁇ 10 3 , the polydispersity was 2.1, and the acid value in terms of solid content was 109 mg-KOH/g.
- the resin B1 has the following structural units.
- Resin (B) Resin B1 obtained in the above (Synthesis example 6)
- Polymerizable compound (C) dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- Example 1 Preparation of colored curable resin composition
- the components shown below were mixed, and a pigment dispersion liquid 1 in which the pigment was sufficiently dispersed using a bead mill was prepared. Using this, the following components were mixed to obtain a colored curable resin composition.
- the obtained colored curable resin composition was evaluated by the following method.
- 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 machine TBE-150RSK; manufactured by Topcon Corp.
- TME-150RSK an exposure machine
- the colored composition layer was irradiated with light with the gap between the photomasks set to 250 ⁇ m.
- Example 2 A pigment dispersion liquid 2, a colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 1 except that the following components were mixed. The results are shown in Table 2. ⁇ Pigment dispersion 2> C. I.
- Pigment Blue 15:6 22.12 parts Acrylic pigment dispersant 7.76 parts Resin B1 obtained in (Synthesis Example 6) (as solid content) 8.87 parts Propylene glycol monomethyl ether acetate 182.91 parts ⁇ Color hardening Resin composition> Colorant (A): 222 parts of Pigment Dispersion Liquid 2 (Synthesis Example 3) xanthene dye 3 parts Resin (B): Resin B1 (solid content conversion) 56 parts Polymerizable compound (C): Dipentaerythritol hexa Acrylate 35 parts Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 parts Thiol compound (E): PEPT 3 parts Solvent (F): Ethyl lactate 33 parts Diacetone alcohol 71 parts Propylene glycol monomethyl ether acetate 424 parts Leveling agent (G): SH8400 (solid content conversion) 0.1 part
- Example 3 A color filter was prepared and evaluated in the same manner as in Example 1 except that the following components were mixed to obtain a colored curable resin composition. The results are shown in Table 3.
- Example 4 A colored curable resin composition was obtained in the same manner as in Example 3 except that 218 parts of Pigment Dispersion Liquid 2, 0.5 part of thiol compound (E), and 473 parts of propylene glycol monomethyl ether acetate were used. .. Using this, a color filter was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.
- Example 5 A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 1 except that the following components were mixed. The results are shown in Table 4. ⁇ Dispersion 3> Dispersion liquid 3 was prepared by mixing the components shown below.
- Example 6 A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 1 except that the following components were mixed. The results are shown in Table 5.
- Example 7 A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 1 except that the following components were mixed. The results are shown in Table 6.
- Polymerizable compound (C) Dipentaerythritol hexaacrylate 45.0 parts
- the obtained color filter has a high film thickness retention rate and can maintain the line width, which is extremely useful industrially.
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Abstract
Description
[2] 前記エーテル結合含有チオール化合物は、式(I)で表される化合物である、[1]に記載の着色硬化性樹脂組成物。
A-(R1-SH)n (I)
[式中、Aは、m個のヒドロキシ基を有する多価アルコールの残基を表し、
前記m個のヒドロキシ基に由来する酸素原子に結合する複数のR1は、それぞれ独立に、炭素数1~10のアルキレン基を表し、
mは2以上の整数であり、nは2以上の整数であり、m≧nである。]
[3] mは2~10である、[2]に記載の着色硬化性樹脂組成物。
[4] 前記多価アルコールは、ペンタエリスリトール又はトリメチロールプロパンである、[2]又は[3]に記載の着色硬化性樹脂組成物。
[5] 前記キサンテン染料は、式(1a)で表される化合物を含む、[1]~[4]のいずれかに記載の着色硬化性樹脂組成物。 [1] A colored curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (E), The colored curable resin composition, wherein the colorant (A) contains a xanthene dye, and the thiol compound (E) contains an ether bond-containing thiol compound.
[2] The colored curable resin composition according to [1], wherein the ether bond-containing thiol compound is a compound represented by the formula (I).
A-(R 1 -SH) n (I)
[In the formula, A represents a residue of a polyhydric alcohol having m hydroxy groups,
The plurality of R 1 bonded to oxygen atoms derived from the m hydroxy groups each independently represents an alkylene group having 1 to 10 carbon atoms,
m is an integer of 2 or more, n is an integer of 2 or more, and m≧n. ]
[3] The colored curable resin composition according to [2], wherein m is 2 to 10.
[4] The colored curable resin composition according to [2] or [3], wherein the polyhydric alcohol is pentaerythritol or trimethylolpropane.
[5] The colored curable resin composition according to any one of [1] to [4], wherein the xanthene dye contains a compound represented by the formula (1a).
R5aは、ハロゲン原子、-OH、-SO3 -、-SO3H、-SO3 -Za+、-CO2H、-CO2 -Za+、-CO2R8a、-SO3R8a、-NR9aR10a又は-SO2NR9aR10aを表す。
R6a及びR7aは、それぞれ独立に、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、対イオンを表す。
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、それぞれ独立に、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。]
[6] 前記式(1a)で表される化合物は、式(2a)で表される化合物である、[5]に記載の着色硬化性樹脂組成物。 [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 a halogen atom, —OH, —SO 3 − , —SO 3 H, —SO 3 − Za + , —CO 2 H, —CO 2 — Za + , —CO 2 R 8a , —SO 3 R 8a. , —NR 9a R 10a or —SO 2 NR 9a 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, a plurality of R 5a 's may be the same or different.
a represents an integer of 0 or 1.
Xa − represents a counter ion.
Za + represents + N(R 11a ) 4 , Na + or K + , and four R 11a 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. ]
[6] The colored curable resin composition according to [5], wherein the compound represented by the formula (1a) is a compound represented by the formula (2a).
R25aは、ハロゲン原子、-SO3 -、-SO3H、-SO3 -Za1+、-NR28aR29a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。
Xa1-は、対イオンを表す。
R28a及びR29aは、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数1~10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-CH2-は、-O-、又は-CO-で置き換っていてもよく、R28a及びR29a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。
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。
Za1+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。]
[7] [1]~[6]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。
[8] [7]に記載のカラーフィルタを含む表示装置。 [In the formula (2a), R 21a to R 24a are each independently a hydrogen atom, —R 26a , an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituted group. It represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a group. 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 a halogen atom, —SO 3 − , —SO 3 H, —SO 3 − Za1 + , —NR 28a R 29a 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.
Xa1 − represents a counter ion.
R 28a and R 29a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and —CH 2 contained in the saturated hydrocarbon group. -May be replaced by -O- or -CO-, and R 28a and R 29a may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. Good.
R 26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a halogen atom or a carboxy group.
Za1 + 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. ]
[7] A color filter formed from the colored curable resin composition according to any one of [1] to [6].
[8] A display device including the color filter according to [7].
[キサンテン染料]
キサンテン染料は、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。 <Colored curable resin composition>
[Xanthene dye]
The xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule. Examples of xanthene dyes include C.I. I. Acid Red 51 (hereinafter, CI Acid Red is omitted and only the 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.
R5aは、ハロゲン原子、-OH、-SO3 -、-SO3H、-SO3 -Za+、-CO2H、-CO2 -Za+、-CO2R8a、-SO3R8a、-NR9aR10a又は-SO2NR9aR10aを表す。
R6a及びR7aは、それぞれ独立に、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、対イオンを表す。
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、それぞれ独立に、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、それぞれ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 a halogen atom, —OH, —SO 3 − , —SO 3 H, —SO 3 − Za + , —CO 2 H, —CO 2 — Za + , —CO 2 R 8a , —SO 3 R 8a. , —NR 9a R 10a or —SO 2 NR 9a 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, a plurality of R 5a 's may be the same or different.
a represents an integer of 0 or 1.
Xa − represents a counter ion.
Za + represents + N(R 11a ) 4 , Na + or K + , and four R 11a 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 which is bonded. 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. ]
-Si(R50a)3 (ii)
[式中、R50aは、水素原子、ヒドロキシ基、炭素数1~4のアルキル基又は炭素数1~4のアルコキシ基を表す。複数のR50aは同一でも異なってもよい。]
R50aは好ましくは、炭素数1~4のアルコキシ基である。ケイ素原子含有基の具体例としては、シリルオキシ基、例えばトリメチルシリルオキシ基、トリエチルシリルオキシ基、トリメトキシシリル基、トリエトキシシリル等が挙げられる。 Examples of the substituent that the aromatic hydrocarbon group may have include a halogen atom, a carboxy group, a silicon atom-containing 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, and -SO 2 NR 9a R 10a thereof. Among these, the substituent is preferably a silicon atom-containing group, —SO 3 − , —SO 3 H, —SO 3 − Za + , —SO 2 NR 9a R 10a , and a silicon atom containing group, —SO 3 — Za + and -SO 2 NR 9a R 10a are more preferred. 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 colored 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. The silicon atom-containing group represents a group containing a silicon atom and may be, for example, a group represented by the formula (ii).
-Si(R 50a ) 3 (ii)
[In the formula, R 50a represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. A plurality of R 50a may be the same or different. ]
R 50a is preferably an alkoxy group having 1 to 4 carbon atoms. Specific examples of the silicon atom-containing group include a silyloxy group such as a trimethylsilyloxy group, a triethylsilyloxy group, a trimethoxysilyl group, and triethoxysilyl.
R1a~R4aにおける該飽和炭化水素基が有していてもよい置換基としては、カルボキシ基及びケイ素原子含有基であることが好ましい。 Examples of the substituent which the saturated hydrocarbon group in R 1a to R 4a may have include a carboxy group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a silicon atom-containing group, and a halogen atom. To be Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms are the same as the aromatic hydrocarbon group for R 1a to R 4a . Examples and preferred ranges of the silicon atom-containing group are the same as those described as the substituents that the aromatic hydrocarbon group for R 1a to R 4a may have.
The substituent that the saturated hydrocarbon group in R 1a to R 4a may have is preferably a carboxy group and a silicon atom-containing group.
-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.
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-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-(1,1-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-(2-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-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-(2-エチルヘキシル)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-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group Group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(2-ethylhexyl)sulfamoyl group Group, N-1 substituted sulfamoyl group such as 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 Examples thereof include N,N-2 substituted sulfamoyl groups and the like.
R9a及びR10aは、それぞれ独立に、置換基を有していてもよい炭素数1~6の飽和炭化水素基であることが好ましい。 R 5a is preferably a halogen atom, —CO 2 H, —CO 2 − Za + , —CO 2 R 8a , —SO 3 − , —SO 3 — Za + , —SO 3 H or SO 2 NHR 9a , and SO 3 − , —SO 3 − Za + , —SO 3 H, —NR 9a R 10a or SO 2 NHR 9a is more preferable.
R 9a and R 10a are preferably each independently a saturated hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.
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。
Xa-で表される対イオンは、ハロゲン化物イオン、式(y1)及び式(y2)で表される対イオンが挙げられる。 Za + is + N(R 11a ) 4 , Na + or K + , and preferably + N(R 11a ) 4 .
As the + N(R 11a ) 4 , at least two of the four R 11a are preferably 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 colored curable resin composition of the present invention contains less foreign matter. Can be formed.
Examples of the counter ion represented by Xa − include halide ions and counter ions represented by formula (y1) and formula (y2).
式(y2)において、RB2及びRB3は、それぞれ独立に、ハロゲン原子又は炭素数1~12のフッ化アルキル基を表す。]
ハロゲン化物イオンとしては、フッ化物イオン、塩化物イオン、臭化物イオン及びヨウ化物イオンが挙げられる。 [In the formula (y1), R B1 represents a fluorinated alkyl group having 1 to 12 carbon atoms.
In formula (y2), R B2 and R B3 each independently represent a halogen atom or a fluorinated alkyl group having 1 to 12 carbon atoms. ]
Examples of the halide ion include fluoride ion, chloride ion, bromide ion and iodide ion.
RB2及びRB3で表される炭素数1~12のフッ化アルキル基としては、RB1で表されるフッ化アルキル基と同じものが挙げられ、好ましくは炭素数1~4のペルフルオロアルキル基が挙げられる。
RB2及びRB3は、互いに結合して-SO2-N--SO2-を含む環を形成してもよい。 Examples of the halogen atom represented by R B2 and R B3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Examples of the fluorinated alkyl group having 1 to 12 carbon atoms represented by R B2 and R B3 include the same as the fluorinated alkyl group represented by R B1 , and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Is mentioned.
R B2 and R B3 may combine with each other to form a ring containing —SO 2 —N — —SO 2 —.
R25aは、ハロゲン原子、-SO3 -、-SO3H、-SO3 -Za1+、-NR28aR29a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。
Xa1-は、対イオンを表す。
R28a及びR29aは、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数1~10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-CH2-は、-O-、又は-CO-で置き換っていてもよく、R28a及びR29a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。
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。
Za1+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。] [In the formula (2a), R 21a to R 24a 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. And optionally represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. 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 a halogen atom, —SO 3 − , —SO 3 H, —SO 3 − Za1 + , —NR 28a R 29a 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.
Xa1 − represents a counter ion.
R 28a and R 29a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and —CH 2 contained in the saturated hydrocarbon group. -May be replaced by -O- or -CO-, and R 28a and R 29a may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. Good.
R 26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a halogen atom or a carboxy group.
Za1 + 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の組合せとしては、R21a及びR23aが、それぞれ独立に、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、ケイ素原子含有基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、それぞれ独立に、炭素数6~10の1価の芳香族炭化水素基(該芳香族炭化水素基に含まれる水素原子は、カルボキシ基、ケイ素原子含有基、-SO3 -、-SO3H、-SO3 -Za1+、-SO3R26a又は-SO2NHR26aで置換されていてもよい。)であるものが好ましい。より好ましい組合せは、R21a及びR23aが、それぞれ独立に、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、ケイ素原子含有基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(該芳香族炭化水素基に含まれる水素原子は、カルボキシ基、ケイ素原子含有基、-SO3 -Za1+又は-SO2NHR26aで置換されていていてもよい。)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。ケイ素原子含有基の例示及び好ましい範囲は、上述の式(1a)の説明における例示及び好ましい範囲と同じである。 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 . The hydrogen atom contained in the aromatic hydrocarbon group is a carboxy group, a silicon atom-containing group, —SO 3 − , —SO 3 H, —SO 3 − Za1 + , —SO 3 R 26a or —SO 2 NHR 26a . It may be substituted.
As a combination of R 21a to R 24a , R 21a and R 23a each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms (the saturated hydrocarbon group is a halogen atom, a silicon atom-containing group or a carboxy group). R 22a and R 24a each independently represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (a hydrogen atom contained in the aromatic hydrocarbon group). the carboxy group, a silicon atom-containing group, -SO 3 -, -SO 3 H , -SO 3 -. which Za1 +, -SO 3 R 26a or optionally substituted with -SO 2 NHR 26a) and is intended Is preferred. In a more preferred combination, R 21a and R 23a each independently have a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (the alkyl group may have a halogen atom, a silicon atom-containing group or a carboxy group). And R 22a and R 24a each represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group is a carboxy group, a silicon atom-containing group, —SO 3 — Za1 + or -SO 2 NHR 26a may be substituted). 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). The exemplary and preferred ranges of the silicon atom-containing group are the same as the exemplary and preferred ranges in the description of the above formula (1a).
R28a及びR29aは、式(1a)におけるR9a及びR10aと同様のものが挙げられる。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R 21a to R 24a are the same as those listed as the aromatic hydrocarbon group for R 1a to R 4a . Groups. The hydrogen atom contained in the aromatic hydrocarbon group is substituted with a silicon atom-containing group, —SO 3 − , —SO 3 H, —SO 3 − Za1 + , —SO 3 R 26a or —SO 2 NHR 26a. May be. The exemplary and preferred ranges of the silicon atom-containing group are the same as the exemplary and preferred ranges in the description of the above formula (1a).
Examples of R 28a and R 29a include the same as R 9a and R 10a in formula (1a).
R21a~R24aが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である場合、R21a~R24a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 monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent, R 21a to R 24a are each independently a methyl group or an ethyl group. It is preferable. 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 one 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).
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。 Za1 + is + N(R 27a ) 4 , Na + or K + , and preferably + N(R 27a ) 4 .
As the + N(R 27a ) 4 , at least two of the four R 27a are preferably 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), if 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.
R33a及びR34aは、それぞれ独立に、ケイ素原子含有基、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、それぞれ独立に、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. The aromatic hydrocarbon group of 10 may be substituted with a carboxy group, a silicon atom-containing group or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be a silicon atom-containing group or a group having 1 to 3 carbon atoms. It may be substituted with an alkoxy group, and —CH 2 — contained in the saturated hydrocarbon group may be replaced with —O—, —CO— or —NR 11a —.
R 33a and R 34a each independently represent a silicon atom-containing group, 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 described above. ]
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、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。
炭素数1~3のアルコキシ基としては、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、それぞれ独立に、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。
ケイ素原子含有基の例示及び好ましい範囲は、上述の式(1a)の説明における例示及び好ましい範囲と同じである。 Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R 31a and R 32a include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Groups and the like.
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be contained as a substituent include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.
Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy group, ethoxy group, propoxy group and the like.
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).
The exemplary and preferred ranges of the silicon atom-containing group are the same as the exemplary and preferred ranges in the description of the above formula (1a).
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、それぞれ独立に、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。
R33a及びR34aにおけるケイ素原子含有基の例示及び好ましい範囲は、上述の式(1a)の説明における例示及び好ましい範囲と同じである。 Examples of the alkyl group having 1 to 4 carbon atoms for 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 for 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 each independently preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
Examples and preferable ranges of the silicon atom-containing group for R 33a and R 34a are the same as the examples and preferable ranges in the above description of the formula (1a).
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80質量%以下であり、より好ましくは5質量%以上70質量%以下であり、さらに好ましくは5質量%以上60質量%以下である。着色剤(A)の含有率が前記の範囲内であると、所望とする分光や色濃度を得ることができる。 [1] Colorant (A)
The content of the colorant (A) in the colored curable resin composition is preferably 5% by mass or more and 80% 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 70% by mass to 70% by mass, and more preferably from 5% by mass to 60% by mass. When the content of the colorant (A) is within the above range, desired spectrum and color density can be obtained.
着色剤(A1)は、上述のキサンテン染料以外の染料及び顔料からなる群から選択される少なくとも1種を含んでいてよい。 The colorant (A) may further contain a colorant other than the above-mentioned xanthene dye [hereinafter, also referred to as a colorant (A1)].
The colorant (A1) may include at least one selected from the group consisting of dyes and pigments other than the xanthene dyes described above.
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 (hereinafter, CI Solvent Yellow and the like are omitted and only numbers are described), 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 green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like C.I. I. Direct dyes,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. C. such as Disperse Blue 1, 14, 56, 60. 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.
本発明の着色硬化性樹脂組成物は、着色剤(A)が染料としてトリアリールメタン系染料を含有することが好ましい。着色剤(A)がトリアリールメタン系染料を含有すると、得られるカラーフィルタの明度が向上する傾向にあるため好ましい。 Further, as the dye, according to the chemical structure, triarylmethane dye, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, Examples thereof include acridine dye, styryl dye, coumarin dye, quinoline dye, nitro dye and tetraazaporphyrin dye.
In the colored curable resin composition of the present invention, the colorant (A) preferably contains a triarylmethane dye as a dye. It is preferable that the colorant (A) contains a triarylmethane-based dye since the brightness of the obtained color filter tends to be improved.
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、180、185、194、214、231等の黄色顔料;
C.I.ピグメントオレンジ13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等のオレンジ色の顔料;
C.I.ピグメントブルー15、15:3、15:4、15:6、21、28、60、64及び76等の青色顔料;
C.I.ピグメントバイオレット1、14、19、23、29、32、33、36、37、38等のバイオレット色顔料;
C.I.ピグメントグリーン7、10、15、25、36、47、58、59等の緑色顔料;
C.I.ピグメントブラウン23、25、28等のブラウン色顔料;
C.I.ピグメントブラック1、7等の黒色顔料等が挙げられる。 Examples of the pigment include C.I. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, 291,
C. 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, 180, 185, 194, 214, 231;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like; orange pigments;
C. I. Pigment Blue 15, 15:3, 15:4, 15:6, 21, 28, 60, 64, and 76 blue pigments;
C. I. Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38 and other violet color pigments;
C. I. Pigment Green 7, 10, 15, 25, 36, 47, 58, 59 and other green pigments;
C. I. Pigment Brown 23, 25, 28 and other brown color pigments;
C. I. Pigment Black 1 and 7 and the like black pigments and the like.
着色剤(A)がトリアリールメタン系染料を含む場合、着色剤(A)中のトリアリールメタン系染料の含有率は、上記着色剤(A1)の含有率の範囲であってもよいが、より好ましくは着色剤(A)の固形分の総量を基準に98質量%以下であり、さらに好ましくは95質量%以下であり、またより好ましくは10質量%以上であり、さらに好ましくは20質量%以上である。なお、着色剤(A)が、トリアリールメタン系染料を含む場合、着色剤(A)はキサンテン染料及びトリアリールメタン系染料のみを含んでもよいし、これらに加えて他の着色剤(A1)を含んでもよい。 When the colorant (A) contains the colorant (A1), the content of the colorant (A1) in the colorant (A) is, for example, 0.1 based on the total solid content of the colorant (A). The content may be from 9 to 99.9% by mass, more preferably from 0.1 to 99% by mass, still more preferably from 0.5 to 97% by mass.
When the colorant (A) contains a triarylmethane dye, the content of the triarylmethane dye in the colorant (A) may be in the range of the content of the colorant (A1). More preferably, it is 98% by mass or less, further preferably 95% by mass or less, more preferably 10% by mass or more, still more preferably 20% by mass, based on the total solid content of the colorant (A). That is all. When the colorant (A) contains a triarylmethane dye, the colorant (A) may contain only a xanthene dye and a triarylmethane dye, or in addition to these, another colorant (A1). May be included.
本発明の着色硬化性樹脂組成物は、1種又は2種以上の樹脂(B)を含有する。樹脂(B)は、アルカリ可溶性樹脂であることが好ましい。アルカリ可溶性とは、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(B)としては、以下の樹脂[K1]~[K6]等が挙げられる。 [2] Resin (B)
The colored curable resin composition of the present invention contains one type or two or more types of resin (B). The resin (B) 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 (B) include the following resins [K1] to [K6].
樹脂[K2]:(a)と(b)と、(a)と共重合可能な単量体(c)(ただし、(a)及び(b)とは異なる。)〔以下「(c)」ということがある。〕との共重合体。
樹脂[K3]:(a)と(c)との共重合体。
樹脂[K4]:(a)と(c)との共重合体に(b)を反応させて得られる樹脂。
樹脂[K5]:(b)と(c)との共重合体に(a)を反応させて得られる樹脂。
樹脂[K6]:(b)と(c)との共重合体に(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 kind (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides [hereinafter sometimes referred to as "(a)". ] And a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter, sometimes referred to as “(b)”. ) And a copolymer.
Resin [K2]: (a) and (b), and a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) [hereinafter "(c)". There is a thing. ] The copolymer with.
Resin [K3]: A copolymer of (a) and (c).
Resin [K4]: A resin obtained by reacting (b) with the copolymer of (a) and (c).
Resin [K5]: Resin obtained by reacting (a) with the copolymer of (b) and (c).
Resin [K6]: A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.
(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く、アクリル酸及び無水マレイン酸がより好ましい。 As (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 polyvalent carboxylic 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, more preferably acrylic acid and maleic anhydride, from the viewpoints of copolymerization reactivity and solubility in an alkaline aqueous solution.
(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(b1)〔以下、「(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単量体(b2)〔以下、「(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(b3)〔以下、「(b3)」ということがある。〕等が挙げられる。 (B) is a polymerization having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. Refers to a sex compound. (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter, referred to as "(b1)". ], a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as “(b2)”. ], a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "(b3)". ] Etc. are mentioned.
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。
Ra及びRb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。
Rc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 a and R b 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 c 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.
式(B-I)で表される化合物の具体例として、式(B-I-1)~式(B-I-15)で表される化合物が挙げられ、好ましくは式(B-I-1)、式(B-I-3)、式(B-I-5)、式(B-I-7)、式(B-I-9)、式(B-I-11)~式(B-I-15)で表される化合物が挙げられ、より好ましくは式(B-I-1)、式(B-I-7)、式(B-I-9)、式(B-I-15)で表される化合物が挙げられる。 X 1 and X 2 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 (BI) include compounds represented by the formulas (BI-1) to (BI-15), and preferably the formula (BI- 1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9), formula (BI-11) to formula (BI-11) And a compound represented by the formula (BI-15), more preferably the formula (BI-1), the formula (BI-7), the formula (BI-9) and the formula (BI). Examples of the compound include -15).
オキセタニル基とエチレン性不飽和結合とを有する単量体(b2)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。
(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。
テトラヒドロフリル基とエチレン性不飽和結合とを有する単量体(b3)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。
(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 (BI) and the compound represented by the formula (B-II) can be used alone. They can be mixed in any ratio. When mixing, the mixing ratio is represented by formula (BI): formula (B-II) [molar ratio], preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and further It is preferably 20:80 to 80:20.
The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group.
As preferable examples of (b2), 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyl oxetane may be mentioned.
The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group.
Preferable examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.
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 (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 is also sometimes referred to as “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, diethyl itaconic acid;
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) Oxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclo unsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Maleimide propionate, dicarbonylimide derivatives such as 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, as (c), 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) since they are excellent in developability during pattern formation.
(a)に由来する構造単位;2~50モル%(より好ましくは10~45モル%)、
(b)に由来する構造単位、特に(b1)に由来する構造単位;50~98モル%(より好ましくは55~90モル%)。
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、(a)及び(b)(特に(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(F)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(F)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].
A structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol %),
Structural units derived from (b), particularly structural units derived from (b1); 50 to 98 mol% (more preferably 55 to 90 mol%).
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, March 1, 1972) and the literature. It can be manufactured with reference to the cited references.
Specifically, a method of charging a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent and the like into a reaction vessel and stirring, heating, and keeping the temperature in a deoxygenated atmosphere is a method. Can be mentioned. 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.). To be Any solvent can be used as long as it can dissolve each monomer, and the solvent (F) described below can be used as the solvent for 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 (F) 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.
(a)に由来する構造単位;4~45モル%、より好ましくは10~40モル%、さらに好ましくは15~35モル%、
(b)に由来する構造単位、特に(b1)に由来する構造単位;2~95モル%、より好ましくは3~70モル%、さらに好ましくは5~45モル%、
(c)に由来する構造単位;1~94モル%、より好ましくは20~85モル%、さらに好ましくは40~80モル%。
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、(a)、(b)(特に(b1))及び(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 (a): 4-45 mol%, more preferably 10-40 mol%, further preferably 15-35 mol%,
Structural unit derived from (b), particularly structural unit derived from (b1); 2-95 mol%, more preferably 3-70 mol%, further preferably 5-45 mol%,
Structural unit derived from (c); 1 to 94 mol%, more preferably 20 to 85 mol%, further preferably 40 to 80 mol%.
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability, the developability, the solvent resistance of the obtained pattern, the heat resistance and the 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 (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. There is a method of doing. 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.
(a)に由来する構造単位;2~55モル%、より好ましくは10~50モル%、さらに好ましくは15~50モル%、特に好ましくは25~50モル%、
(c)に由来する構造単位;45~98モル%、より好ましくは50~90モル%、さらに好ましくは50~85モル%、特に好ましくは50~75モル%。
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 (a): 2-55 mol%, more preferably 10-50 mol%, further preferably 15-50 mol%, particularly preferably 25-50 mol%,
Structural unit derived from (c): 45 to 98 mol%, more preferably 50 to 90 mol%, further preferably 50 to 85 mol%, particularly preferably 50 to 75 mol%.
The resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1].
(a)に由来する構造単位;5~50モル%(より好ましくは10~45モル%)、
(c)に由来する構造単位;50~95モル%(より好ましくは55~90モル%)。 In the resin [K4], a copolymer of (a) and (c) is obtained, and the cyclic ether structure having 2 to 4 carbon atoms contained in (b), particularly the oxirane ring contained in (b1) is It can be produced by addition to the carboxylic acid and/or carboxylic acid anhydride. Specifically, first, the copolymer of (a) and (c) is produced in the same manner as the method described as the method of producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range in all the structural units constituting the copolymer of (a) and (c).
A structural unit derived from (a); 5 to 50 mol% (more preferably 10 to 45 mol %),
Structural unit derived from (c); 50 to 95 mol% (more preferably 55 to 90 mol %).
(b)の使用量、特に(b1)の使用量は、(a)100モルに対して、好ましくは5~80モル、より好ましくは10~75モルである。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(b)が残存しにくいことから、樹脂[K4]に用いる(b)としては(b1)が好ましく、(b1-1)がより好ましい。
上記反応触媒の使用量は、(a)、(b)(特に(b1))及び(c)の合計量に対して0.001~5質量%であることが好ましい。上記重合禁止剤の使用量は、(a)、(b)及び(c)の合計量に対して0.001~5質量%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 (a) in the above copolymer has a cyclic ether structure having 2 to 4 carbon atoms, which is contained in (b), particularly (b1). React the oxirane ring. Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with nitrogen from air to produce (b) (particularly (b1)), a carboxylic acid or a carboxylic acid anhydride. A reaction catalyst (eg, tris(dimethylaminomethyl)phenol etc.) and a polymerization inhibitor (eg hydroquinone etc.) between the and the cyclic ether structure are put in a flask and reacted at 60 to 130° C. for 1 to 10 hours. , Resin [K4] can be obtained.
The amount of (b) used, particularly (b1), is preferably 5 to 80 mol, and more preferably 10 to 75 mol, per 100 mol of (a). Within this range, the storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tend to be well balanced. Since the cyclic ether structure has high reactivity and the unreacted (b) is unlikely to remain, the (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).
The amount of the reaction catalyst used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) (particularly (b1)) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) and (c).
Reaction conditions such as charging method, reaction temperature and 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.
(b)(特に(b1))及び(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。
(b)に由来する構造単位、特に(b1)に由来する構造単位;5~95モル%(より好ましくは10~90モル%)、
(c)に由来する構造単位;5~95モル%(より好ましくは10~90モル%)。 As the resin [K5], as a first step, a copolymer of (b) (particularly (b1)) and (c) is obtained in the same manner as in the above-mentioned method for producing the resin [K1]. 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 (b) (particularly (b1)) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the above copolymer.
A structural unit derived from (b), particularly a structural unit derived from (b1); 5 to 95 mol% (more preferably 10 to 90 mol%),
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol %).
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。 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.
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. To be
樹脂(B)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/gmg-KOH/gであり、さらに好ましくは80mg-KOH/g以上150mg-KOH/g以下であり、特に好ましくは95mg-KOH/g以上150mg-KOH/g以下である。酸価は、樹脂1gを中和する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 polystyrene equivalent weight average molecular weight (Mw) of the resin (B) 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, and particularly preferably 10,000 or more and 30,000 or less. When the weight average molecular weight (Mw) is in the above range, the unexposed portion has a high solubility in a developing solution, and the resulting colored pattern tends to have a high film thickness retention rate and a high hardness. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 or more and 6 or less, more preferably 1.2 or more and 4 or less.
The acid value of the resin (B) 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 mg-KOH/g. Yes, more preferably 80 mg-KOH/g or more and 150 mg-KOH/g or less, and particularly preferably 95 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 using an aqueous potassium hydroxide solution.
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い。
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、ジペンタエリスリトールポリ(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。 [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.
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, dipentaerythritol poly(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate , Tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol Hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc. Is mentioned. Of these, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.
重合開始剤(D)は、光や熱の作用により活性ラジカル、酸等を発生し、重合を開始しうる化合物であれば特に限定されることなく、公知の重合開始剤を用いることができる。活性ラジカルを発生する重合開始剤としては、例えば、O-アシルオキシム化合物、アルキルフェノン化合物、トリアジン化合物、アシルホスフィンオキサイド化合物及びビイミダゾール化合物が挙げられる。 [4] Polymerization initiator (D)
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids and the like by the action of light or heat and initiating polymerization, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.
式(d3)で表される部分構造を有する化合物としては、例えば、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(d2)で表される部分構造を有する化合物が好ましい。 Examples of the compound having the partial structure represented by the formula (d2) 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 Etc. Commercially available products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having the partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4-(2 -Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomer, α,α-diethoxy Acetophenone, benzyl dimethyl ketal, etc. are mentioned.
From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).
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 included, 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).
チオール化合物(E)は、エーテル結合含有チオール化合物を含む。着色硬化性樹脂組成物がエーテル結合含有チオール化合物を含む場合、膜厚保持率が高くなる傾向にある。本発明の着色硬化性樹脂組成物は、エーテル結合含有チオール化合物を1種又は2種以上含んでもよい。 [6] Thiol compound (E)
The thiol compound (E) contains an ether bond-containing thiol compound. When the colored curable resin composition contains an ether bond-containing thiol compound, the film thickness retention tends to increase. The colored curable resin composition of the present invention may contain one or more ether bond-containing thiol compounds.
エーテル結合含有チオール化合物は、エーテル結合を例えば2以上6以下有するものであってよく、好ましくは3以上5以下有する。 The ether bond-containing thiol compound may contain, for example, a sulfanyl group (—SH) in an amount of 2 or more and 6 or less, and preferably 3 or more and 5 or less.
The ether bond-containing thiol compound may have an ether bond, for example, 2 or more and 6 or less, preferably 3 or more and 5 or less.
A-(R1-SH)n (I)
[式中、Aは、m個のヒドロキシ基を有する多価アルコールの残基を表し、
前記m個のヒドロキシ基に由来する酸素原子に結合する複数のR1は、それぞれ単独に、炭素数1~10のアルキレン基を表し、
mは2以上の整数であり、nは2以上の整数であり、m≧nである。] The ether bond-containing thiol compound is preferably a compound represented by the formula (I).
A-(R 1 -SH) n (I)
[In the formula, A represents a residue of a polyhydric alcohol having m hydroxy groups,
The plurality of R 1 bonded to oxygen atoms derived from the m hydroxy groups each independently represents an alkylene group having 1 to 10 carbon atoms,
m is an integer of 2 or more, n is an integer of 2 or more, and m≧n. ]
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(F)を含むことが好ましい。溶剤(F)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。 [7] Solvent (F)
The colored curable resin composition of the present invention preferably contains one or more solvents (F). As the solvent (F), 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—), Other than the ester solvent, a ketone solvent (a solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like can be mentioned.
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 methyl anisole.
レベリング剤(G)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。 [8] Leveling agent (G)
Examples of the leveling agent (G) 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.
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、凝集防止剤、有機酸、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。 [9] Other components In the colored curable resin composition of the present invention, a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an anticoagulant, an organic acid may be added, if necessary. One or two or more kinds of additives such as a curing agent can be contained.
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、チオール化合物(E)、溶剤(F)、レベリング剤(G)、重合開始助剤(D1)、酸化防止剤(H)、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, if necessary, a thiol compound (E), a solvent ( It can be prepared by mixing F), the leveling agent (G), the polymerization initiation aid (D1), the antioxidant (H), and other components.
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である。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, manufacturing method thereof, and display device>
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 the photolithographic method is preferable. The photolithography method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithographic method, a colored coating film 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.
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質量%以上10質量%以下であり、より好ましくは0.03質量%以上5質量%以下である。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 in the developing solution and removed.
The developing solution 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% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less. Further, the developing solution may contain a surfactant.
装置 ;HLC-8120GPC(東ソー(株)製)
カラム ;TSK-GELG2000HXL
カラム温度 ;40℃
溶剤 ;THF
流速 ;1.0mL/min
被検液固形分濃度;0.001~0.01質量%
注入量 ;50μL
検出器 ;RI
校正用標準物質 ;TSK STANDARD POLYSTYRENE
F-40、F-4、F-288、A-2500、A-500
(東ソー(株)製)
上記で得られたポリスチレン換算の重量平均分子量及び数平均分子量の比(Mw/Mn)を分散度とした。 The polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
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 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.
17.4部のtert-アミルアルコールと金属ナトリウム2.22部を窒素雰囲気下130℃で反応させてナトリウムtert-アミルアルコラートを合成した。これを60℃に加熱し、4-ブロモベンゾニトリル9.1部、琥珀酸ジ-tert-アミルエステル7.105部、tert-アミルアルコール10.89部を加え、液温が85℃以下になるように2時間攪拌した。この懸濁液をさらに18時間以上攪拌し、その後、-10℃に冷却したメタノール20部と水100部と硫酸4.921部の混合液に加えた。懸濁液の添加が終了した後、0℃に保ち5時間攪拌して反応を完了させた後、固形分を濾過した。固形分は、メタノールと水で交互に、濾液の着色がなくなり、かつ塩の析出がなくなるまで繰り返し洗った。その後、固形分を80℃の真空乾燥機で18時間乾燥し、目的の赤色顔料1を10.7部得た。 (Synthesis example 1)
Sodium tert-amyl alcoholate was synthesized by reacting 17.4 parts of tert-amyl alcohol with 2.22 parts of metallic sodium at 130° C. under a nitrogen atmosphere. This is heated to 60° C., and 9.1 parts of 4-bromobenzonitrile, 7.105 parts of succinic acid di-tert-amyl ester, and 10.89 parts of tert-amyl alcohol are added to bring the liquid temperature to 85° C. or lower. Stirring for 2 hours. This suspension was further stirred for 18 hours or more, and then added to a mixed solution of 20 parts of methanol cooled to -10°C, 100 parts of water and 4.921 parts of sulfuric acid. After the addition of the suspension was completed, the mixture was kept at 0° C. and stirred for 5 hours to complete the reaction, and then the solid content was filtered. The solid content was repeatedly washed with methanol and water alternately until the filtrate was no longer colored and no salt was deposited. After that, the solid content was dried in a vacuum dryer at 80° C. for 18 hours to obtain 10.7 parts of the target red pigment 1.
特開2016-277075号の実施例1に記載の方法に従い、式(1-34)で表される化合物52部を得た。 (Synthesis example 2)
According to the method described in Example 1 of JP-A-2016-277075, 52 parts of the compound represented by the formula (1-34) was obtained.
(質量分析)イオン化モード=ESI+: m/z=[M+H]+ 599.2
Exact Mass: 598.1 Identification of Compound Represented by Formula (1-34) (Mass Spectrometry) Ionization Mode=ESI+: m/z=[M+H] + 599.2
Exact Mass: 598.1
特開2017-226814号の実施例2に記載の方法に従い、式(1-87)で表される化合物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 (1-87) was obtained.
(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
特開2016-176075号の合成例2に記載の方法に従い、式(1-22)で表される化合物24部を得た。収率は80%であった。 (Synthesis example 4)
According to the method described in Synthesis Example 2 of JP-A No. 2016-176075, 24 parts of a compound represented by the formula (1-22) was obtained. The yield was 80%.
(質量分析)イオン化モード=ESI+: m/z=[M+H]+ 659.9
Exact Mass: 658.9 Identification of Compound Represented by Formula (1-32) (Mass Spectrometry) Ionization Mode=ESI+: m/z=[M+H] + 659.9
Exact Mass: 658.9
以下の反応は、窒素雰囲気下で行った。冷却管及び攪拌装置を備えたフラスコに、チオシアン酸カリウム26.4部及びアセトニトリル156部を投入した後、室温下で30分攪拌した。2,6-ジフルオロ安息香酸クロリド(東京化成(株)社製)40.0部を30分かけて前記フラスコに滴下した後、室温にて1時間攪拌した。N-エチル-o-トルイジン(東京化成(株)社製)30.6部を30分かけて前記フラスコに滴下した後、室温にて1時間攪拌した。前記フラスコに、モノクロロ酢酸ナトリウム79.2部をイオン交換水120部に溶解させた水溶液を投入し、30%水酸化ナトリウム水溶液60.4部を投入した後、室温にて18時間攪拌した。前記フラスコにさらに、イオン交換水600部を加えた後1時間攪拌し、析出した黄白色固体をろ取した。得られた黄白色固体をアセトニトリル120部にて洗浄した後イオン交換水560部にて洗浄した。攪拌装置を備えたフラスコに洗浄後の黄白色固体、イオン交換水156部、99%酢酸35.0部(和光純薬工業(株)社製)及びトルエン156部を投入し、室温にて2時間攪拌した。ここに30%水酸化ナトリウム水溶液80.8部を10分かけて滴下した後5分攪拌し、分液操作により水層を除去した。得られた有機層にイオン交換水156部を加え分液洗浄した後、イオン交換水156部と35%塩酸0.1部を加え分液洗浄した。得られた有機層をエバポレーターにて濃縮した後35℃減圧下にて乾燥し式(t-1)で表される化合物を白色固体として得た。収量は43.4部、収率は58.0%であった。 (Synthesis example 5)
The following reactions were carried out under a nitrogen atmosphere. After charging 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile into a flask equipped with a condenser and a stirrer, the mixture was stirred at room temperature for 30 minutes. After 40.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) was dropped into the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise to the flask over 30 minutes, and the mixture was stirred at room temperature for 1 hour. An aqueous solution prepared by dissolving 79.2 parts of sodium monochloroacetate in 120 parts of ion-exchanged water was added to the flask, 60.4 parts of a 30% sodium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 18 hours. After further adding 600 parts of ion-exchanged water to the flask, the mixture was stirred for 1 hour, and the precipitated yellowish white solid was collected by filtration. The obtained yellowish white solid was washed with 120 parts of acetonitrile and then with 560 parts of ion-exchanged water. A yellow white solid after washing, 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 156 parts of toluene were charged into a flask equipped with a stirrer, and the mixture was allowed to stand at room temperature for 2 hours. Stir for hours. 80.8 parts of a 30% sodium hydroxide aqueous solution was added dropwise thereto over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by liquid separation operation. After 156 parts of ion-exchanged water was added to the obtained organic layer for liquid separation cleaning, 156 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added for liquid separation cleaning. The obtained organic layer was concentrated with an evaporator and then dried under reduced pressure at 35° C. to obtain the compound represented by the formula (t-1) as a white solid. The yield was 43.4 parts and the yield was 58.0%.
(質量分析)イオン化モード=ESI-: m/z=949.5[M-Ba+2H]-
Exact Mass[M-Ba]:947.28 Identification of Compound Represented by Formula (t-5) (Mass Spectrometry) Ionization Mode=ESI−: m/z=949.5 [M−Ba+2H] −
Exact Mass [M-Ba]: 947.28
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151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25.4%の共重合体(樹脂B1)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109mg-KOH/gであった。樹脂B1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, 151 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 the dropping, the mixture was kept at 85° C. for 4 hours, then cooled to room temperature to obtain a copolymer (resin B1) solution having a viscosity of 23 mPas measured by a B-type viscometer (23° C.) and a solid content of 25.4%. It was The weight average molecular weight Mw of the produced copolymer was 8.0×10 3 , the polydispersity was 2.1, and the acid value in terms of solid content was 109 mg-KOH/g. The resin B1 has the following structural units.
樹脂(B):上記(合成例6)で得られた樹脂B1
重合性化合物(C):ジペンタエリスリトールヘキサアクリレート(新中村化学工業(株)製)
重合開始剤(D):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)
チオール化合物(E):ペンタエリスリトールトリスプロパンチオール(PEPT)
レベリング剤(G):ポリエーテル変性シリコーンオイル(トーレシリコーンSH8400;東レダウコーニング(株)製)、実施例では「SH8400」と記載 In the preparation of the colored curable resin composition in the following examples, any of the following was used as each component.
Resin (B): Resin B1 obtained in the above (Synthesis example 6)
Polymerizable compound (C): dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF; oxime compound)
Thiol compound (E): Pentaerythritol Trispropanethiol (PEPT)
Leveling agent (G): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.), described as "SH8400" in Examples.
[着色硬化性樹脂組成物の調製]
以下に示す成分を混合し、ビーズミルを用いて顔料を十分に分散させた顔料分散液1を調製した。これを用い、以下に示す各成分を混合して、着色硬化性樹脂組成物を得た。
<顔料分散液1>
(合成例1)で得られた赤色顔料1 66.22部
アクリル系顔料分散剤 14.17部
(合成例6)で得られた樹脂B1(固形分換算) 28.38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 361.87部
<着色硬化性樹脂組成物>
着色剤(A):顔料分散液1 471部
(合成例2)で得られたキサンテン染料 10部
樹脂(B):樹脂B1(固形分換算) 37部
重合性化合物(C):ジペンタエリスリトールヘキサアクリレート
35部
重合開始剤(D):イルガキュア(登録商標)OXE-01 10部
チオール化合物(E):PEPT 3部
溶剤(F):乳酸 22部
ジアセトンアルコール 348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
262部
レベリング剤(G):SH8400(固形分換算) 0.2部 [Example 1]
[Preparation of colored curable resin composition]
The components shown below were mixed, and a pigment dispersion liquid 1 in which the pigment was sufficiently dispersed using a bead mill was prepared. Using this, the following components were mixed to obtain a colored curable resin composition.
<Pigment dispersion 1>
Red pigment 1 obtained in (Synthesis example 1) 66.22 parts Acrylic pigment dispersant 14.17 parts Resin B1 obtained in (synthesis example 6) (solid content conversion) 28.38 parts Propylene glycol monomethyl ether acetate 361.87 parts <colored curable resin composition>
Colorant (A): Pigment Dispersion Liquid 1 471 parts Xanthene dye obtained in (Synthesis Example 2) 10 parts Resin (B): Resin B1 (solid content conversion) 37 parts Polymerizable compound (C): Dipentaerythritol hexa Acrylate 35 parts Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 parts Thiol compound (E): PEPT 3 parts Solvent (F): Lactic acid 22 parts Diacetone alcohol 348 parts Propylene glycol monomethyl ether acetate 262 parts Leveling Agent (G): SH8400 (solid content conversion) 0.2 part
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)でフォトマスク(線幅100μm)を用いて、ガラス基板及びフォトマスク間のギャップを250μmとして、着色組成物層に光照射した。光照射後、水酸化カリウム0.04%溶液をスプレー圧0.1Paにて60秒間現像し、水洗し、エアナイフにより水切りした後、カラーフィルタの膜厚を、膜厚測定装置(DEKTAK3;日本真空技術(株)製)を用いて測定した(ポストベーク前の膜厚)。オーブン中、230℃で20分間ポストベークを行うことにより、カラーフィルタを得た。放冷後、得られたカラーフィルタの膜厚を、膜厚測定装置(DEKTAK3;日本真空技術(株)製)を用いて測定した(ポストベーク後の膜厚)。
下記式により膜厚保持率を求めた。結果を表1に示す。
膜厚保持率[%]=(ポストベーク後の膜厚[μm]/ポストベーク前の膜厚[μm])×100 <Formation of color filter>
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 machine (TME-150RSK; manufactured by Topcon Corp.) was used to expose a glass substrate and a line using a photomask (line width: 100 μm) with an exposure amount of 60 mJ/cm 2 (reference of 365 nm) in an air atmosphere. The colored composition layer was irradiated with light with the gap between the photomasks set to 250 μm. After the light irradiation, a 0.04% solution of potassium hydroxide was developed for 60 seconds at a spray pressure of 0.1 Pa, washed with water, and drained with an air knife. (Manufactured by Technology Co., Ltd.) (film thickness before post-baking). A color filter was obtained by post-baking in an oven at 230° C. for 20 minutes. After cooling, the film thickness of the obtained color filter was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) (film thickness after post-baking).
The film thickness retention rate was calculated by the following formula. The results are shown in Table 1.
Film thickness retention rate [%]=(film thickness after post-baking [μm]/film thickness before post-baking [μm])×100
得られたカラーフィルタは、走査型電子顕微鏡(S-4000:(株)日立製作所製)を用いてパターニングされた線幅を測定し、形状(断面)を確認した。フォトマスク線幅100μmに対するカラーフィルタのパターン線幅[μm]を表1に示す。 <Line width>
The color filter thus obtained was measured for the patterned line width using a scanning electron microscope (S-4000: manufactured by Hitachi, Ltd.) to confirm the shape (cross section). Table 1 shows the pattern line width [μm] of the color filter with respect to the photomask line width 100 μm.
チオール化合物(E)ペンタエリスリトールトリスプロパンチオール(PEPT)に代えてトリメチロールプロパントリス(3-メルカプトプロピオネート)(TMMP)を用いたこと以外は実施例1と同様にして着色硬化性樹脂組成物、及びカラーフィルタを作製し、評価を行った。結果を表1に示す。 [Comparative Example 1]
Colored curable resin composition in the same manner as in Example 1 except that trimethylolpropane tris(3-mercaptopropionate) (TMMP) was used in place of the thiol compound (E) pentaerythritol trispropanethiol (PEPT). , And a color filter were produced and evaluated. The results are shown in Table 1.
チオール化合物(E)ペンタエリスリトールトリスプロパンチオール(PEPT)に代えてペンタエリスリトールテトラキス(3-メルカプトプロピオネート)(PEMP)を用いたこと以外は実施例1と同様にして着色硬化性樹脂組成物、及びカラーフィルタを作製し、評価を行った。結果を表1に示す。 [Comparative Example 2]
Colored curable resin composition in the same manner as in Example 1 except that pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) was used in place of the thiol compound (E) pentaerythritol trispropanethiol (PEPT). And a color filter was produced and evaluated. The results are shown in Table 1.
以下に示す各成分を混合したこと以外は、実施例1と同様にして顔料分散液2、着色硬化性樹脂組成物及びカラーフィルタを作製し、評価を行った。結果を表2に示す。
<顔料分散液2>
C.I.ピグメントブルー15:6 22.12部
アクリル系顔料分散剤 7.76部
(合成例6)で得られた樹脂B1(固形分換算) 8.87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 182.91部
<着色硬化性樹脂組成物>
着色剤(A):顔料分散液2 222部
(合成例3)で得られたキサンテン染料 3部
樹脂(B):樹脂B1(固形分換算) 56部
重合性化合物(C):ジペンタエリスリトールヘキサアクリレート
35部
重合開始剤(D):イルガキュア(登録商標)OXE-01 10部
チオール化合物(E):PEPT 3部
溶剤(F):乳酸エチル 33部
ジアセトンアルコール 71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
424部
レベリング剤(G):SH8400(固形分換算) 0.1部 [Example 2]
A pigment dispersion liquid 2, a colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 1 except that the following components were mixed. The results are shown in Table 2.
<Pigment dispersion 2>
C. I. Pigment Blue 15:6 22.12 parts Acrylic pigment dispersant 7.76 parts Resin B1 obtained in (Synthesis Example 6) (as solid content) 8.87 parts Propylene glycol monomethyl ether acetate 182.91 parts <Color hardening Resin composition>
Colorant (A): 222 parts of Pigment Dispersion Liquid 2 (Synthesis Example 3) xanthene dye 3 parts Resin (B): Resin B1 (solid content conversion) 56 parts Polymerizable compound (C): Dipentaerythritol hexa Acrylate 35 parts Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 parts Thiol compound (E): PEPT 3 parts Solvent (F): Ethyl lactate 33 parts Diacetone alcohol 71 parts Propylene glycol monomethyl ether acetate 424 parts Leveling agent (G): SH8400 (solid content conversion) 0.1 part
チオール化合物(E)ペンタエリスリトールトリスプロパンチオール(PEPT)に代えてトリメチロールプロパントリス(3-メルカプトプロピオネート)(TMMP)を用いたこと以外は実施例2と同様にして着色硬化性樹脂組成物、及びカラーフィルタを作製し、評価を行った。結果を表2に示す。 [Comparative Example 3]
Colored curable resin composition in the same manner as in Example 2 except that trimethylolpropane tris(3-mercaptopropionate) (TMMP) was used instead of thiol compound (E) pentaerythritol trispropanethiol (PEPT). , And a color filter were produced and evaluated. The results are shown in Table 2.
以下に示す各成分を混合して、着色硬化性樹脂組成物を得たこと以外は、実施例1と同様にカラーフィルタを作製し、評価を行った。結果を表3に示す。
着色剤(A):顔料分散液2 222部
(合成例4)で得られたキサンテン染料 3部
樹脂(B):樹脂B1(固形分換算) 56部
重合性化合物(C):ジペンタエリスリトールヘキサアクリレート
35部
重合開始剤(D):イルガキュア(登録商標)OXE-01 10部
チオール化合物(E):PEPT 3部
溶剤(F):乳酸エチル 33部
ジアセトンアルコール 11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
485部
レベリング剤(G):SH8400(固形分換算) 0.1部 [Example 3]
A color filter was prepared and evaluated in the same manner as in Example 1 except that the following components were mixed to obtain a colored curable resin composition. The results are shown in Table 3.
Colorant (A): Pigment dispersion 2 222 parts Xanthene dye obtained in (Synthesis example 4) 3 parts Resin (B): Resin B1 (solid content conversion) 56 parts Polymeric compound (C): Dipentaerythritol hexa Acrylate 35 parts Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 parts Thiol compound (E): PEPT 3 parts Solvent (F): Ethyl lactate 33 parts Diacetone alcohol 11 parts Propylene glycol monomethyl ether acetate 485 parts Leveling agent (G): SH8400 (solid content conversion) 0.1 part
顔料分散液2を218部、チオール化合物(E)を0.5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を473部に変更した以外は、実施例3と同様にして着色硬化性樹脂組成物を得た。これを用いて、実施例1と同様にカラーフィルタを作製し、評価を行った。結果を表3に示す。 [Example 4]
A colored curable resin composition was obtained in the same manner as in Example 3 except that 218 parts of Pigment Dispersion Liquid 2, 0.5 part of thiol compound (E), and 473 parts of propylene glycol monomethyl ether acetate were used. .. Using this, a color filter was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.
チオール化合物(E)ペンタエリスリトールトリスプロパンチオール(PEPT)に代えてトリメチロールプロパントリス(3-メルカプトプロピオネート)(TMMP)を用いたこと以外は実施例3と同様にして着色硬化性樹脂組成物、及びカラーフィルタを作製し、評価を行った。結果を表3に示す。 [Comparative Example 4]
Colored curable resin composition in the same manner as in Example 3 except that trimethylolpropane tris(3-mercaptopropionate) (TMMP) was used in place of the thiol compound (E) pentaerythritol trispropanethiol (PEPT). , And a color filter were produced and evaluated. The results are shown in Table 3.
チオール化合物(E)ペンタエリスリトールトリスプロパンチオール(PEPT)に代えてペンタエリスリトールテトラキス(3-メルカプトプロピオネート)(PEMP)を用いたこと以外は実施例3と同様にして着色硬化性樹脂組成物、及びカラーフィルタを作製し、評価を行った。結果を表3に示す。 [Comparative Example 5]
Colored curable resin composition in the same manner as in Example 3 except that pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) was used in place of the thiol compound (E) pentaerythritol trispropanethiol (PEPT). And a color filter was produced and evaluated. The results are shown in Table 3.
以下に示す各成分を混合したこと以外は、実施例1と同様にして着色硬化性樹脂組成物及びカラーフィルタを作製し、評価を行った。結果を表4に示す。
<分散液3>
以下に示す成分を混合して分散液3を調製した。
(合成例5)で得られた式(t-5)で表される化合物 10部
アクリル系顔料分散剤 8部
(合成例6)で得られた樹脂B1(固形分換算) 3部
ジアセトンアルコール 12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 91部
<着色硬化性樹脂組成物>
着色剤(A):分散液3 119部
顔料分散液2 134部
(合成例4)で得られたキサンテン染料 3部
樹脂(B):樹脂B1(固形分換算) 57部
重合性化合物(C):ジペンタエリスリトールヘキサアクリレート
35部
重合開始剤(D):イルガキュア(登録商標)OXE-01 10部
チオール化合物(E):PEPT 3部
溶剤(F):乳酸エチル 34部
ジアセトンアルコール 11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
481部
レベリング剤(G):SH8400(固形分換算) 0.1部 [Example 5]
A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 1 except that the following components were mixed. The results are shown in Table 4.
<Dispersion 3>
Dispersion liquid 3 was prepared by mixing the components shown below.
Compound represented by formula (t-5) obtained in (Synthesis example 5) 10 parts Acrylic pigment dispersant 8 parts Resin B1 (as solid content) obtained in (Synthesis example 6) 3 parts Diacetone alcohol 12 parts Propylene glycol monomethyl ether acetate 91 parts <Colored curable resin composition>
Colorant (A): Dispersion 3 119 parts Pigment Dispersion 2 134 parts Xanthene dye obtained in Synthesis Example 4 3 parts Resin (B): Resin B1 (solid content conversion) 57 parts Polymerizable compound (C) : Dipentaerythritol hexaacrylate 35 parts Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 parts Thiol compound (E): PEPT 3 parts Solvent (F): Ethyl lactate 34 parts Diacetone alcohol 11 parts Propylene glycol Monomethyl ether acetate 481 parts Leveling agent (G): SH8400 (solid content conversion) 0.1 part
チオール化合物(E)ペンタエリスリトールトリスプロパンチオール(PEPT)に代えてトリメチロールプロパントリス(3-メルカプトプロピオネート)(TMMP)を用いたこと以外は実施例5と同様にして着色硬化性樹脂組成物、及びカラーフィルタを作製し、評価を行った。結果を表4に示す。 [Comparative Example 6]
Colored curable resin composition in the same manner as in Example 5 except that trimethylolpropane tris(3-mercaptopropionate) (TMMP) was used in place of the thiol compound (E) pentaerythritol trispropanethiol (PEPT). , And a color filter were produced and evaluated. The results are shown in Table 4.
以下に示す各成分を混合したこと以外は、実施例1と同様にして着色硬化性樹脂組成物及びカラーフィルタを作製し、評価を行った。結果を表5に示す。
着色剤(A):(合成例4)で得られたキサンテン染料 23部
樹脂(B):樹脂B1(固形分換算) 65部
重合性化合物(C):ジペンタエリスリトールヘキサアクリレート
35部
重合開始剤(D):イルガキュア(登録商標)OXE-01 10部
チオール化合物(E):PEPT 3部
溶剤(F):乳酸エチル 38部
ジアセトンアルコール 93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
534部
レベリング剤(G):SH8400(固形分換算) 0.1部 [Example 6]
A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 1 except that the following components were mixed. The results are shown in Table 5.
Colorant (A): Xanthene dye obtained in (Synthesis example 4) 23 parts Resin (B): Resin B1 (solid content conversion) 65 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate 35 parts Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 parts Thiol compound (E): PEPT 3 parts Solvent (F): Ethyl lactate 38 parts Diacetone alcohol 93 parts Propylene glycol monomethyl ether acetate 534 parts Leveling agent (G): SH8400 (solid content conversion) 0.1 part
チオール化合物(E)ペンタエリスリトールトリスプロパンチオール(PEPT)に代えてトリメチロールプロパントリス(3-メルカプトプロピオネート)(TMMP)を用いたこと以外は実施例6と同様にして着色硬化性樹脂組成物、及びカラーフィルタを作製し、評価を行った。結果を表5に示す。 [Comparative Example 7]
Colored curable resin composition in the same manner as in Example 6 except that trimethylolpropane tris(3-mercaptopropionate) (TMMP) was used in place of the thiol compound (E) pentaerythritol trispropanethiol (PEPT). , And a color filter were produced and evaluated. The results are shown in Table 5.
チオール化合物(E)ペンタエリスリトールトリスプロパンチオール(PEPT)に代えてペンタエリスリトールテトラキス(3-メルカプトプロピオネート)(PEMP)を用いたこと以外は実施例6と同様にして着色硬化性樹脂組成物、及びカラーフィルタを作製し、評価を行った。結果を表5に示す。 [Comparative Example 8]
Colored curable resin composition in the same manner as in Example 6 except that pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) was used in place of the thiol compound (E) pentaerythritol trispropanethiol (PEPT). And a color filter was produced and evaluated. The results are shown in Table 5.
以下に示す各成分を混合したこと以外は、実施例1と同様にして着色硬化性樹脂組成物及びカラーフィルタを作製し、評価を行った。結果を表6に示す。
着色剤(A):分散液3 227.1部
(合成例3)で得られたキサンテン染料 2.8部
樹脂(B):樹脂B1(固形分換算) 50.4部
重合性化合物(C):ジペンタエリスリトールヘキサアクリレート
45.0部
重合開始剤(D):イルガキュア(登録商標)OXE-01 5.0部
チオール化合物(E):PEPT 1.0部
溶剤(F):ジアセトンアルコール 137.1部
乳酸エチル 29.5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
442.2部
レベリング剤(G):SH8400(固形分換算) 0.1部 [Example 7]
A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 1 except that the following components were mixed. The results are shown in Table 6.
Colorant (A): Dispersion 3 227.1 parts Xanthene dye obtained in (Synthesis example 3) 2.8 parts Resin (B): Resin B1 (solid content conversion) 50.4 parts Polymerizable compound (C) : Dipentaerythritol hexaacrylate 45.0 parts Polymerization initiator (D): Irgacure (registered trademark) OXE-01 5.0 parts Thiol compound (E): PEPT 1.0 part Solvent (F): diacetone alcohol 137. 1 part Ethyl lactate 29.5 parts Propylene glycol monomethyl ether acetate 442.2 parts Leveling agent (G): SH8400 (solid content conversion) 0.1 parts
チオール化合物(E)ペンタエリスリトールトリスプロパンチオール(PEPT)に代えてトリメチロールプロパントリス(3-メルカプトプロピオネート)(TMMP)を用いたこと以外は実施例7と同様にして着色硬化性樹脂組成物、及びカラーフィルタを作製し、評価を行った。結果を表6に示す。 [Comparative Example 9]
Colored curable resin composition in the same manner as in Example 7 except that trimethylolpropane tris(3-mercaptopropionate) (TMMP) was used in place of the thiol compound (E) pentaerythritol trispropanethiol (PEPT). , And a color filter were produced and evaluated. The results are shown in Table 6.
チオール化合物(E)ペンタエリスリトールトリスプロパンチオール(PEPT)に代えてペンタエリスリトールテトラキス(3-メルカプトプロピオネート)(PEMP)を用いたこと以外は実施例7と同様にして着色硬化性樹脂組成物、及びカラーフィルタを作製し、評価を行った。結果を表6に示す。 [Comparative Example 10]
Colored curable resin composition in the same manner as in Example 7 except that pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) was used in place of the thiol compound (E) pentaerythritol trispropanethiol (PEPT). And a color filter was produced and evaluated. The results are shown in Table 6.
Claims (8)
- 着色剤(A)と、樹脂(B)と、重合性化合物(C)と、重合開始剤(D)と、チオール化合物(E)とを含む着色硬化性樹脂組成物であって、前記着色剤(A)は、キサンテン染料を含み、前記チオール化合物(E)は、エーテル結合含有チオール化合物を含む、着色硬化性樹脂組成物。 A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (E), wherein the colorant (A) is a colored curable resin composition containing a xanthene dye, and said thiol compound (E) contains an ether bond-containing thiol compound.
- 前記エーテル結合含有チオール化合物は、式(I)で表される化合物である、請求項1に記載の着色硬化性樹脂組成物。
A-(R1-SH)n (I)
[式中、Aは、m個のヒドロキシ基を有する多価アルコールの残基を表し、
前記m個のヒドロキシ基に由来する酸素原子に結合する複数のR1は、それぞれ独立に、炭素数1~10のアルキレン基を表し、
mは2以上の整数であり、nは2以上の整数であり、m≧nである。] The colored curable resin composition according to claim 1, wherein the ether bond-containing thiol compound is a compound represented by the formula (I).
A-(R 1 -SH) n (I)
[In the formula, A represents a residue of a polyhydric alcohol having m hydroxy groups,
The plurality of R 1 bonded to oxygen atoms derived from the m hydroxy groups each independently represents an alkylene group having 1 to 10 carbon atoms,
m is an integer of 2 or more, n is an integer of 2 or more, and m≧n. ] - mは2~10である、請求項2に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to claim 2, wherein m is 2 to 10.
- 前記多価アルコールは、ペンタエリスリトール又はトリメチロールプロパンである、請求項2又は3に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to claim 2 or 3, wherein the polyhydric alcohol is pentaerythritol or trimethylolpropane.
- 前記キサンテン染料は、式(1a)で表される化合物を含む、請求項1~4のいずれか一項に記載の着色硬化性樹脂組成物。
[式(1a)中、R1a~R4aは、それぞれ独立に、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、ハロゲン原子、-OH、-SO3 -、-SO3H、-SO3 -Za+、-CO2H、-CO2 -Za+、-CO2R8a、-SO3R8a、-NR9aR10a又は-SO2NR9aR10aを表す。
R6a及びR7aは、それぞれ独立に、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、対イオンを表す。
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、それぞれ独立に、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。] The colored curable resin composition according to any one of claims 1 to 4, wherein the xanthene dye contains a compound represented by the formula (1a).
[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 a halogen atom, —OH, —SO 3 − , —SO 3 H, —SO 3 − Za + , —CO 2 H, —CO 2 — Za + , —CO 2 R 8a , —SO 3 R 8a. , —NR 9a R 10a or —SO 2 NR 9a 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, a plurality of R 5a 's may be the same or different.
a represents an integer of 0 or 1.
Xa − represents a counter ion.
Za + represents + N(R 11a ) 4 , Na + or K + , and four R 11a 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. ] - 前記式(1a)で表される化合物は、式(2a)で表される化合物である、請求項5に記載の着色硬化性樹脂組成物。
[式(2a)中、R21a~R24aは、それぞれ独立に、水素原子、-R26a、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、ハロゲン原子、-SO3 -、-SO3H、-SO3 -Za1+、-NR28aR29a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。
Xa1-は、対イオンを表す。
R28a及びR29aは、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数1~10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-CH2-は、-O-、又は-CO-で置き換っていてもよく、R28a及びR29a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。
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。
Za1+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。] The colored curable resin composition according to claim 5, wherein the compound represented by the formula (1a) is a compound represented by the formula (2a).
[In the formula (2a), R 21a to R 24a are each independently a hydrogen atom, —R 26a , an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituted group. It represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a group. 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 a halogen atom, —SO 3 − , —SO 3 H, —SO 3 − Za1 + , —NR 28a R 29a 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.
Xa1 − represents a counter ion.
R 28a and R 29a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and —CH 2 contained in the saturated hydrocarbon group. -May be replaced by -O- or -CO-, and R 28a and R 29a may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. Good.
R 26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a halogen atom or a carboxy group.
Za1 + 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. ] - 請求項1~6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 6.
- 請求項7に記載のカラーフィルタを含む表示装置。 A display device including the color filter according to claim 7.
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JP2012237985A (en) * | 2011-04-25 | 2012-12-06 | Fujifilm Corp | Photosensitive resin composition, color filter, protective film, photospacer, substrate for liquid crystal display device, liquid crystal display device, and solid-state imaging element |
JP2013210577A (en) * | 2012-03-30 | 2013-10-10 | Fujifilm Corp | Colored curable composition, color filter, method for producing color filter, and display device |
JP2013257356A (en) * | 2012-06-11 | 2013-12-26 | Sumitomo Chemical Co Ltd | Colored photosensitive resin composition |
JP2016102191A (en) * | 2014-03-31 | 2016-06-02 | 富士フイルム株式会社 | Colored composition, cured film, color filter, method for manufacturing color filter, solid-state image sensing device, image display device, organic electroluminescence device, pigment, and method for manufacturing pigment |
WO2016171072A1 (en) * | 2015-04-20 | 2016-10-27 | Sc有機化学株式会社 | Ether bond-containing sulfur compound and resin composition |
JP2017128708A (en) * | 2016-01-20 | 2017-07-27 | 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. | Colored curable resin composition |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2021004921A (en) * | 2019-06-25 | 2021-01-14 | 東洋インキScホールディングス株式会社 | Photosensitive coloring composition, and color filter and liquid-crystal display using the same |
JP7415342B2 (en) | 2019-06-25 | 2024-01-17 | 東洋インキScホールディングス株式会社 | Photosensitive coloring composition, color filter and liquid crystal display device using the same |
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KR20210127982A (en) | 2021-10-25 |
CN113439092B (en) | 2023-07-21 |
CN113439092A (en) | 2021-09-24 |
TW202035572A (en) | 2020-10-01 |
JPWO2020170944A1 (en) | 2021-12-23 |
JP7499747B2 (en) | 2024-06-14 |
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