TWI621667B - Colored curable resin composition - Google Patents
Colored curable resin composition Download PDFInfo
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- TWI621667B TWI621667B TW102111994A TW102111994A TWI621667B TW I621667 B TWI621667 B TW I621667B TW 102111994 A TW102111994 A TW 102111994A TW 102111994 A TW102111994 A TW 102111994A TW I621667 B TWI621667 B TW I621667B
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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
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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
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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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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- 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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
- G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
- G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
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Abstract
本發明之著色硬化性樹脂組合物包含式(1)所表示之化合物、樹脂、聚合性化合物及聚合起始劑。[式(1)中,Q1及Q2分別獨立地表示氫原子或-CO2M,其中Q1及Q2中之任一者表示-CO2M。R1~R4分別獨立地表示氫原子或碳數1~20之1價烴基,或者R1及R3鍵結而與鄰接之苯環上之碳原子及鄰接之氮原子一起形成環,或R2及R4鍵結而與鄰接之苯環上之碳原子及鄰接之氮原子一起形成環,或R1及R2鍵結而與鄰接之氮原子一起形成環。R5表示氫原子或碳數1~20之1價烴基。於R5存在複數個之情形時,該等彼此相同或不同。M表示氫原子或鹼金屬原子。] The colored curable resin composition of the present invention includes a compound represented by formula (1), a resin, a polymerizable compound, and a polymerization initiator. [In formula (1), Q 1 and Q 2 each independently represent a hydrogen atom or -CO 2 M, and any one of Q 1 and Q 2 represents -CO 2 M. R 1 to R 4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R 1 and R 3 are bonded to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom, or R 2 and R 4 are bonded to form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom, or R 1 and R 2 are bonded to form a ring with an adjacent nitrogen atom. R 5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R 5 exist, these are the same or different from each other. M represents a hydrogen atom or an alkali metal atom. ]
Description
本發明係關於一種著色硬化性樹脂組合物。 The present invention relates to a coloring curable resin composition.
染料例如用於在纖維材料、液晶顯示裝置、噴墨等領域中利用反射光或透射光而進行色顯示。作為該染料,已知有香豆素6(下述式所表示之化合物)等香豆素化合物(JP2006-154740-A之實施例8)。 Dyes are used, for example, to perform color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, inkjet, and the like. As the dye, a coumarin compound such as coumarin 6 (a compound represented by the following formula) is known (Example 8 of JP2006-154740-A).
於由含有上述香豆素化合物之著色硬化性樹脂組合物製成彩色濾光片之步驟中,存在著色劑昇華之方面之問題。 In the step of making a color filter from a coloring curable resin composition containing the above-mentioned coumarin compound, there is a problem in that the colorant is sublimated.
本發明包含以下之發明。 The present invention includes the following inventions.
[1]一種著色硬化性樹脂組合物,其包含式(1)所表示之化合物、樹脂、聚合性化合物及聚合起始劑,式(1)
[式(1)中,Q1及Q2分別獨立地表示氫原子或-CO2M,Q1及Q2中之任一者表示-CO2M;R1~R4分別獨立地表示氫原子或碳數1~20之1價烴基,或者R1及R3鍵結而與鄰接之苯環上之碳原子及鄰接之氮原子一起形成環,R2及R4鍵結而與鄰接之苯環上之碳原子及鄰接之氮原子一起形成環,或R1及R2鍵結而與鄰接之氮原子一起形成環;構成該1價烴基之亞甲基可經氧原子、硫原子、-N(R5)-、磺醯基或羰基取代,該1價烴基所含之氫原子可經鹵素原子、氰基、硝基、胺甲醯基、胺磺醯基、-SO3M、-CO2M、羥基或胺基取代;R5表示氫原子或碳數1~20之1價烴基;於R5存在複數個之情形時,該等彼此相同或不同;M表示氫原子或鹼金屬原子]。 [In formula (1), Q 1 and Q 2 each independently represent a hydrogen atom or -CO 2 M, and any one of Q 1 and Q 2 represents -CO 2 M; R 1 to R 4 each independently represent hydrogen An atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R 1 and R 3 are bonded to form a ring with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring, and R 2 and R 4 are bonded to an adjacent one The carbon atom on the benzene ring and the adjacent nitrogen atom form a ring together, or R 1 and R 2 are bonded to form a ring with the adjacent nitrogen atom; the methylene group constituting the monovalent hydrocarbon group may pass through an oxygen atom, a sulfur atom, -N (R 5 )-, sulfofluorenyl or carbonyl, the hydrogen atom contained in the monovalent hydrocarbon group may be substituted by halogen atom, cyano, nitro, carbamoyl, sulfamoyl, -SO 3 M, -CO 2 M, hydroxyl or amine group substitution; R 5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; when there are a plurality of R 5 , these are the same or different from each other; M represents a hydrogen atom or a base Metal atom].
[2]如[1]之著色硬化性樹脂組合物,其中R1~R4分別獨立地表示氫原子或碳數1~20之1價烴基,或者R1及R3鍵結而與鄰接之苯環上之碳原子及鄰接之氮原子一起形成環,或R2及R4鍵結而與鄰接之苯環上之碳原子及鄰接之氮原子一起形成環。 [2] The colored curable resin composition according to [1], wherein R 1 to R 4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R 1 and R 3 are bonded to be adjacent to each other. The carbon atom on the benzene ring and the adjacent nitrogen atom form a ring together, or R 2 and R 4 are bonded to form a ring with the carbon atom on the adjacent benzene ring and the adjacent nitrogen atom.
[3]如[1]或[2]之著色硬化性樹脂組合物,其中R1~R4分別獨立地表示氫原子或碳數1~20之1價烴基,或者R1及R3鍵結而與鄰接之苯環上之碳原子及鄰接之氮原子一起形成環,且R2及R4鍵結而與鄰接之苯環上之碳原子及鄰接之氮原子一起形成環。 [3] The colored hardening resin composition according to [1] or [2], wherein R 1 to R 4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R 1 and R 3 are bonded The carbon atom on the adjacent benzene ring and the adjacent nitrogen atom form a ring together, and R 2 and R 4 are bonded to form a ring with the carbon atom on the adjacent benzene ring and the adjacent nitrogen atom.
[4]如[1]至[3]中任一項之著色硬化性樹脂組合物,其進而包含顏 料。 [4] The coloring curable resin composition according to any one of [1] to [3], further comprising a pigment material.
[5]如[4]之著色硬化性樹脂組合物,其中顏料為選自由鹵化銅酞菁顏料及鹵化鋅酞菁顏料所組成之群中之至少一種。 [5] The colored curable resin composition according to [4], wherein the pigment is at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment.
[6]如[4]或[5]之著色硬化性樹脂組合物,其中顏料為選自由氯化銅酞菁顏料、溴化銅酞菁顏料及溴化鋅酞菁顏料所組成之群中之至少一種。 [6] The colored hardening resin composition according to [4] or [5], wherein the pigment is selected from the group consisting of a copper chloride phthalocyanine pigment, a copper bromide phthalocyanine pigment, and a zinc bromide phthalocyanine pigment. At least one.
[7]如[4]至[6]中任一項之著色硬化性樹脂組合物,其中顏料為綠色顏料。 [7] The colored curable resin composition according to any one of [4] to [6], wherein the pigment is a green pigment.
[8]如[4]至[7]中任一項之著色硬化性樹脂組合物,其中顏料為選自由C.I.顏料綠7、C.I.顏料綠36及C.I.顏料綠58所組成之群中之至少一種。 [8] The colored hardening resin composition according to any one of [4] to [7], wherein the pigment is at least one selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58 .
[9]如[8]之著色硬化性樹脂組合物,其中顏料為C.I.顏料綠7。 [9] The colored curable resin composition according to [8], wherein the pigment is C.I. Pigment Green 7.
[10]一種彩色濾光片,其係使用如[1]至[9]中任一項之著色硬化性樹脂組合物而形成。 [10] A color filter formed using the coloring curable resin composition according to any one of [1] to [9].
[11]一種液晶顯示裝置,其包含如[10]之彩色濾光片。 [11] A liquid crystal display device including the color filter as in [10].
根據本發明,可提供一種可抑制著色劑之昇華而形成彩色濾光片之著色硬化性樹脂組合物。 According to the present invention, it is possible to provide a coloring curable resin composition capable of suppressing sublimation of a colorant to form a color filter.
本發明之著色硬化性樹脂組合物包含著色劑(A)、樹脂(B)及聚合性化合物(C)、聚合起始劑(D)。 The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
著色劑(A)包含式(1)所表示之化合物。 The colorant (A) contains a compound represented by the formula (1).
本發明之著色硬化性樹脂組合物較佳為進而含有選自由溶劑(E)及調平劑(F)所組成之群中之至少一種。 The colored curable resin composition of the present invention preferably further contains at least one selected from the group consisting of a solvent (E) and a leveling agent (F).
本發明之著色硬化性樹脂組合物亦可進而含有聚合起始助劑 (D1)。 The colored curable resin composition of the present invention may further contain a polymerization initiator (D1).
於本說明書中,只要無特別說明,則作為各成分而例示之化合物可單獨使用或組合複數種使用。 In this specification, unless otherwise specified, the compounds exemplified as each component may be used alone or in combination of plural kinds.
著色劑(A)較佳為包含式(1)所表示之化合物(以下有時稱為「化合物(1)」),進而包含顏料(P)。 The colorant (A) preferably contains a compound represented by formula (1) (hereinafter sometimes referred to as "compound (1)"), and further contains a pigment (P).
化合物(1)亦包含其互變異構物或其等之鹽。 The compound (1) also includes a tautomer or a salt thereof.
式(1)中,作為R1~R4中之鹵素原子,可列舉氟原子、氯原子、溴原子、碘原子。 In the formula (1), examples of the halogen atom in R 1 to R 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
式(1)中,作為R1~R4中之碳數1~20之1價烴基,例如可列舉:甲基、乙基、丙基、異丙基、異丙烯基、1-丙烯基、2-丙烯基、丁基、異丁基、第二丁基、第三丁基、(2-乙基)丁基、2-丁烯基、1,3-丁二烯基、戊基、異戊基、3-戊基、新戊基、第三戊基、1-甲基戊基、2-甲基戊基、2-戊烯基、(3-乙基)戊基、己基、異己基、5-甲基己基、(2-乙基)己基、庚基、(3-乙基)庚基、辛基、壬基、癸基、十一烷基、十二烷基、十八烷基等脂肪族烴基;環丙基、環丁基、環戊基、環己基、環己烯基、環庚基、1-甲基環己基、2-甲基環己基、3-甲基環己基、4-甲基環己基、1,2-二甲基環己基、1,3-二甲基環己基、1,4-二甲基環己基、2,3-二甲基環己基、2,4-二甲基環己基、2,5-二甲基環己基、2,6-二甲基環己基、3,4-二甲基環己基、3,5-二甲基環己基、2,2-二甲基環己基、3,3-二甲基環己基、4,4-二甲基環己基、2,4,6-三甲基環己基、2,2,6,6-四甲基環己基、3,3,5,5-四甲基環己基等脂環式烴基;苯基、鄰甲苯基、間甲苯基、對甲苯基、二甲苯基、2,4,6-三甲苯基、鄰異丙苯基、間異丙苯基、對異丙苯基、苄基、苯乙基、聯苯基、1-萘基、2-萘基等芳香族烴基; 及由該等之組合形成之基。 Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R 1 to R 4 in formula (1) include methyl, ethyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, butyl, isobutyl, second butyl, third butyl, (2-ethyl) butyl, 2-butenyl, 1,3-butadienyl, pentyl, iso Pentyl, 3-pentyl, neopentyl, third pentyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, (3-ethyl) pentyl, hexyl, isohexyl , 5-methylhexyl, (2-ethyl) hexyl, heptyl, (3-ethyl) heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl And other aliphatic hydrocarbon groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4 -Dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2 -Dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4,4-di Cycloaliphatic hydrocarbon groups such as cyclohexyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl; benzene Methyl, o-tolyl, m-tolyl, p-tolyl, xylyl, 2,4,6-trimethylphenyl, o-cumyl, m-cumyl, p-cumyl, benzyl, benzene Aromatic hydrocarbon groups such as ethyl, biphenyl, 1-naphthyl, and 2-naphthyl; and groups formed from a combination of these.
作為構成該等1價烴基之亞甲基經氧原子、硫原子、-N(R5)-、磺醯基或羰基取代,或1價烴基所含之氫原子經鹵素原子、氰基、硝基、胺甲醯基、胺磺醯基、-SO3M、-CO2M、羥基或胺基取代而成之基,例如可列舉:甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第二丁氧基、第三丁氧基、戊氧基、(2-乙基)己氧基等烷氧基;苯氧基等芳氧基;苄氧基等芳烷氧基;甲氧基羰基、乙氧基羰基、丙氧基羰基等烷氧基羰基;乙醯氧基、苯甲醯氧基等醯氧基;N-甲基胺甲醯基、N-乙基胺甲醯基、N-丙基胺甲醯基、N-異丙基胺甲醯基、N-丁基胺甲醯基、N-異丁基胺甲醯基、N-第二丁基胺甲醯基、N-第三丁基胺甲醯基、N-戊基胺甲醯基、N-(1-乙基丙基)胺甲醯基、N-(1,1-二甲基丙基)胺甲醯基、N-(1,2-二甲基丙基)胺甲醯基、N-(2,2-二甲基丙基)胺甲醯基、N-(1-甲基丁基)胺甲醯基、N-(2-甲基丁基)胺甲醯基、N-(3-甲基丁基)胺甲醯基、N-環戊基胺甲醯基、N-己基胺甲醯基、N-(1,3-二甲基丁基)胺甲醯基、N-(3,3-二甲基丁基)胺甲醯基、N-庚基胺甲醯基、N-(1-甲基己基)胺甲醯基、N-(1,4-二甲基戊基)胺甲醯基、N-辛基胺甲醯基、N-(2-乙基己基)胺甲醯基、N-(1,5-二甲基)己基胺甲醯基、N-(1,1,2,2-四甲基丁基)胺甲醯基等N-1取代胺甲醯基;N,N-二甲基胺甲醯基、N,N-乙基甲基胺甲醯基、N,N-二乙基胺甲醯基、N,N-丙基甲基胺甲醯基、N,N-異丙基甲基胺甲醯基、N,N-第三丁基甲基胺甲醯基、N,N-丁基乙基胺甲醯基、N,N-雙(1-甲基丙基)胺甲醯基、N,N-庚基甲基胺甲醯基、N,N-雙(2-乙基己基)胺甲醯基等 N,N-2取代胺甲醯基;N-甲基胺磺醯基、N-乙基胺磺醯基、N-丙基胺磺醯基、N-異丙基胺磺醯基、N-丁基胺磺醯基、N-異丁基胺磺醯基、N-第二丁基胺磺醯基、N-第三丁基胺磺醯基、N-戊基胺磺醯基、N-(1-乙基丙基)胺磺醯基、N-(1,1-二甲基丙基)胺磺醯基、N-(1,2-二甲基丙基)胺磺醯基、N-(2,2-二甲基丙基)胺磺醯基、N-(1-甲基丁基)胺磺醯基、N-(2-甲基丁基)胺磺醯基、N-(3-甲基丁基)胺磺醯基、N-環戊基胺磺醯基、N-己基胺磺醯基、N-(1,3-二甲基丁基)胺磺醯基、N-(3,3-二甲基丁基)胺磺醯基、N-庚基胺磺醯基、N-(1-甲基己基)胺磺醯基、N-(1,4-二甲基戊基)胺磺醯基、N-辛基胺磺醯基、N-(2-乙基己基)胺磺醯基、N-(1,5-二甲基)己基胺磺醯基、N-(1,1,2,2-四甲基丁基)胺磺醯基等N-1取代胺磺醯基;N,N-二甲基胺磺醯基、N,N-乙基甲基胺磺醯基、N,N-二乙基胺磺醯基、N,N-丙基甲基胺磺醯基、N,N-異丙基甲基胺磺醯基、N,N-第三丁基甲基胺磺醯基、N,N-丁基乙基胺磺醯基、N,N-雙(1-甲基丙基)胺磺醯基、N,N-庚基甲基胺磺醯基、N,N-雙(2-乙基己基)胺磺醯基等N,N-2取代胺磺醯基;N-甲基胺基、N-乙基胺基、N-丙基胺基、N-異丙基胺基、N-丁基胺基、N-異丁基胺基、N-第二丁基胺基、N-第三丁基胺基、N-戊基胺基、N-(1-乙基丙基)胺基、N-(1,1-二甲基丙基)胺基、N-(1,2-二甲基丙基)胺基、N-(2,2-二甲基丙基)胺基、N-(1-甲基丁基)胺基、N-(2-甲基丁基)胺基、N-(3-甲基丁基)胺基、N-環戊基胺基、N-己基胺基、N-(1,3-二甲基丁基)胺基、N-(3,3-二甲基丁基)胺基、N-庚基胺基、N-(1-甲基己基)胺基、N-(1,4-二甲基戊基)胺基、N-辛基胺基、N-(2-乙基己基)胺基、N-(1,5-二甲基)己基胺基、N-(1,1,2,2-四甲基丁基)胺基等N-烷基胺基; N,N-二甲基胺基、N,N-乙基甲基胺基、N,N-二乙基胺基、N,N-丙基甲基胺基、N,N-異丙基甲基胺基、N,N-第三丁基甲基胺基、N,N-丁基乙基胺基、N,N-雙(1-甲基丙基)胺基、N,N-庚基甲基胺基、N,N-雙(2-乙基己基)胺基等N,N-二烷基胺基;N-甲基胺基甲基、N-乙基胺基甲基、N-丙基胺基甲基、N-異丙基胺基甲基、N-丁基胺基甲基、N-異丁基胺基甲基、N-第二丁基胺基甲基、N-第三丁基胺基甲基、N-戊基胺基甲基、N-(1-乙基丙基)胺基甲基、N-(1,1-二甲基丙基)胺基甲基、N-(1,2-二甲基丙基)胺基甲基、N-(2,2-二甲基丙基)胺基甲基、N-(1-甲基丁基)胺基甲基、N-(2-甲基丁基)胺基甲基、N-(3-甲基丁基)胺基甲基、N-環戊基胺基甲基、N-己基胺基甲基、N-(1,3-二甲基丁基)胺基甲基、N-(3,3-二甲基丁基)胺基甲基、N-庚基胺基甲基、N-(1-甲基己基)胺基甲基、N-(1,4-二甲基戊基)胺基甲基、N-辛基胺基甲基、N-(2-乙基己基)胺基甲基、N-(1,5-二甲基)己基胺基甲基、N-(1,1,2,2-四甲基丁基)胺基甲基等N-烷基胺基甲基;N,N-二甲基胺基甲基、N,N-乙基甲基胺基甲基、N,N-二乙基胺基甲基、N,N-丙基甲基胺基甲基、N,N-異丙基甲基胺基甲基、N,N-第三丁基甲基胺基甲基、N,N-丁基乙基胺基甲基、N,N-雙(1-甲基丙基)胺基甲基、N,N-庚基甲基胺基甲基、N,N-雙(2-乙基己基)胺基甲基等N,N-二烷基胺基甲基;三氟甲基、全氟乙基、全氟丙基、全氟異丙基、全氟異丙烯基、全氟(1-丙烯基)、全氟(2-丙烯基)、全氟丁基、全氟異丁基、全氟(第二丁基)、全氟(第三丁基)、全氟(2-丁烯基)、全氟(1,3-丁二烯基)、全氟戊基、全氟(異戊基)、全氟(3-戊基)、全氟新戊基、全氟(第三戊基)、全氟(1-甲基戊基)、全氟(2-甲基戊基)、全氟(2-戊烯基)、全氟己基、全氟異己基、全氟(5-甲基己基)、全氟(2-乙基己基)、全氟 庚基、全氟辛基、全氟壬基、全氟癸基、全氟十一烷基、全氟十二烷基、全氟十八烷基等具有氟原子之脂肪族烴基;全氟環丙基、全氟環丁基、全氟環戊基、全氟環己基、全氟環己烯基、全氟環庚基、全氟(1-甲基環己基)、全氟(2-甲基環己基)、全氟(3-甲基環己基)、全氟(4-甲基環己基)、全氟(1,2-二甲基環己基)、全氟(1,3-二甲基環己基)、全氟(1,4-二甲基環己基)、全氟(2,3-二甲基環己基)、全氟(2,4-二甲基環己基)、全氟(2,5-二甲基環己基)、全氟(2,6-二甲基環己基)、全氟(3,4-二甲基環己基)、全氟(3,5-二甲基環己基)、全氟(2,2-二甲基環己基)、全氟(3,3-二甲基環己基)、全氟(4,4-二甲基環己基)、全氟(2,4,6-三甲基環己基)、全氟(2,2,6,6-四甲基環己基)、全氟(3,3,5,5-四甲基環己基)等具有氟原子之脂環式烴基;全氟苯基、全氟(鄰甲苯基)、全氟(間甲苯基)、全氟(對甲苯基)、全氟二甲苯基、全氟2,4,6-三甲苯基、全氟(鄰異丙苯基)、全氟(間異丙苯基)、全氟(對異丙苯基)、全氟苄基、全氟苯乙基、全氟聯苯基、全氟(1-萘基)、全氟(2-萘基)、1-三氟甲基苯基、2-三氟甲基苯基、3-三氟甲基苯基、4-三氟甲基苯基等具有氟原子之芳香族烴基;全氟甲氧基、全氟乙氧基、全氟丙氧基、全氟(異丙氧基)、全氟丁氧基、全氟(異丁氧基)、全氟(第二丁氧基)、全氟(第三丁氧基)、全氟戊氧基、全氟苯氧基、全氟苄氧基、2,2,2-三氟乙氧基、(全氟乙基)甲氧基、(全氟丙基)甲氧基、(全氟(異丙基))甲氧基、(全氟(異丙烯基))甲氧基、(全氟(1-丙烯基))甲氧基、(全氟(2-丙烯基))甲氧基、(全氟丁基)甲氧基、(全氟(異丁基))甲氧基、(全氟(第二丁基))甲氧基、(全氟(第三丁基))甲氧基、(全氟(2-丁烯基))甲氧基、(全氟(1,3-丁二烯基))甲氧基、(全氟戊基)甲氧基、(全氟(異戊基))甲氧基、(全氟(3-戊基))甲氧基、(全氟(新戊基))甲氧基、(全氟(第三戊基))甲氧基、(全氟(1-甲基戊基))甲氧基、(全氟(2-甲基戊基))甲氧基、(全氟(2-戊烯 基))甲氧基、(全氟己基)甲氧基、(全氟(異己基))甲氧基、(全氟(5-甲基己基))甲氧基、(全氟((2-乙基)己基))甲氧基、(全氟庚基)甲氧基、(全氟辛基)甲氧基、(全氟壬基)甲氧基、(全氟癸基)甲氧基、(全氟十一烷基)甲氧基、(全氟十二烷基)甲氧基、(全氟十八烷基)甲氧基等具有氟原子之取代氧基;2,3-雙(三氟甲基)苯基甲基、2,4-雙(三氟甲基)苯基甲基、2,5-雙(三氟甲基)苯基甲基、2,6-雙(三氟甲基)苯基甲基、3,4-雙(三氟甲基)苯基甲基、3,5-雙(三氟甲基)苯基甲基等。 The methylene group constituting the monovalent hydrocarbon group is substituted with an oxygen atom, a sulfur atom, -N (R 5 )-, a sulfonyl group or a carbonyl group, or a hydrogen atom contained in the monovalent hydrocarbon group is substituted with a halogen atom, a cyano group, or a nitrate A group substituted with a carbamoyl group, amidinomethyl group, sulfamoyl group, -SO 3 M, -CO 2 M, a hydroxyl group, or an amine group. Examples include methoxy, ethoxy, propoxy, and isopropyl. Alkoxy groups such as oxy, butoxy, isobutoxy, second butoxy, third butoxy, pentyloxy, (2-ethyl) hexyloxy; aryloxy such as phenoxy; Aryloxy groups such as benzyloxy; alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, and propoxycarbonyl; fluorenyl groups such as ethoxyl and benzyloxy; N-methylamine methyl Fluorenyl, N-ethylaminoformamyl, N-propylaminoformamyl, N-isopropylamineformamyl, N-butylamineformamyl, N-isobutylamineformamyl, N-second butylaminoformamyl, N-third butylaminoformamyl, N-pentylaminoformamyl, N- (1-ethylpropyl) aminoformamyl, N- (1 , 1-dimethylpropyl) carbamoyl, N- (1,2-dimethylpropyl) carbamoyl, N- (2,2-dimethylpropyl) carbamoyl, N- (1-methylbutyl) amine Fluorenyl, N- (2-methylbutyl) aminomethane, N- (3-methylbutyl) aminomethane, N-cyclopentylaminomethane, N-hexylaminemethane , N- (1,3-dimethylbutyl) aminomethyl, N- (3,3-dimethylbutyl) aminomethyl, N-heptylaminomethyl, N- (1 -Methylhexyl) carbamyl, N- (1,4-dimethylpentyl) carbamyl, N-octylaminocarbamyl, N- (2-ethylhexyl) carbamyl N-1 substituted carbamoyl groups, such as N- (1,5-dimethyl) hexylaminocarbamyl, N- (1,1,2,2-tetramethylbutyl) aminoformamyl; N , N-dimethylaminoformamyl, N, N-ethylmethylaminoformamyl, N, N-diethylaminoformamyl, N, N-propylmethylaminoformamyl, N , N-Isopropylmethylamine formamyl, N, N-Third-butylmethylamine formamyl, N, N-butylethylamine formamyl, N, N-bis (1-methylpropane N) N-2 substituted carbamoyl groups such as carbamoyl, N, N-heptylmethylcarbamoyl, N, N-bis (2-ethylhexyl) carbamoyl; N- Methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropylaminesulfonyl, N-butylaminesulfonyl, N-isobutylamine Sulfonyl, N-second butylamine, sulfonyl, N-third butylamine Fluorenyl, N-pentylaminosulfonyl, N- (1-ethylpropyl) sulfanilino, N- (1,1-dimethylpropyl) sulfanilino, N- (1, 2-dimethylpropyl) sulfamomidino, N- (2,2-dimethylpropyl) sulfamomidino, N- (1-methylbutyl) sulfamomidino, N- (2 -Methylbutyl) sulfamomidino, N- (3-methylbutyl) sulfamomidino, N-cyclopentylaminesulfonamidino, N-hexylaminesulfamonium, N- (1,3 -Dimethylbutyl) sulfamoyl, N- (3,3-dimethylbutyl) sulfamoyl, N-heptylaminesulfamoyl, N- (1-methylhexyl) sulfamoyl Fluorenyl, N- (1,4-dimethylpentyl) aminosulfonyl, N-octylaminesulfonyl, N- (2-ethylhexyl) aminesulfonyl, N- (1,5 -Dimethyl) hexylaminesulfonyl, N- (1,1,2,2-tetramethylbutyl) aminesulfonyl and other N-1 substituted aminesulfonyl; N, N-dimethylamine Sulfonyl, N, N-ethylmethylaminesulfonyl, N, N-diethylaminesulfonyl, N, N-propylmethylaminesulfonyl, N, N-isopropylmethyl N-aminosulfonyl, N, N-tert-butylmethylaminesulfonyl, N, N-butylethylaminesulfonyl, N, N-bis (1-methylpropyl) aminesulfonyl, N, N-Heptylmethylaminesulfonyl, N, N-bis (2-ethylhexyl) aminesulfonyl and other N, N-2 substituted amines Fluorenyl; N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamino, N-isobutylamino, N- Dibutylamino, N-thirdbutylamino, N-pentylamino, N- (1-ethylpropyl) amino, N- (1,1-dimethylpropyl) amino , N- (1,2-dimethylpropyl) amino, N- (2,2-dimethylpropyl) amino, N- (1-methylbutyl) amino, N- (2 -Methylbutyl) amino, N- (3-methylbutyl) amino, N-cyclopentylamino, N-hexylamino, N- (1,3-dimethylbutyl) amine Base, N- (3,3-dimethylbutyl) amino, N-heptylamino, N- (1-methylhexyl) amino, N- (1,4-dimethylpentyl) Amine, N-octylamino, N- (2-ethylhexyl) amino, N- (1,5-dimethyl) hexylamino, N- (1,1,2,2-tetramethyl) N-alkylamino groups such as butyl) amino groups; N, N-dimethylamino groups, N, N-ethylmethylamino groups, N, N-diethylamino groups, N, N-propyl Methylmethylamino, N, N-isopropylmethylamino, N, N-third butylmethylamino, N, N-butylethylamino, N, N-bis (1-methyl (Propyl) amino, N, N-heptylmethylamino, N, N-bis (2-ethylhexyl) amino, and other N, N-dialkylamino groups; N-methylaminomethyl , N-ethylaminomethyl, N-propylaminomethyl, N-isopropylaminomethyl, N-butylaminomethyl, N-isobutylaminomethyl, N- Second butylaminomethyl, N-third butylaminomethyl, N-pentylaminomethyl, N- (1-ethylpropyl) aminomethyl, N- (1,1 -Dimethylpropyl) aminomethyl, N- (1,2-dimethylpropyl) aminomethyl, N- (2,2-dimethylpropyl) aminomethyl, N- (1-methylbutyl) aminomethyl, N- (2-methylbutyl) aminomethyl, N- (3-methylbutyl) aminomethyl, N-cyclopentylamino Methyl, N-hexylaminomethyl, N- (1,3-dimethylbutyl) aminomethyl, N- (3,3-dimethylbutyl) aminomethyl, N-heptyl Aminoaminomethyl, N- (1-methylhexyl) aminomethyl, N- (1,4-dimethylpentyl) aminomethyl, N-octylaminomethyl, N- ( 2-ethylhexyl) aminomethyl, N- (1,5-dimethyl) hexylaminomethyl, N- (1,1,2,2-tetramethylbutyl) aminomethyl, etc. N-alkylaminomethyl; N, N-dimethylaminomethyl, N, N-ethylmethylaminomethyl, N, N-diethylaminomethyl, N, N- Propylmethylaminomethyl, N, N-isopropylmethylaminomethyl, N, N-third butyl Aminoaminomethyl, N, N-butylethylaminomethyl, N, N-bis (1-methylpropyl) aminomethyl, N, N-heptylmethylaminomethyl, N, N-bis (2-ethylhexyl) aminomethyl and other N, N-dialkylaminomethyl; trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, Perfluoroisopropenyl, perfluoro (1-propenyl), perfluoro (2-propenyl), perfluorobutyl, perfluoroisobutyl, perfluoro (second butyl), perfluoro (third butyl) Group), perfluoro (2-butenyl), perfluoro (1,3-butadienyl), perfluoropentyl, perfluoro (isopentyl), perfluoro (3-pentyl), perfluoro Neopentyl, perfluoro (third pentyl), perfluoro (1-methylpentyl), perfluoro (2-methylpentyl), perfluoro (2-pentenyl), perfluorohexyl, perfluoro Fluoroisohexyl, perfluoro (5-methylhexyl), perfluoro (2-ethylhexyl), perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, perfluoroundecyl , Perfluorododecyl, perfluorooctadecyl and other aliphatic hydrocarbon groups having a fluorine atom; perfluorocyclopropyl, perfluorocyclobutyl, perfluorocyclopentyl, perfluorocyclohexyl, perfluorocyclohexyl Alkenyl, perfluorocycloheptyl, perfluoro (1-methylcyclohexyl), perfluoro (2- Cyclohexyl), perfluoro (3-methylcyclohexyl), perfluoro (4-methylcyclohexyl), perfluoro (1,2-dimethylcyclohexyl), perfluoro (1,3-dimethyl Cyclohexyl), perfluoro (1,4-dimethylcyclohexyl), perfluoro (2,3-dimethylcyclohexyl), perfluoro (2,4-dimethylcyclohexyl), perfluoro ( 2,5-dimethylcyclohexyl), perfluoro (2,6-dimethylcyclohexyl), perfluoro (3,4-dimethylcyclohexyl), perfluoro (3,5-dimethylcyclo Hexyl), perfluoro (2,2-dimethylcyclohexyl), perfluoro (3,3-dimethylcyclohexyl), perfluoro (4,4-dimethylcyclohexyl), perfluoro (2, 4,6-trimethylcyclohexyl), perfluoro (2,2,6,6-tetramethylcyclohexyl), perfluoro (3,3,5,5-tetramethylcyclohexyl), etc. have fluorine atoms Alicyclic hydrocarbon groups; perfluorophenyl, perfluoro (o-tolyl), perfluoro (m-tolyl), perfluoro (p-tolyl), perfluoroxylyl, perfluoro2,4,6-tri Tolyl, perfluoro (o-cumyl), perfluoro (m-cumyl), perfluoro (p-cumyl), perfluorobenzyl, perfluorophenethyl, perfluorobiphenyl, Perfluoro (1-naphthyl), perfluoro (2-naphthyl), 1-trifluoromethylphenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethyl Phenylbenzene Aromatic hydrocarbon groups having a fluorine atom, such as perfluoromethoxy; perfluoromethoxy, perfluoroethoxy, perfluoropropoxy, perfluoro (isopropoxy), perfluorobutoxy, perfluoro (isobutoxy ), Perfluoro (second butoxy), perfluoro (third butoxy), perfluoropentoxy, perfluorophenoxy, perfluorobenzyloxy, 2,2,2-trifluoroethoxy (Perfluoroethyl) methoxy, (perfluoropropyl) methoxy, (perfluoro (isopropyl)) methoxy, (perfluoro (isopropenyl)) methoxy, (all Fluoro (1-propenyl)) methoxy, (perfluoro (2-propenyl)) methoxy, (perfluorobutyl) methoxy, (perfluoro (isobutyl)) methoxy, ( Perfluoro (second butyl)) methoxy, (perfluoro (third butyl)) methoxy, (perfluoro (2-butenyl)) methoxy, (perfluoro (1,3- Butadienyl)) methoxy, (perfluoropentyl) methoxy, (perfluoro (isopentyl)) methoxy, (perfluoro (3-pentyl)) methoxy, (perfluoro (Neopentyl)) methoxy, (perfluoro (third pentyl)) methoxy, (perfluoro (1-methylpentyl)) methoxy, (perfluoro (2-methylpentyl) )) Methoxy, (perfluoro (2-pentenyl)) methoxy, (perfluorohexyl) methoxy, (perfluoro (isohexyl)) methoxy, (perfluoro (5-methyl )) Methoxy, (perfluoro ((2-ethyl) hexyl)) methoxy, (perfluoroheptyl) methoxy, (perfluorooctyl) methoxy, (perfluorononyl) Methoxy, (perfluorodecyl) methoxy, (perfluoroundecyl) methoxy, (perfluorododecyl) methoxy, (perfluorooctadecyl) methoxy, etc. Substituted oxygen with a fluorine atom; 2,3-bis (trifluoromethyl) phenylmethyl, 2,4-bis (trifluoromethyl) phenylmethyl, 2,5-bis (trifluoromethyl) ) Phenylmethyl, 2,6-bis (trifluoromethyl) phenylmethyl, 3,4-bis (trifluoromethyl) phenylmethyl, 3,5-bis (trifluoromethyl) benzene Methyl and so on.
作為R1及R2,較佳為脂肪族烴基、脂環式烴基或芳香族烴基。該脂肪族烴基所含之氫原子可經脂環式烴基或芳香族烴基取代。該脂環式烴基所含之氫原子可經脂肪族烴基、脂環式烴基或芳香族烴基取代。該芳香族烴基所含之氫原子可經脂肪族烴基、脂環式烴基或芳香族烴基取代。 R 1 and R 2 are preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
作為R1,較佳為碳數1~10之脂肪族烴基。其中,更佳為乙基、丁基、己基、(2-乙基)己基及辛基,進而較佳為乙基、丁基、己基及(2-乙基)己基,尤佳為(2-乙基)己基。R1為該等基之本發明之化合物於溶劑中之溶解性優異。 R 1 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Among these, ethyl, butyl, hexyl, (2-ethyl) hexyl, and octyl are more preferred, and ethyl, butyl, hexyl, and (2-ethyl) hexyl are more preferred, and (2- (Ethyl) hexyl. The compound of the present invention in which R 1 is such a group has excellent solubility in a solvent.
作為R2,較佳為碳數1~10之脂肪族烴基。其中,更佳為乙基、丁基、己基、(2-乙基)己基及辛基,進而較佳為乙基、丁基、己基及(2-乙基)己基,尤佳為己基及(2-乙基)己基。R2為該等基之本發明之化合物於溶劑中之溶解性優異。 R 2 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Among these, ethyl, butyl, hexyl, (2-ethyl) hexyl, and octyl are more preferred, and ethyl, butyl, hexyl, and (2-ethyl) hexyl are more preferred, and hexyl and ( 2-ethyl) hexyl. The compound of the present invention in which R 2 is such a group has excellent solubility in a solvent.
就製造容易性之方面而言,R3及R4較佳為氫原子。 In terms of ease of production, R 3 and R 4 are preferably hydrogen atoms.
於R1及R3鍵結而與鄰接之苯環上之碳原子及鄰接之氮原子一起形成環之情形、及/或R2及R4鍵結而與鄰接之苯環上之碳原子及鄰接之氮原子一起形成環之情形時,作為*-R1-R3-*及*-R2-R4-*,可列舉:*-CH2-CH2-*、*-CF2-CF2-*、*-CH2-C(CH2)5-*或*-CH2- C(CH3)2-*等,較佳為*-CH2-CH2-*及*-CH2-C(CH3)2-*,其中更佳為*-CH2-C(CH3)2-*。*表示鍵結鍵。 When R 1 and R 3 are bonded to form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom, and / or R 2 and R 4 are bonded to a carbon atom on an adjacent benzene ring and When adjacent nitrogen atoms form a ring together, examples of * -R 1 -R 3- * and * -R 2 -R 4- * include: * -CH 2 -CH 2- *, * -CF 2- CF 2- *, * -CH 2 -C (CH 2 ) 5- * or * -CH 2 -C (CH 3 ) 2- *, etc., preferably * -CH 2 -CH 2- * and * -CH 2 -C (CH 3 ) 2- *, more preferably * -CH 2 -C (CH 3 ) 2- *. * Indicates a bond key.
於R1及R2鍵結而與鄰接之氮原子一起形成環之情形時,作為*-R1-R2-*,可列舉:*-(CH2)2-*、*-(CH2)3-*、*-(CH2)4-*、*-(CH2)5-*、*-(CH2)6-*、*-(CH2)7-*、*-(CF2)2-*、*-(CF2)3-*、*-(CF2)4-*、*-(CF2)5-*、*-(CF2)6-*、*-(CF2)7-*等,較佳為*-(CH2)4-*、*-(CH2)5-*、*-(CH2)6-*、*-(CF2)4-*、*-(CF2)5-*及*-(CF2)6-,其中更佳為*-(CH2)4-*、*-(CH2)5-*及*-(CH2)6-*,尤佳為*-(CH2)4-*及*-(CH2)5-*。*表示鍵結鍵。 When R 1 and R 2 are bonded to form a ring with an adjacent nitrogen atom, examples of * -R 1 -R 2- * include: *-(CH 2 ) 2- *, *-(CH 2 ) 3- *, *-(CH 2 ) 4- *, *-(CH 2 ) 5- *, *-(CH 2 ) 6- *, *-(CH 2 ) 7- *, *-(CF 2 ) 2- *, *-(CF 2 ) 3- *, *-(CF 2 ) 4- *, *-(CF 2 ) 5- *, *-(CF 2 ) 6- *, *-(CF 2 ) 7- *, etc., preferably *-(CH 2 ) 4- *, *-(CH 2 ) 5- *, *-(CH 2 ) 6- *, *-(CF 2 ) 4- *, * -(CF 2 ) 5- * and *-(CF 2 ) 6- , more preferably *-(CH 2 ) 4- *, *-(CH 2 ) 5- * and *-(CH 2 ) 6- *, Particularly preferably *-(CH 2 ) 4- * and *-(CH 2 ) 5- *. * Indicates a bond key.
作為R5中之碳數1~20之1價烴基,可列舉:甲基、乙基、丙基、異丙基、異丙烯基、1-丙烯基、2-丙烯基、丁基、異丁基、第二丁基、第三丁基、(2-乙基)丁基、2-丁烯基、1,3-丁二烯基、戊基、異戊基、3-戊基、新戊基、第三戊基、1-甲基戊基、2-甲基戊基、2-戊烯基、(3-乙基)戊基、己基、異己基、5-甲基己基、(2-乙基)己基、庚基、(3-乙基)庚基、辛基、壬基、癸基、十一烷基、十二烷基、十八烷基等脂肪族烴基;環丙基、環丁基、環戊基、環己基、環己烯基、環庚基、1-甲基環己基、2-甲基環己基、3-甲基環己基、4-甲基環己基、1,2-二甲基環己基、1,3-二甲基環己基、1,4-二甲基環己基、2,3-二甲基環己基、2,4-二甲基環己基、2,5-二甲基環己基、2,6-二甲基環己基、3,4-二甲基環己基、3,5-二甲基環己基、2,2-二甲基環己基、3,3-二甲基環己基、4,4-二甲基環己基、2,4,6-三甲基環己基、2,2,6,6-四甲基環己基、3,3,5,5-四甲基環己基等脂環式烴基;苯基、鄰甲苯基、間甲苯基、對甲苯基、二甲苯基、2,4,6-三甲苯基、鄰異丙苯基、間異丙苯基、對異丙苯基、苄基、苯乙基、聯苯基、1-萘基、2-萘基等芳香族烴基; 及由該等之組合形成之基。 Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R 5 include methyl, ethyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, butyl, and isobutyl Base, second butyl, third butyl, (2-ethyl) butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, 3-pentyl, neopentyl Base, tertiary pentyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, (3-ethyl) pentyl, hexyl, isohexyl, 5-methylhexyl, (2- (Ethyl) hexyl, heptyl, (3-ethyl) heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl and other aliphatic hydrocarbon groups; cyclopropyl, cyclo Butyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2 -Dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5 -Dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3 -Dimethylcyclohexyl, 4,4-dimethylcyclohexyl, 2,4,6- Alicyclic hydrocarbon groups such as trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl; phenyl, o-tolyl, m-tolyl, P-tolyl, xylyl, 2,4,6-trimethylphenyl, o-cumyl, m-cumyl, p-cumyl, benzyl, phenethyl, biphenyl, 1-naphthalene Aromatic hydrocarbon groups such as methyl, 2-naphthyl, and the like; and groups formed from a combination of these.
M表示氫原子或鹼金屬原子,較佳為氫原子、鈉原子或鉀原子,更佳為氫原子。 M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom, a sodium atom, or a potassium atom, and more preferably a hydrogen atom.
作為Q1為-CO2M之化合物(1),例如可列舉式(1-1)~式(1-44)分別所表示之化合物及其等之鹽。 Examples of the compound (1) in which Q 1 is -CO 2 M include compounds represented by the formulae (1-1) to (1-44), and salts thereof.
作為Q2為-CO2M之化合物(1),例如可列舉式(1-45)~式(1-88)分別所表示之化合物及其等之鹽。 Examples of the compound (1) in which Q 2 is -CO 2 M include compounds represented by the formulae (1-45) to (1-88), and salts thereof.
就合成之容易性之觀點而言,作為化合物(1),較佳為化合物(1-1)~化合物(1-8)、化合物(1-15)~化合物(1-42)、化合物(1-45)~化合物(1-52)及化合物(1-59)~化合物(1-86),其中更佳為化合物(1-1)~化合物(1-4)、化合物(1-15)~化合物(1-32)、化合物(1-39)~化合物(1-42)、化合物(1-45)~化合物(1-48)、化合物(1-59)~化合物(1-76)及化合物(1-83)~化合物(1-86),其中進而較佳為化合物(1-1)~化合物(1- 4)、化合物(1-15)~化合物(1-20)、化合物(1-27)~化合物(1-28)、化合物(1-31)~化合物(1-32)、化合物(1-39)~化合物(1-42)、化合物(1-45)~化合物(1-48)、化合物(1-59)~化合物(1-64)、化合物(1-71)~化合物(1-72)、化合物(1-75)~化合物(1-76)及化合物(1-83)~化合物(1-86)。 From the viewpoint of ease of synthesis, the compound (1) is preferably a compound (1-1) to a compound (1-8), a compound (1-15) to a compound (1-42), and a compound (1). -45) ~ compound (1-52) and compound (1-59) ~ compound (1-86), more preferably compound (1-1) ~ compound (1-4), compound (1-15) ~ Compound (1-32), compound (1-39) to compound (1-42), compound (1-45) to compound (1-48), compound (1-59) to compound (1-76), and compound (1-83) to compound (1-86), among which compound (1-1) to compound (1- 4), compound (1-15) to compound (1-20), compound (1-27) to compound (1-28), compound (1-31) to compound (1-32), compound (1-39 ) ~ Compound (1-42), Compound (1-45) ~ Compound (1-48), Compound (1-59) ~ Compound (1-64), Compound (1-71) ~ Compound (1-72) Compound (1-75) to compound (1-76) and compound (1-83) to compound (1-86).
化合物(1)例如可依據染料與顏料(Dyes and Pigments)(2008),77,556-558.中所記載之方法而製造。 The compound (1) can be produced, for example, according to the method described in Dyes and Pigments (2008), 77, 556-558.
具體而言,化合物(1)可藉由使式(q1)所表示之化合物、式(q2)所表示之化合物及氰基乙酸乙酯於苯甲酸及溶劑之存在下進行環化反應而製造。反應溫度較佳為0℃~200℃,更佳為100℃~150℃。反應時間較佳為1小時~24小時,更佳為8小時~16小時。作為上述溶劑,較佳為甲醇、乙醇、2-丙醇、1-丁醇、1-戊醇、1-辛醇或N-甲基吡咯啶酮等,較佳為1-戊醇。 Specifically, the compound (1) can be produced by subjecting a compound represented by the formula (q1), a compound represented by the formula (q2), and ethyl cyanoacetate to a cyclization reaction in the presence of benzoic acid and a solvent. The reaction temperature is preferably 0 ° C to 200 ° C, and more preferably 100 ° C to 150 ° C. The reaction time is preferably 1 hour to 24 hours, and more preferably 8 hours to 16 hours. As said solvent, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, N-methylpyrrolidone, etc. are preferable, and 1-pentanol is preferable.
[式(q1)及式(q2)中,R1~R4、Q1及Q2分別表示與上述相同之含義。] [In formulae (q1) and (q2), R 1 to R 4 , Q 1 and Q 2 each have the same meaning as described above. ]
於化合物(1)之製造中,式(q1)所表示之化合物之使用量相對於式(q2)所表示之化合物1莫耳,較佳為1莫耳~10莫耳,更佳為1莫耳~4莫耳,進而較佳為1莫耳~3莫耳,進而更佳為1莫耳。 In the production of the compound (1), the amount of the compound represented by the formula (q1) is 1 mole, preferably 1 mole to 10 moles, and more preferably 1 mole relative to the compound represented by the formula (q2). Ears to 4 moles, more preferably 1 mole to 3 moles, even more preferably 1 mole.
於化合物(1)之製造中,氰基乙酸乙酯之使用量相對於式(q2)所表示之化合物1莫耳,較佳為1莫耳~10莫耳,更佳為1莫耳~4莫耳,進而較佳為1莫耳~3莫耳,進而更佳為1莫耳。 In the production of compound (1), the amount of ethyl cyanoacetate used is 1 mole, preferably 1 mole to 10 moles, and more preferably 1 mole to 4 relative to the compound represented by formula (q2). The mole is more preferably 1 to 3 moles, and even more preferably 1 mole.
於化合物(1)之製造中,苯甲酸之使用量相對於式(q2)所表示之化合物1莫耳,較佳為0.1莫耳~3莫耳,更佳為0.3莫耳~3莫耳,進而較佳為0.3莫耳~1.2莫耳,進而更佳為0.3~0.4莫耳。 In the production of compound (1), the amount of benzoic acid used is 1 mole, preferably 0.1 mole to 3 moles, more preferably 0.3 mole to 3 moles, relative to the compound represented by formula (q2). It is more preferably 0.3 to 1.2 moles, and still more preferably 0.3 to 0.4 moles.
由反應混合物獲取作為目標化合物之化合物(1)之方法並無特別限定,可採用公知之各種方法。例如,較佳為藉由適當調整反應混合物之溫度之方法、或於不使化合物(1)溶解之溶劑中添加反應混合物之方法使結晶析出,並濾取該結晶。所濾取之結晶較佳為於水、乙腈、甲醇、乙醇、2-丙醇、1-丁醇、1-戊醇、1-辛醇、四氫呋喃、丙酮、乙酸、乙酸乙酯、己烷、甲苯、N,N-二甲基甲醯胺、N-甲基吡咯啶酮、氯仿或該等之混合液等溶劑中進行清洗或再結晶,繼而進行乾燥。又,視需要亦可藉由管柱層析法或再結晶等公知之方法進一步進行精製。 The method for obtaining the compound (1) as a target compound from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, it is preferable to precipitate the crystals by a method of appropriately adjusting the temperature of the reaction mixture or a method of adding the reaction mixture to a solvent that does not dissolve the compound (1), and the crystals are collected by filtration. The filtered crystals are preferably water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, Toluene, N, N-dimethylformamidine, N-methylpyrrolidone, chloroform, or a mixture of these solvents are used for washing or recrystallization, and then drying. If necessary, further purification can be performed by a known method such as column chromatography or recrystallization.
作為顏料(P),並無特別限定,可使用公知之顏料,例如可列舉以色指數(Colour Index)(染色家協會會誌(The Society of Dyers and Colourists)出版)分類為顏料(Pigment)之顏料。 The pigment (P) is not particularly limited, and known pigments can be used, and examples thereof include those classified as pigments by the Color Index (published by The Society of Dyers and Colourists). pigment.
作為顏料,例如可列舉:C.I.顏料黃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、194、214等黃色顏料;C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料;C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265等紅色顏料;C.I.顏料藍15、15:3、15:4、15:6、60等藍色顏料;C.I.顏料紫1、14、19、23、29、32、33、36、37、38等紫色顏料; C.I.顏料綠7、10、15、25、36、47、58等綠色顏料;C.I.顏料棕23、25等棕色顏料;C.I.顏料黑1、7等黑色顏料等。 Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI Pigment Violet 1, 14, 19, 23 , 29, 32, 33, 36, 37, 38 and other purple pigments; C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58 and other green pigments; C.I. Pigment Brown 23 and 25 and other brown pigments; C.I. Pigment Black 1, 7 and other black pigments.
顏料(P)較佳為酞菁顏料,更佳為選自由鹵化銅酞菁顏料及鹵化鋅酞菁顏料所組成之群中之至少一種,進而較佳為選自由C.I.顏料綠7、36及58所組成之群中之至少一種。該等顏料可較佳地用於綠色色素,藉由含有上述顏料,而容易實現透射光譜之最佳化,使彩色濾光片之耐光性及耐化學品性變得良好。 The pigment (P) is preferably a phthalocyanine pigment, more preferably at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment, and further preferably selected from CI Pigment Green 7, 36, and 58 At least one of the groups formed. These pigments can be preferably used for green pigments. By containing the pigments described above, it is easy to optimize the transmission spectrum, so that the light resistance and chemical resistance of the color filter become good.
顏料視需要亦可實施松香處理、使用導入有酸性基或鹼性基之顏料衍生物等之表面處理、利用高分子化合物等對顏料表面進行之接枝處理、利用硫酸微粒化法等之微粒化處理、或用以去除雜質之利用有機溶劑或水等之清洗處理、離子性雜質之利用離子交換法等之去除處理等。顏料之粒徑較佳為分別均勻。 If necessary, the pigment may be subjected to rosin treatment, surface treatment using pigment derivatives introduced with an acidic group or a basic group, grafting treatment of the pigment surface with a polymer compound, etc., and micronization by a sulfuric acid micronization method, etc. Treatment, or cleaning treatment using organic solvents or water to remove impurities, removal treatment using ionic exchange methods, etc. for ionic impurities. The particle diameters of the pigments are preferably each uniform.
顏料藉由含有顏料分散劑而進行分散處理,可製成於顏料分散劑溶液中均勻地分散之狀態之顏料分散液。顏料可分別單獨進行分散處理,亦可將複數種混合進行分散處理。 The pigment is subjected to a dispersion treatment by containing a pigment dispersant, and can be made into a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the pigment dispersant solution. The pigment may be separately dispersed, or a plurality of pigments may be mixed and dispersed.
作為上述顏料分散劑,例如可列舉:陽離子系、陰離子系、非離子系、兩性、聚酯系、聚胺系、丙烯酸系等顏料分散劑等。該等顏料分散劑可單獨使用,亦可組合2種以上使用。作為顏料分散劑,按照商品名可列舉:KP(信越化學工業股份有限公司製造)、Flowlen(共榮社化學股份有限公司製造)、Solsperse(Zeneca股份有限公司製造)、EFKA(CIBA公司製造)、Ajisper(Ajinomoto Fine-Techno股份有限公司製造)、Disperbyk(BYK-Chemie公司製造)等。 Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more. Examples of pigment dispersants include KP (made by Shin-Etsu Chemical Industry Co., Ltd.), Flowlen (made by Kyoeisha Chemical Co., Ltd.), Solsperse (made by Zeneca Co., Ltd.), EFKA (made by CIBA), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), and the like.
於使用顏料分散劑之情形時,其使用量相對於顏料100質量份,較佳為100質量份以下,更佳為5質量份以上且50質量份以下。若顏料分散劑之使用量在上述範圍內,則有可獲得分散狀態更均勻之顏料分 散液之傾向。 When a pigment dispersant is used, its use amount is preferably 100 parts by mass or less with respect to 100 parts by mass of the pigment, and more preferably 5 parts by mass or more and 50 parts by mass or less. If the amount of the pigment dispersant is within the above range, it is possible to obtain a pigment component with a more uniform dispersion state. The tendency to spit.
化合物(1)之含有率相對於著色劑(A)之總量,較佳為0.01質量%以上且90質量%以下,更佳為0.1質量%以上且80質量%以下,進而較佳為1質量%以上且65質量%以下,進而更佳為2質量%以上且60質量%以下。 The content rate of the compound (1) with respect to the total amount of the colorant (A) is preferably 0.01 mass% or more and 90 mass% or less, more preferably 0.1 mass% or more and 80 mass% or less, and further preferably 1 mass % To 65% by mass, and more preferably 2% to 60% by mass.
於含有顏料(P)之情形時,其含有率相對於著色劑(A)之總量,較佳為10質量%以上且99.99質量%以下,更佳為20質量%以上且99.9質量%以下,進而較佳為35質量%以上且99質量%以下,進而更佳為40質量%以上且98質量%以下。 When the pigment (P) is contained, its content rate is preferably 10% by mass or more and 99.99% by mass or less, more preferably 20% by mass or more and 99.9% by mass or less with respect to the total amount of the colorant (A). It is more preferably 35 mass% or more and 99 mass% or less, and still more preferably 40 mass% or more and 98 mass% or less.
著色劑(A)之含有率相對於固形物成分之總量,通常為1質量%以上且99質量%以下,較佳為2質量%以上且90質量%以下,更佳為3質量%以上且80質量%以下,進而較佳為5質量%以上且70質量%以下,進而更佳為5質量%以上且60質量%以下,尤佳為5質量%以上且50質量%以下。若著色劑(A)之含有率在上述範圍內,則可獲得所期望之分光或色濃度。 The content of the colorant (A) is usually 1% by mass or more and 99% by mass or less, preferably 2% by mass or more and 90% by mass or less, more preferably 3% by mass or more with respect to the total amount of the solid components. 80 mass% or less, more preferably 5 mass% or more and 70 mass% or less, still more preferably 5 mass% or more and 60 mass% or less, even more preferably 5 mass% or more and 50 mass% or less. When the content of the colorant (A) is within the above range, a desired spectroscopic or color density can be obtained.
於本說明書中,所謂「固形物成分之總量」係指自本發明之著色硬化性樹脂組合物去除溶劑(E)後之成分之合計量。固形物成分之總量及各成分相對於其之含量例如可利用液相層析法或氣相層析法等公知之分析方法而測定。 As used herein, the "total amount of solid components" refers to the total amount of components after the solvent (E) is removed from the colored curable resin composition of the present invention. The total amount of the solid component and the content of each component with respect to the solid component can be measured by a known analysis method such as liquid chromatography or gas chromatography.
樹脂(B)並無特別限定,較佳為鹼可溶性樹脂,更佳為具有源自選自由不飽和羧酸及不飽和羧酸酐所組成之群中之至少一種之結構單元之加成聚合物。作為此種樹脂,可列舉以下之樹脂[K1]~[K6]等。 The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably an addition polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. Examples of such resins include the following resins [K1] to [K6].
樹脂[K1]選自由不飽和羧酸及不飽和羧酸酐所組成之群中之至少一種(a)(以下有時稱為「(a)」)、與具有碳數2~4之環狀醚結構與乙烯性不飽和鍵之單體(b)(以下有時稱為「(b)」)之共聚物; 樹脂[K2](a)、(b)、及可與(a)共聚合之單體(c)(其中,(a)及(b)不同)(以下有時稱為「(c)」)之共聚物;樹脂[K3](a)與(c)之共聚物;樹脂[K4]使(b)與(a)及(c)之共聚物反應而成之樹脂;樹脂[K5]使(a)與(b)及(c)之共聚物反應而成之樹脂;樹脂[K6]使(a)與(b)及(c)之共聚物反應,進而與羧酸酐反應而成之樹脂。 Resin [K1] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)"), and a cyclic ether having 2 to 4 carbon atoms A copolymer of a monomer (b) (hereinafter sometimes referred to as "(b)") having a structure and an ethylenically unsaturated bond; Resin [K2] (a), (b), and monomer (c) copolymerizable with (a) (wherein (a) and (b) are different) (hereinafter sometimes referred to as "(c)") Copolymers of resins; copolymers of resins [K3] (a) and (c); resins [K4] resins made by reacting (b) with copolymers of (a) and (c); resins [K5] make ( a) Resin formed by reacting with copolymers of (b) and (c); Resin [K6] is a resin formed by reacting (a) with copolymers of (b) and (c) and then reacting with carboxylic anhydride.
作為(a),具體而言,例如可列舉:丙烯酸、甲基丙烯酸、丁烯酸、鄰、間、對乙烯基苯甲酸等不飽和單羧酸類;順丁烯二酸、反丁烯二酸、檸康酸、中康酸、伊康酸、3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲基四氫鄰苯二甲酸、1,4-環己烯二羧酸等不飽和二羧酸類;甲基-5-降烯-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯等含有羧基之雙環不飽和化合物類;順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯酐等不飽和二羧酸類酐;琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等2價以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯類;如α-(羥基甲基)丙烯酸之於同一分子中含有羥基及羧基之不飽和丙烯酸酯類等。 於該等中,就共聚合反應性之方面或所獲得之樹脂於鹼性水溶液中之溶解性之方面而言,較佳為丙烯酸、甲基丙烯酸及順丁烯二酸酐。 Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, o-, m-, and p-vinylbenzoic acid; maleic acid and fumaric acid , Citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, Unsaturated dicarboxylic acids such as 3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid; methyl-5-decane Ene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methyl Dicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2 -Ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl Phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride; succinic acid mono [2- (meth) acrylic acid ethoxyethyl Unsaturated mono [(meth) acrylic alkoxyalkyl] esters of polyvalent carboxylic acids, such as poly] carboxylic acid esters, mono [2- (meth) acryloxyethyl] phthalates, and the like ; For example, α- (hydroxymethyl) acrylic unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule. Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable in terms of the copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.
(b)為具有碳數2~4之環狀醚結構(例如選自由環氧乙烷環、氧雜環丁烷環及四氫呋喃環所組成之群中之至少1種)與乙烯性不飽和鍵之聚合性化合物。(b)較佳為具有碳數2~4之環狀醚與(甲基)丙烯醯氧基之單體。 (b) a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Polymerizable compound. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group is preferred.
再者,於本說明書中,所謂「(甲基)丙烯酸」係表示選自由丙烯酸及甲基丙烯酸所組成之群中之至少1種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等之記法亦具有相同之含義。 In addition, in this specification, "(meth) acrylic acid" means at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. The terms "(meth) acrylfluorenyl" and "(meth) acrylate" also have the same meaning.
作為(b),例如可列舉:具有環氧乙基與乙烯性不飽和鍵之單體(b1)(以下有時稱為「(b1)」)、具有氧雜環丁基與乙烯性不飽和鍵之單體(b2)(以下有時稱為「(b2)」)、具有四氫呋喃基與乙烯性不飽和鍵之單體(b3)(以下有時稱為「(b3)」)等。 Examples of (b) include a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxetanyl group and an ethylenic unsaturated group. A monomer (b2) (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.
作為(b1),例如可列舉:具有直鏈狀或支鏈狀之脂肪族不飽和烴經環氧化之結構之單體(b1-1)(以下有時稱為「(b1-1)」)、具有脂環式不飽和烴經環氧化之結構之單體(b1-2)(以下有時稱為「(b1-2)」)。 Examples of (b1) include a monomer (b1-1) (hereinafter referred to as "(b1-1)") having an epoxidized structure of a linear or branched aliphatic unsaturated hydrocarbon. A monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter sometimes referred to as "(b1-2)").
作為(b1-1),可列舉:(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸β-甲基縮水甘油酯、(甲基)丙烯酸β-乙基縮水甘油酯、縮水甘油基乙烯醚、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、α-甲基-鄰乙烯基苄基縮水甘油醚、α-甲基-間乙烯基苄基縮水甘油醚、α-甲基-對乙烯基苄基縮水甘油醚、2,3-雙(縮水甘油氧基甲基)苯乙烯、2,4-雙(縮水甘油氧基甲基)苯乙烯、2,5-雙(縮水甘油氧基甲基)苯乙烯、2,6-雙(縮水甘油氧基甲基)苯乙烯、2,3,4-三(縮水甘油氧基甲基)苯乙烯、2,3,5-三(縮水甘油氧基甲基)苯乙烯、2,3,6-三(縮水甘油氧基甲基)苯乙烯、3,4,5-三(縮水甘油氧基甲基)苯 乙烯、2,4,6-三(縮水甘油氧基甲基)苯乙烯等。 Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. , O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinyl Benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) benzene Ethylene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) benzene Ethylene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxy) (Methyl) benzene Ethylene, 2,4,6-tris (glycidyloxymethyl) styrene, etc.
作為(b1-2),可列舉:一氧化乙烯基環己烯、1,2-環氧-4-乙烯基環己烷、(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸3,4-環氧環己基甲酯(例如,Cyclomer M100;Daicel股份有限公司製造)、式(I)所表示之化合物及式(II)所表示之化合物等。 Examples of (b1-2) include vinyl cyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexyl methyl (meth) acrylate, ( 3,4-epoxycyclohexyl methyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), a compound represented by formula (I), a compound represented by formula (II), and the like.
[式(I)及式(II)中,Ra及Rb表示氫原子、或碳數1~4之烷基,該烷基所含之氫原子亦可經羥基取代。 [In formulae (I) and (II), R a and R b 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 hydroxyl group.
Xa及Xb表示單鍵、-Rc-、*-Rc-O-、*-Rc-S-或*-Rc-NH-。 X a and X b represents a single bond, -R c -, * - R c -O -, * - R c -S- or * -R c -NH-.
Rc表示碳數1~6之烷二基。 R c represents an alkanediyl group having 1 to 6 carbon atoms.
*表示與O之鍵結鍵。] * Indicates bonding with O. ]
作為碳數1~4之烷基,可列舉:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, and third butyl.
作為氫原子經羥基取代之烷基,可列舉:羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥基丁基、2-羥基丁基、3-羥基丁基、4-羥基丁基等。 Examples of the hydroxy-substituted alkyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxyl. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.
作為Ra及Rb,較佳為列舉氫原子、甲基、羥基甲基、1-羥基乙基及2-羥基乙基,更佳為列舉氫原子及甲基。 R a and R b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.
作為烷二基,可列舉:亞甲基、伸乙基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基等。 Examples of the alkanediyl group include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5. -Diyl, hexane-1,6-diyl and the like.
作為Xa及Xb,較佳為列舉:單鍵、亞甲基、伸乙基、*-CH2-O- 及*-CH2CH2-O-,更佳為列舉單鍵及*-CH2CH2-O-(*表示與O之鍵結鍵)。 As X a and X b , a single bond, methylene, ethylidene, * -CH 2 -O- and * -CH 2 CH 2 -O- are preferred, and a single bond and *-are more preferred. CH 2 CH 2 -O- (* indicates a bond with O).
作為式(I)所表示之化合物,可列舉式(I-1)~式(I-15)中之任一者所表示之化合物等。其中,較佳為式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)或式(I-11)~式(I-15)所表示之化合物,更佳為式(I-1)、式(I-7)、式(I-9)或式(I-15)所表示之化合物。 Examples of the compound represented by the formula (I) include compounds represented by any one of the formulae (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I) are preferred. The compound represented by -15) is more preferably a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).
作為式(II)所表示之化合物,可列舉式(II-1)~式(II-15)中之任一者所表示之化合物等。其中,較佳為式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)或式(II-11)~式(II-15)所表示之化合物,更佳為式(II-1)、式(II-7)、式(II-9)或式(II-15)所表示之化合物。 Examples of the compound represented by the formula (II) include compounds represented by any one of the formulae (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11) to formula (II) are preferred. The compound represented by -15) is more preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).
式(I)所表示之化合物及式(II)所表示之化合物可分別單獨使用,亦可將式(I)所表示之化合物與式(II)所表示之化合物併用。於將該等併用之情形時,式(I)所表示之化合物及式(II)所表示之化合物之含有比率以莫耳基準計較佳為5:95~95:5,更佳為10:90~90:10,進而較佳為20:80~80:20。 The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone, or the compound represented by the formula (I) and the compound represented by the formula (II) may be used in combination. When these are used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 on a Moore basis. ~ 90: 10, more preferably 20: 80 ~ 80: 20.
作為(b2),更佳為具有氧雜環丁基與(甲基)丙烯醯氧基之單體。作為(b2),可列舉:3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-丙烯醯氧基乙基氧雜環丁烷等。 As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-propenemethyloxetane, 3-methyl-3-methacryloxy Ethylethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, 3 -Ethyl-3-propenyloxyethyloxetane and the like.
作為(b3),更佳為具有四氫呋喃基與(甲基)丙烯醯氧基之單體。作為(b3),具體而言,可列舉:丙烯酸四氫糠酯(例如,Viscoat V#150,大阪有機化學工業股份有限公司製造)、甲基丙烯酸四氫糠酯 等。 As (b3), a monomer having a tetrahydrofuranyl group and a (meth) acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and tetrahydrofurfuryl methacrylate. Wait.
作為(b),就可進一步提高所獲得之彩色濾光片之耐熱性、耐化學品性等可靠性之方面而言,較佳為(b1)。進而,就著色硬化性樹脂組合物之保存穩定性優異之方面而言,更佳為(b1-2)。 As (b), (b1) is preferable in terms of further improving the reliability such as heat resistance and chemical resistance of the obtained color filter. Furthermore, (b1-2) is more preferable at the point which is excellent in the storage stability of a coloring curable resin composition.
作為(c),例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02.6]癸烷-8-酯(於該技術領域中,作為慣用名,稱為「(甲基)丙烯酸二環戊酯」。又,有時稱為「(甲基)丙烯酸三環癸酯」)、(甲基)丙烯酸三環[5.2.1.02.6]癸烯-8-酯(於該技術領域中,作為慣用名,稱為「(甲基)丙烯酸二環戊烯酯」)、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯類;(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等含有羥基之(甲基)丙烯酸酯類;順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等二羧酸二酯;雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2- 烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物類;N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-丁二醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-丁二醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-丁二醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順丁烯二醯亞胺等二羰基醯亞胺衍生物類;苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and Tributyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic ring Amyl ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2.6 ] decane-8-ester (in the technical field As a common name, it is called "dicyclopentyl (meth) acrylate". It is also sometimes called "tricyclodecyl (meth) acrylate", and tricyclo (meth) acrylate [5.2.1.0 2.6 ] Decene-8-ester (in this technical field, as a common name, "dicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate, (methyl Acrylic iso Ester, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) acrylic acid (Meth) acrylates such as benzyl esters; (meth) acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; maleic acid di Dicarboxylic acid diesters such as ethyl acetate, diethyl fumarate, diethyl iconate; 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-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6 -Bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxy Bicyclo [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 Ene, 5-hydroxymethyl-5- Dicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene Ene, 5-phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (third butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (Cyclohexyloxycarbonyl) Bicyclic unsaturated compounds such as bicyclo [2.2.1] hept-2-ene; N-phenylcis-butenedifluorene imine, N-cyclohexylcisbutenedifluorene, N -Benzyl cis-butene diimide, N- succinimide imide 3-cis-butene diimide benzoate, N-butanimide-imino-4- cis butadiene Iminobutyrate, N-butanebiimino-6-cisbutenediamidohexanoate, N-butadiamidoimino-3-cisbutanediiminopropionate, N- (9-acridyl) cis-butene difluorenimide and other dicarbonylfluorenimine derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl Toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene Ene, 2,3-dimethyl-1,3-butadiene and the like.
於該等中,就共聚合反應性及耐熱性之方面而言,較佳為苯乙烯、乙烯基甲苯、(甲基)丙烯酸苄酯、(甲基)丙烯酸三環[5.2.1.02.6]癸烷-8-酯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、雙環[2.2.1]庚-2-烯等。 Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth) acrylate, and tricyclic (meth) acrylate [5.2.1.0 2.6 ] decane are preferred. Alk-8-ester, N-phenylcis-butenedifluoreneimine, N-cyclohexylcisbutenedifluoreneimine, N-benzylcisbutenedifluoreneimine, bicyclo [2.2.1] heptane- 2-ene and so on.
於樹脂[K1]中,源自各者之結構單元之比率較佳為於構成樹脂[K1]之全部結構單元中,源自(a)之結構單元:2~60莫耳%源自(b)之結構單元:40~98莫耳%,更佳為源自(a)之結構單元:10~50莫耳%源自(b)之結構單元:50~90莫耳%。 In the resin [K1], the ratio of the structural unit derived from each is preferably the structural unit derived from (a) among all the structural units constituting the resin [K1]: 2 to 60 mol% derived from (b ) Structural unit: 40 ~ 98 mol%, more preferably the structural unit derived from (a): 10 ~ 50 mol% structural unit derived from (b): 50 ~ 90 mol%.
若樹脂[K1]之結構單元之比率在上述範圍內,則有著色硬化性樹脂組合物之保存穩定性、形成著色圖案時之顯影性、及所獲得之彩色 濾光片之耐溶劑性優異之傾向。 When the ratio of the structural unit of the resin [K1] is within the above range, there are storage stability of the colored curable resin composition, developability when a colored pattern is formed, and obtained color The filter tends to have excellent solvent resistance.
樹脂[K1]例如可參考文獻「高分子合成之實驗法」(大津隆行著,發行社:化學同人股份有限公司,第1版第1刷,1972年3月1日發行)中記載之方法及該文獻中記載之引用文獻而製造。 The resin [K1] can be referred to, for example, the method described in the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki, Issuer: Chemical Dojin Co., Ltd., 1st Edition, 1st Brush, March 1, 1972) and It is manufactured by citing documents described in this document.
具體而言,可列舉如下方法:將(a)及(b)之特定量、聚合起始劑及溶劑等添加至反應容器中,例如藉由利用氮氣置換氧氣而形成脫氧環境,一面攪拌一面加熱及保溫。再者,此處所使用之聚合起始劑及溶劑等並無特別限定,可使用該領域中通常使用者。例如,作為聚合起始劑,可列舉:偶氮化合物(2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)等)或有機過氧化物(過氧化苯甲醯基等),作為溶劑,只要為使各單體溶解者即可,可列舉下文中作為本發明之著色硬化性樹脂組合物之溶劑(E)所列舉之溶劑等。 Specifically, the following methods can be cited: adding a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like to a reaction vessel, for example, forming a deoxidizing environment by replacing oxygen with nitrogen, and heating while stirring And insulation. The polymerization initiator, solvent, and the like used herein are not particularly limited, and ordinary users in the field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or organic compounds. The solvent (such as benzamyl peroxide) may be any solvent as long as it dissolves each monomer. Examples of the solvent include solvents listed below as the solvent (E) of the coloring curable resin composition of the present invention. Wait.
再者,所獲得之共聚物可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,還可使用利用再沈澱等方法而以固體(粉體)之形式取出者。尤其於該聚合時,藉由使用本發明之著色硬化性樹脂組合物中所含之溶劑作為溶劑,可將反應後之溶液直接使用於本發明之著色硬化性樹脂組合物之製備,故而可簡化本發明之著色硬化性樹脂組合物之製造步驟。 In addition, the obtained copolymer may be used directly after the reaction, or may be a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. Especially during the polymerization, by using the solvent contained in the colored curable resin composition of the present invention as a solvent, the solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention, so that it can be simplified. The manufacturing process of the coloring curable resin composition of this invention.
於樹脂[K2]中,源自各者之結構單元之比率較佳為於構成樹脂[K2]之全部結構單元中,源自(a)之結構單元:2~45莫耳%源自(b)之結構單元:2~95莫耳%源自(c)之結構單元:1~65莫耳%,更佳為源自(a)之結構單元:5~40莫耳%源自(b)之結構單元:5~80莫耳%源自(c)之結構單元:5~60莫耳%。 In the resin [K2], the ratio of the structural unit derived from each is preferably the structural unit derived from (a) among all the structural units constituting the resin [K2]: 2 to 45 mol% derived from (b ) Structural unit: 2 ~ 95 mole% from (c) structural unit: 1 ~ 65 mole%, more preferably from (a) structural unit: 5 ~ 40 mole% from (b) Structural unit: 5 ~ 80 mole% Structural unit derived from (c): 5 ~ 60 mole%.
若樹脂[K2]之結構單元之比率在上述範圍內,則有著色硬化性樹脂組合物之保存穩定性、形成著色圖案時之顯影性、及所獲得之彩色濾光片之耐溶劑性、耐熱性及機械強度優異之傾向。 When the ratio of the structural unit of the resin [K2] is within the above range, there are storage stability of the colored curable resin composition, developability when a colored pattern is formed, and solvent resistance and heat resistance of the obtained color filter It tends to have excellent properties and mechanical strength.
樹脂[K2]例如可與作為樹脂[K1]之製造方法而記載之方法同樣地製造。 The resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1], for example.
於樹脂[K3]中,源自各者之結構單元之比率較佳為於構成樹脂[K3]之全部結構單元中,源自(a)之結構單元:2~60莫耳%源自(c)之結構單元:40~98莫耳%,更佳為源自(a)之結構單元:10~50莫耳%源自(c)之結構單元:50~90莫耳%。 In the resin [K3], the ratio of the structural unit derived from each is preferably the structural unit derived from (a) among all the structural units constituting the resin [K3]: 2 to 60 mol% derived from (c ) Structural unit: 40 ~ 98 mol%, more preferably the structural unit derived from (a): 10 ~ 50 mol% structural unit derived from (c): 50 ~ 90 mol%.
樹脂[K3]例如可與作為樹脂[K1]之製造方法而記載之方法同樣地製造。 The resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1], for example.
樹脂[K4]可藉由獲得(a)與(c)之共聚物,且使(b)具有之碳數2~4之環狀醚加成於(a)具有之羧酸及/或羧酸酐而製造。 The resin [K4] can be obtained by copolymerizing (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid and / or carboxylic acid anhydride in (a). While manufacturing.
首先,與作為樹脂[K1]之製造方法而記載之方法同樣地製造(a)與(c)之共聚物。於此情形時,源自各者之結構單元之比率較佳為與樹脂[K3]中所列舉者相同。 First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as those listed in the resin [K3].
其次,使(b)具有之碳數2~4之環狀醚與上述共聚物中之源自(a)之羧酸及/或羧酸酐之一部分反應。 Next, the cyclic ether having a carbon number of 2 to 4 in (b) is reacted with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer.
繼(a)與(c)之共聚物之製造之後,將燒瓶內環境由氮氣置換成空氣,將(b)、羧酸或羧酸酐與環狀醚之反應觸媒(例如三(二甲基胺基甲基)苯酚等)及聚合抑制劑(例如對苯二酚等)等添加至燒瓶內,例如於60~130℃下反應1~10小時,藉此可製造樹脂[K4]。 Following the manufacture of the copolymer of (a) and (c), the environment in the flask is replaced by nitrogen with air, and the reaction catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (such as tris (dimethyl) Aminomethyl) phenol, etc.) and polymerization inhibitors (such as hydroquinone, etc.) are added to the flask, and reacted at, for example, 60 to 130 ° C for 1 to 10 hours, thereby producing a resin [K4].
(b)之使用量相對於(a)100莫耳,較佳為5~80莫耳,更佳為10~75莫耳。藉由設為該範圍,而有著色硬化性樹脂組合物之保存穩定 性、形成圖案時之顯影性、及所獲得之圖案之耐溶劑性、耐熱性、機械強度及感度之平衡變得良好之傾向。由於環狀醚之反應性較高,未反應之(b)不易殘留,故而作為樹脂[K4]中使用之(b),較佳為(b1),進而較佳為(b1-1)。 The amount of (b) used is preferably 5 to 80 mols, and more preferably 10 to 75 mols relative to (a) 100 mols. By setting it as this range, the storage stability of the colored curable resin composition is stable The balance of the properties, the developability during pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good. Since the cyclic ether has high reactivity and unreacted (b) does not easily remain, the (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1).
上述反應觸媒之使用量相對於(a)、(b)及(c)之合計量100質量份,較佳為0.001~5質量份。上述聚合抑制劑之使用量相對於(a)、(b)及(c)之合計量100質量份,較佳為0.001~5質量份。 The used amount of the reaction catalyst is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c). The used amount of the polymerization inhibitor is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c).
添加方法、反應溫度及時間等反應條件可考慮製造設備或聚合所引起之發熱量等而適當調整。再者,可與聚合條件同樣地,考慮製造設備或聚合所引起之發熱量等而適當調整添加方法或反應溫度。 The reaction conditions such as the addition method, reaction temperature, and time can be appropriately adjusted in consideration of the amount of heat generated by the manufacturing equipment or polymerization. In addition, the addition method and reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the manufacturing equipment or polymerization, as with the polymerization conditions.
關於樹脂[K5],作為第一階段,以與上述樹脂[K1]之製造方法相同之方式獲得(b)與(c)之共聚物。與上述同樣地,所獲得之共聚物可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,還可使用利用再沈澱等方法而以固體(粉體)之形式取出者。 As for the resin [K5], as the first stage, the copolymers of (b) and (c) were obtained in the same manner as the method for producing the above-mentioned resin [K1]. In the same manner as above, the obtained copolymer may be used directly after the reaction, or may be a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation.
源自(b)及(c)之結構單元之比率較佳為相對於構成上述共聚物之全部結構單元之合計莫耳數,分別為源自(b)之結構單元:5~95莫耳%源自(c)之結構單元:5~95莫耳%,更佳為源自(b)之結構單元:10~90莫耳%源自(c)之結構單元:10~90莫耳%。 The ratio of the structural units derived from (b) and (c) is preferably relative to the total number of moles of all the structural units constituting the above copolymer, which are the structural units derived from (b): 5 ~ 95 mole% Structural unit derived from (c): 5 ~ 95 mole%, more preferably structural unit derived from (b): 10 ~ 90 mole% structural unit derived from (c): 10 ~ 90 mole%.
進而,以與樹脂[K4]之製造方法相同之條件,使(a)具有之羧酸或羧酸酐、與(b)及(c)之共聚物具有之源自(b)之環狀醚反應,藉此可獲得樹脂[K5]。 Furthermore, under the same conditions as in the method for producing the resin [K4], the carboxylic acid or carboxylic anhydride possessed by (a) and the cyclic ether derived from (b) possessed by the copolymer of (b) and (c) were reacted. In this way, a resin [K5] can be obtained.
與上述共聚物反應之(a)之使用量相對於(b)100莫耳,較佳為5~80莫耳。由於環狀醚之反應性較高,未反應之(b)不易殘留,故而作為樹脂[K5]中使用之(b),較佳為(b1),進而較佳為(b1-1)。 The amount of (a) used in the reaction with the copolymer is preferably 5 to 80 moles relative to (b) 100 moles. Since the cyclic ether has high reactivity and unreacted (b) is difficult to remain, (b) used as the resin [K5] is preferably (b1), and more preferably (b1-1).
樹脂[K6]為進而使羧酸酐與樹脂[K5]反應而成之樹脂。使羧酸酐與藉由環狀醚與羧酸或羧酸酐之反應而產生之羥基反應。 The resin [K6] is a resin obtained by further reacting a carboxylic anhydride with a resin [K5]. The carboxylic acid anhydride is reacted with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.
作為羧酸酐,可列舉:順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯酐等。羧酸酐之使用量相對於(a)之使用量1莫耳,較佳為0.5~1莫耳。 Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetraphthalic anhydride Hydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2- Ene anhydride, etc. The amount of carboxylic acid anhydride used is 1 mole, preferably 0.5 to 1 mole, relative to the amount of (a).
作為樹脂(B),具體而言,可列舉:(甲基)丙烯酸3,4-環氧環己基甲酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯/(甲基)丙烯酸共聚物等樹脂[K1];(甲基)丙烯酸縮水甘油酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸縮水甘油酯/苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯/(甲基)丙烯酸/N-環己基順丁烯二醯亞胺共聚物、(甲基)丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯/(甲基)丙烯酸/乙烯基甲苯共聚物、3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷/(甲基)丙烯酸/苯乙烯共聚物等樹脂[K2];(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸苄酯/(甲基)丙烯酸三環癸酯/(甲基)丙烯酸共聚物等樹脂[K3];使(甲基)丙烯酸縮水甘油酯加成於(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物而成之樹脂、使(甲基)丙烯酸縮水甘油酯加成於(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物而成之樹脂、使(甲基)丙烯酸縮水甘油酯加成於(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物而成之樹脂等樹脂[K4];使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯之共聚物反應而成之樹脂、使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸縮水甘油酯之共聚物反應而成之樹脂等樹脂[K5];使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯之共聚物反應而成之樹 脂進而與四氫鄰苯二甲酸酐反應而獲得之樹脂等樹脂[K6]等。 Specific examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic copolymer, and 3,4-epoxy tricyclic (meth) acrylate. [5.2.1.0 2.6 ] resins such as decyl ester / (meth) acrylic copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) ) Glycidyl acrylate / styrene / (meth) acrylic copolymer, 3,4-epoxy tricyclic (meth) acrylate [5.2.1.0 2.6 ] decyl ester / (meth) acrylic acid / N-cyclohexylcis Butene difluorene imine copolymer, 3,4-epoxy tricyclic (meth) acrylic acid [5.2.1.0 2.6 ] decyl / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- Resins such as (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymers [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymers, styrene / (Meth) acrylic copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic copolymer and other resins [K3]; add glycidyl (meth) acrylate Resin made from benzyl (meth) acrylate / (meth) acrylic copolymer, Glycidyl acrylate is added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, and glycidyl (meth) acrylate is added to (meth) Tricyclodecyl acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer resin [K4]; (meth) acrylic acid and tricyclodecyl (meth) acrylate / (formaldehyde) A resin obtained by reacting a copolymer of glycidyl acrylate and a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin and other resins [K5]; a resin obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and further reacting with tetrahydrophthalic anhydride The obtained resin [K6] and the like.
樹脂(B)較佳為選自由樹脂[K1]、樹脂[K2]及樹脂[K3]所組成之群中之一種,更佳為選自由樹脂[K2]及樹脂[K3]所組成之群中之一種。若為該等樹脂,則著色硬化性樹脂組合物之顯影性優異。就著色圖案與基板之密接性之觀點而言,進而較佳為樹脂[K2]。 The resin (B) is preferably selected from the group consisting of the resin [K1], the resin [K2], and the resin [K3], and more preferably selected from the group consisting of the resin [K2] and the resin [K3] One kind. With these resins, the developability of the colored curable resin composition is excellent. From the viewpoint of adhesion between the colored pattern and the substrate, the resin [K2] is more preferable.
樹脂(B)之聚苯乙烯換算之重量平均分子量通常為3,000~100,000,較佳為5,000~50,000,更佳為5,000~35,000,進而較佳為5,000~30,000,尤佳為6,000~30,000。若分子量在上述範圍內,則有如下傾向:塗膜硬度提高,殘膜率亦較高,未曝光部對於顯影液之溶解性良好,著色圖案之解像度提高。 The polystyrene equivalent weight average molecular weight of the resin (B) is usually 3,000 to 100,000, preferably 5,000 to 50,000, more preferably 5,000 to 35,000, still more preferably 5,000 to 30,000, and even more preferably 6,000 to 30,000. When the molecular weight is within the above range, there is a tendency that the hardness of the coating film is increased, the residual film ratio is also high, the solubility of the unexposed portion to the developing solution is good, and the resolution of the colored pattern is improved.
樹脂(B)之分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.1~6,更佳為1.2~4。 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.
樹脂(B)之酸值通常為20mg-KOH/g~170mg-KOH/g,較佳為30mg-KOH/g~170mg-KOH/g,更佳為40mg-KOH/g~170mg-KOH/g,進而較佳為50mg-KOH/g~170mg-KOH/g。其中,較佳為50mg-KOH/g~150mg-KOH/g,更佳為60mg-KOH/g~150mg-KOH/g,進而較佳為60mg-KOH/g~135mg-KOH/g,尤佳為70mg-KOH/g~135mg-KOH/g。此處,酸值係指作為中和樹脂(B)1g所需之氫氧化鉀之量(mg)而測定之值,例如可藉由使用氫氧化鉀水溶液滴定而求出。 The acid value of the resin (B) is usually 20mg-KOH / g ~ 170mg-KOH / g, preferably 30mg-KOH / g ~ 170mg-KOH / g, more preferably 40mg-KOH / g ~ 170mg-KOH / g , And more preferably 50 mg-KOH / g to 170 mg-KOH / g. Among them, 50 mg-KOH / g to 150 mg-KOH / g is preferred, 60 mg-KOH / g to 150 mg-KOH / g is more preferred, and 60 mg-KOH / g to 135 mg-KOH / g is more preferred, and particularly preferred It is 70mg-KOH / g ~ 135mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and it can be obtained by, for example, titration with an aqueous potassium hydroxide solution.
樹脂(B)之含量相對於固形物成分之總量,較佳為7質量%~65質量%,更佳為10質量%~60質量%,進而較佳為13質量%~60質量%,尤佳為17質量%~55質量%。若樹脂(B)之含量在上述範圍內,則有容易形成著色圖案,又,著色圖案之解像度及殘膜率提高之傾向。 The content of the resin (B) is preferably 7 mass% to 65 mass%, more preferably 10 mass% to 60 mass%, and further preferably 13 mass% to 60 mass%, particularly preferably It is preferably 17% by mass to 55% by mass. When the content of the resin (B) is within the above range, a colored pattern tends to be easily formed, and the resolution and residual film rate of the colored pattern tend to increase.
聚合性化合物(C)為可藉由自聚合起始劑(D)產生之活性自由基及/或酸而聚合之化合物,例如可列舉聚合性之具有乙烯性不飽和鍵之 化合物等,較佳為(甲基)丙烯酸酯化合物。 The polymerizable compound (C) is a compound that can be polymerized by living radicals and / or acids generated from the polymerization initiator (D), and examples thereof include polymerizable compounds having an ethylenically unsaturated bond. The compound or the like is preferably a (meth) acrylate compound.
作為具有1個乙烯性不飽和鍵之聚合性化合物,例如可列舉:壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙酯、N-乙烯基吡咯啶酮等;及上述(a)、(a)及(c)。 Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexylcarbitol acrylic acid. Esters, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like; and (a), (a), and (c) above.
作為具有2個乙烯性不飽和鍵之聚合性化合物,例如可列舉:1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、雙酚A之雙(丙烯醯氧基乙基)醚、3-甲基戊二醇二(甲基)丙烯酸酯等。 Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, and neopentyl glycol di ( (Meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.
其中,聚合性化合物(C)較佳為具有3個以上之乙烯性不飽和鍵之聚合性化合物。作為此種聚合性化合物,例如可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、四季戊四醇十(甲基)丙烯酸酯、四季戊四醇九(甲基)丙烯酸酯、三(2-(甲基)丙烯醯氧基乙基)異氰尿酸酯、乙二醇改性季戊四醇四(甲基)丙烯酸酯、乙二醇改性二季戊四醇六(甲基)丙烯酸酯、丙二醇改性季戊四醇四(甲基)丙烯酸酯、丙二醇改性二季戊四醇六(甲基)丙烯酸酯、己內酯改性季戊四醇四(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylic acid. Ester, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nine (meth) acrylate Ester, tris (2- (meth) acryloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylic acid Ester, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa ( (Meth) acrylates and the like.
其中,較佳為二季戊四醇五(甲基)丙烯酸酯及二季戊四醇六(甲基)丙烯酸酯。 Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.
聚合性化合物(C)之重量平均分子量較佳為150以上且2,900以下,更佳為250~1,500以下。 The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.
聚合性化合物(C)之含量相對於固形物成分之總量,較佳為1~70質量%,其中較佳為2~65質量%,其中更佳為5~65質量%,較佳為7 ~65質量%,其中更佳為10~60質量%,更佳為13~60質量%,進而較佳為17~55質量%。 The content of the polymerizable compound (C) is preferably 1 to 70% by mass, and more preferably 2 to 65% by mass, more preferably 5 to 65% by mass, and more preferably 7 to the total amount of solid components. ~ 65 mass%, more preferably 10 to 60 mass%, more preferably 13 to 60 mass%, and still more preferably 17 to 55 mass%.
又,樹脂(B)與聚合性化合物(C)之含量比[樹脂(B):聚合性化合物(C)]以質量基準計,較佳為20:80~80:20,更佳為35:65~80:20。 The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20 on a mass basis, and more preferably 35: 65 ~ 80: 20.
若聚合性化合物(C)之含量在上述範圍內,則有著色圖案形成時之殘膜率及彩色濾光片之耐化學品性提高之傾向。 When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.
聚合起始劑(D)只要為藉由光或熱之作用而產生活性自由基、酸等而可使聚合開始之化合物,則並無特別限定,可使用公知之聚合起始劑。 The polymerization initiator (D) is not particularly limited as long as it is a compound that can start polymerization by generating active radicals, acids, and the like by the action of light or heat, and a known polymerization initiator can be used.
作為聚合起始劑(D),可列舉:苯烷基酮化合物、三化合物、醯基氧化膦化合物、O-醯基肟化合物及聯咪唑化合物等。 Examples of the polymerization initiator (D) include benzoyl ketone compounds, Compounds, fluorenyl phosphine oxide compounds, O-fluorenyl oxime compounds, biimidazole compounds, and the like.
上述O-醯基肟化合物為具有式(d1)所表示之部分結構之化合物。以下,*表示鍵結鍵。 The O-fluorenyl oxime compound is a compound having a partial structure represented by formula (d1). In the following, * indicates a bond key.
作為上述O-醯基肟化合物,例如可列舉:N-苯甲醯氧基-1-(4-苯基硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二烷環戊基甲氧基)苯甲醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧 基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺、N-苯甲醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-酮-2-亞胺等。亦可使用Irgacure OXE01、OXE02(以上為BASF公司製造)、N-1919(ADEKA公司製造)等市售品。其中,O-醯基肟化合物較佳為選自由N-苯甲醯氧基-1-(4-苯基硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺及N-苯甲醯氧基-1-(4-苯基硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺所組成之群中之至少1種,更佳為N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺。 Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-benzidine Oxy-1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) -3- Cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di Alkylcyclopentylmethoxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- (2 -Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- ( 2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (the above are manufactured by BASF), and N-1919 (made by ADEKA) can also be used. Among these, the O-fluorenyl oxime compound is preferably selected from the group consisting of N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-benzidine Oxy-1- (4-phenylthiophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylthiophenyl) -3- At least one of the group consisting of cyclopentylpropane-1-one-2-imine, more preferably N-benzyloxy-1- (4-phenylthiophenyl) octane-1 -Keto-2-imine.
上述苯烷基酮化合物為具有式(d2)所表示之部分結構或式(d3)所表示之部分結構之化合物。該等部分結構中,苯環亦可具有取代基。 The benzoalkyl ketone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.
作為具有式(d2)所表示之部分結構之化合物,例如可列舉:2-甲基-2-啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-啉基苯基)-2-苄基丁烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-啉基)苯基]丁烷-1-酮等。亦可使用Irgacure 369、907、379(以上為BASF公司製造)等市售品。 Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2- Phenyl-1- (4-methylthiophenyl) propane-1-one, 2-dimethylamino-1- (4- Phenylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Phenyl) phenyl] butane-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above manufactured by BASF) can also be used.
作為具有式(d3)所表示之部分結構之化合物,例如可列舉:2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮之低聚物、α,α-二乙氧基苯乙酮、苯偶醯二甲基縮酮等。 Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-hydroxy-2-methyl-1- [4 -(2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1 -Oligomers of ketones, α, α-diethoxyacetophenone, benzophenone dimethyl ketal and the like.
就感度之方面而言,作為苯烷基酮化合物,較佳為具有式(d2)所 表示之部分結構之化合物。 In terms of sensitivity, as the benzoalkyl ketone compound, it is preferable to have a formula (d2) A compound of partial structure indicated.
上述聯咪唑化合物例如為式(d5)所表示之化合物。 The biimidazole compound is, for example, a compound represented by formula (d5).
[式(d5)中,R51~R56表示可具有取代基之碳數6~10之芳基。] [In the formula (d5), R 51 to R 56 represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]
作為碳數6~10之芳基,例如可列舉:苯基、甲苯甲醯基、二甲苯基、乙基苯基及萘基等,較佳為苯基。 Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolylmethyl, xylyl, ethylphenyl, and naphthyl, and phenyl is preferred.
作為取代基,例如可列舉鹵素原子、碳數1~4之烷氧基等。作為鹵素原子,例如可列舉氟原子、氯原子、溴原子、碘原子等,較佳為氯原子。作為碳數1~4之烷氧基,例如可列舉甲氧基、乙氧基、丙氧基、丁氧基等,較佳為甲氧基。 Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A chlorine atom is preferred. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferred.
作為聯咪唑化合物,例如可列舉:2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基聯咪唑(例如參照JPH06-75372-A、JPH06-75373-A號等)、2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(二烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)聯咪唑(例如參照JPS48-38403-B、JPS62-174204-A等)、4,4'5,5'-位之苯基經烷氧羰基(carboalkoxy)取代之咪唑化合物(例如參照JPH07-10913-A等)等。其中,較佳為下述式所表示之化合物及其等之混合物。 Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, refer to JPH06-75372-A, JPH06-75373-A, etc.) Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (alkoxyphenyl) ) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chloro (Phenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (for example, see JPS48-38403-B, JPS62-174204-A, etc.) An imidazole compound in which the phenyl group at the -position is substituted with a carboalkoxy group (for example, refer to JPH07-10913-A). Among them, a compound represented by the following formula and a mixture thereof are preferred.
作為上述三化合物,例如可列舉:2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三等。 As above three Examples of the compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-sunfloweryl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.
作為上述醯基氧化膦化合物,可列舉2,4,6-三甲基苯甲醯基二苯基氧化膦等。 Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylidenediphenylphosphine oxide and the like.
進而,作為聚合起始劑(D),可列舉:安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚等安息香化合物;二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯基硫醚、3,3',4,4'-四(第三丁基過氧基羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等二苯甲酮化合物;9,10-菲醌、2-乙基蒽醌、樟腦醌等醌化合物;10-丁基-2-氯吖啶酮、苯偶醯、苯基乙醛酸甲酯、二茂鈦化合物等。該等較佳為與下述聚合起始助劑(D1)(尤其為胺類)組合使用。 Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and methyl benzophenethylbenzoate , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) di Benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2 -Chloroacridone, benzodiazone, methyl phenylglyoxylate, titanocene compound and the like. These are preferably used in combination with the following polymerization initiation aid (D1) (especially amines).
聚合起始劑(D)較佳為含有選自由苯烷基酮化合物、三化合物、醯基氧化膦化合物、O-醯基肟化合物及聯咪唑化合物所組成之群中之至少一種之聚合起始劑,更佳為含有O-醯基肟化合物之聚合起始 劑。 The polymerization initiator (D) preferably contains a compound selected from the group consisting of The polymerization initiator of at least one of the group consisting of a compound, a fluorenylphosphine oxide compound, an O-fluorenyl oxime compound, and a biimidazole compound, more preferably a polymerization initiator containing an O-fluorenyl oxime compound.
聚合起始劑(D)之含量相對於樹脂(B)及聚合性化合物(C)之合計量100質量份,較佳為0.1~40質量份,更佳為0.1~30質量份,進而較佳為1~30質量份。 The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, and more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 1 to 30 parts by mass.
聚合起始助劑(D1)為用以促進藉由聚合起始劑而開始聚合之聚合性化合物之聚合之化合物、或增感劑。於含有聚合起始助劑(D1)之情形時,通常與聚合起始劑(D)組合使用。 The polymerization initiation aid (D1) is a compound or a sensitizer for promoting the polymerization of a polymerizable compound that is polymerized by a polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).
作為聚合起始助劑(D1),可列舉:胺化合物、烷氧基蒽化合物、9-氧硫化合物及羧酸化合物等。 Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, and 9-oxosulfur. Compounds and carboxylic acid compounds.
作為上述胺化合物,可列舉:三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(通稱米其勒酮)、4,4'-雙(二乙基胺基)二苯甲酮、4,4'-雙(乙基甲基胺基)二苯甲酮等,其中較佳為4,4'-雙(二乙基胺基)二苯甲酮。亦可使用EAB-F(保土谷化學工業股份有限公司製造)等市售品。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4, 4'-bis (dimethylamino) benzophenone (commonly known as Michelin), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethyl Methylamino) benzophenone and the like, among them, 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.
作為上述烷氧基蒽化合物,可列舉:9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、9,10-二丁氧基蒽、2-乙基-9,10-二丁氧基蒽等。 Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.
作為上述9-氧硫化合物,可列舉:2-異丙基-9-氧硫、4-異丙基-9-氧硫、2,4-二乙基-9-氧硫、2,4-二氯-9-氧硫、1-氯-4-丙氧基-9-氧硫等。 As the above 9-oxysulfur Compounds, including: 2-isopropyl-9-oxysulfur 4-isopropyl-9-oxysulfur , 2,4-diethyl-9-oxysulfur , 2,4-dichloro-9-oxysulfur , 1-chloro-4-propoxy-9-oxysulfur Wait.
作為上述羧酸化合物,可列舉:苯基硫基乙酸、甲基苯基硫基乙酸、乙基苯基硫基乙酸、甲基乙基苯基硫基乙酸、二甲基苯基硫基乙酸、甲氧基苯基硫基乙酸、二甲氧基苯基硫基乙酸、氯苯基硫基乙 酸、二氯苯基硫基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫乙酸、N-萘基甘胺酸、萘氧基乙酸等。 Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioethyl Acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid, naphthyloxyacetic acid, and the like.
於使用該等聚合起始助劑(D1)之情形時,其含量相對於樹脂(B)及聚合性化合物(C)之合計量100質量份,較佳為0.1~30質量份,更佳為1~20質量份。若聚合起始助劑(D1)之量在該範圍內,則有進而可以高感度形成著色圖案,彩色濾光片之生產性提高之傾向。 When using these polymerization initiation aids (D1), the content is 100 parts by mass with respect to the total amount of the resin (B) and the polymerizable compound (C), preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, there is a tendency that a colored pattern can be formed with high sensitivity, and the productivity of a color filter tends to be improved.
溶劑(E)並無特別限定,可使用該領域中通常使用之溶劑。例如可列舉:酯溶劑(於分子內含有-COO-而不含有-O-之溶劑)、醚溶劑(於分子內含有-O-而不含有-COO-之溶劑)、醚酯溶劑(於分子內含有-COO-與-O-之溶劑)、酮溶劑(於分子內含有-CO-而不含有-COO-之溶劑)、醇溶劑(於分子內含有OH而不含有-O-、-CO-及-COO-之溶劑)、芳香族烴溶劑、醯胺溶劑、二甲基亞碸等。 The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. Examples include: ester solvents (solvents containing -COO- without -O- in the molecule), ether solvents (solvents containing -O- without -COO- in the molecule), ether ester solvents (in the molecule Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- without -COO- in the molecule), alcohol solvents (containing OH without -O-, -CO in the molecule) -And -COO- solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene, and the like.
作為酯溶劑,可列舉:乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己醇乙酸酯、γ-丁內酯等。 Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclamate Hexanol acetate, γ-butyrolactone and the like.
作為醚溶劑,可列舉:乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二烷、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基***、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯***、甲基苯甲醚等。 Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and Ethylene 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-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, methyl Anisole and so on.
作為醚酯溶劑,可列舉:甲氧基乙酸甲酯、甲氧基乙酸乙酯、 甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、二丙二醇甲醚乙酸酯等。 Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, 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 ether acetate, ethylene glycol Monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.
作為酮溶劑,可列舉:4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮、異佛爾酮等。 Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone and so on.
作為醇溶劑,可列舉:甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、甘油等。 Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
作為芳香族烴溶劑,可列舉:苯、甲苯、二甲苯、均三甲苯等。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.
作為醯胺溶劑,可列舉:N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等。 Examples of the amidine solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
該等溶劑可單獨使用,亦可併用2種以上。 These solvents may be used alone or in combination of two or more.
其中,較佳為丙二醇單甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、乙酸3-甲氧基丁酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮、N,N-二甲基甲醯胺、N-甲基吡咯啶酮等,更佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、乙二醇單丁醚、二丙二醇甲醚乙酸酯、乳酸乙酯、乙酸3-甲氧基丁酯、3-甲氧基-1-丁醇、3-乙氧基丙酸乙酯、4-羥基-4-甲基-2-戊酮、N,N-二甲基甲醯胺、N-甲基吡咯啶酮等。 Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol are preferred. Monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-di Methylformamide, N-methylpyrrolidone and the like, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethyl Methylformamide, N-methylpyrrolidone and the like.
溶劑(E)之含量相對於著色硬化性樹脂組合物之總量,較佳為70~95質量%,更佳為75~92質量%。換言之,著色硬化性樹脂組合物之固形物成分較佳為5~30質量%,更佳為8~25質量%。若溶劑(E)之含量在上述範圍內,則有如下傾向:塗佈時之平坦性變得良好,又,因形成彩色濾光片時色濃度並未不足故而顯示特性變得良好。 The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating tends to be good, and the color density is not insufficient when the color filter is formed, so that the display characteristics become good.
作為調平劑(F),可列舉聚矽氧系界面活性劑、氟系界面活性劑及具有氟原子之聚矽氧系界面活性劑等。該等亦可於側鏈具有聚合性基。 Examples of the leveling agent (F) include a polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.
作為聚矽氧系界面活性劑,可列舉於分子內具有矽氧鍵之界面活性劑等。具體而言,可列舉:Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400(商品名:Dow Corning Toray股份有限公司製造)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業股份有限公司製造)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452及TSF4460(邁圖高新材料日本(Momentive Performance Materials Japan)合同公司製造)等。 Examples of the polysiloxane-based surfactant include a surfactant having a silicon-oxygen bond in the molecule. Specific examples include: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Dow Corning Toray Co., Ltd.) , KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 Momentive Performance Materials Japan).
作為上述氟系界面活性劑,可列舉於分子內具有氟碳鏈之界面活性劑等。具體而言,可列舉:Fluorad(註冊商標)FC430、Fluorad FC431(住友3M股份有限公司製造)、Megafac(註冊商標)F142D、Megafac F171、Megafac F172、Megafac F173、Megafac F177、Megafac F183、Megafac F554、Megafac R30、Megafac RS-718-K(DIC股份有限公司製造)、Eftop(註冊商標)EF301、Eftop EF303、Eftop EF351、Eftop EF352(三菱綜合材料電子化成(Mitsubishi Materials Electronic Chemicals)股份有限公司製造)、Surflon(註冊商標)S381、Surflon S382、Surflon SC101、Surflon SC105(旭硝子股份有限公司製造)及E5844(大金精密化學研究所股份有限公司製造)等。 Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Precision Chemical Research Institute Co., Ltd.).
作為上述具有氟原子之聚矽氧系界面活性劑,可列舉於分子內具有矽氧鍵及氟碳鏈之界面活性劑等。具體而言,可列舉:Megafac(註冊商標)R08、Megafac BL20、Megafac F475、Megafac F477及Megafac F443(DIC股份有限公司製造)等。 Examples of the polysiloxane-based surfactant having a fluorine atom include a surfactant having a silicon-oxygen bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Corporation).
調平劑(F)之含量相對於著色硬化性樹脂組合物之總量,較佳為0.0005質量%以上且0.6質量%以下,更佳為0.001質量%以上且0.5質量%,進而較佳為0.001質量%以上且0.2質量%以下,進而更佳為0.002質量%以上且0.1質量%以下,尤佳為0.005質量%以上且0.07質量%以下。若調平劑(F)之含量在上述範圍內,則可使彩色濾光片之平坦性變得良好。 The content of the leveling agent (F) is preferably 0.0005 mass% or more and 0.6 mass% or less, more preferably 0.001 mass% or more and 0.5 mass% or less, and more preferably 0.001% with respect to the total amount of the coloring curable resin composition. Mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, even more preferably 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be made good.
本發明之著色硬化性樹脂組合物視需要亦可含有填充劑、其他高分子化合物、密接促進劑、抗氧化劑、光穩定劑、鏈轉移劑等在該技術領域中公知之添加劑。 The colored curable resin composition of the present invention may contain additives known in the technical field such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like, as necessary.
本發明之著色硬化性樹脂組合物例如可藉由將著色劑(A)、樹脂(B)、聚合性化合物(C)、聚合起始劑(D)、及視需要使用之溶劑(E)、調平劑(F)、聚合起始助劑(D1)及其他成分加以混合而製備。 The coloring curable resin composition of the present invention can be prepared by, for example, coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), and solvent (E) as needed, A leveling agent (F), a polymerization initiation aid (D1), and other components are prepared by mixing.
含有顏料(P)之情形之顏料較佳為預先與溶劑(E)之一部分或全部混合,使用球磨機等使其分散直至顏料之平均粒徑成為0.2μm以下左右為止。此時,視需要亦可調配上述顏料分散劑、樹脂(B)之一部分或全部。於以此方式獲得之顏料分散液中以成為特定之濃度之方式混合殘留之成分,藉此可製備目標之著色硬化性樹脂組合物。 In the case where the pigment (P) is contained, the pigment is preferably partially or fully mixed with the solvent (E) in advance, and dispersed using a ball mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be blended if necessary. Residual components are mixed in the pigment dispersion liquid obtained in this way so as to have a specific concentration, whereby the intended colored curable resin composition can be prepared.
化合物(1)較佳為預先於溶劑(E)之一部分或全部中溶解而製備溶液。較佳為利用孔徑0.01~1μm左右之過濾器對該溶液進行過濾。 The compound (1) is preferably prepared by dissolving a part or all of the solvent (E) in advance to prepare a solution. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
較佳為利用孔徑0.01~10μm左右之過濾器對混合後之著色硬化性樹脂組合物進行過濾。 It is preferable to filter the colored hardening resin composition after mixing with a filter having a pore size of about 0.01 to 10 μm.
作為由本發明之著色硬化性樹脂組合物製造著色圖案之方法,可列舉:光微影法、噴墨法、印刷法等。其中,較佳為光微影法。光微影法為如下方法:將上述著色硬化性樹脂組合物塗佈於基板上,使其乾燥而形成著色組合物層,經由光罩使該著色組合物層曝光,顯影。於光微影法中,於曝光時不使用光罩及/或不進行顯影,藉此可形成上述著色組合物層之硬化物即著色塗膜。如此形成之著色圖案或著色塗膜為本發明之彩色濾光片。 Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, photolithography is preferred. The photolithography method is a method in which the colored curable resin composition is coated on a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film, which is a hardened product of the coloring composition layer described above, can be formed without using a mask and / or developing during exposure. The colored pattern or colored coating film thus formed is the color filter of the present invention.
所製作之彩色濾光片之膜厚並無特別限定,可根據目的或用途等而適當調整,例如為0.1~30μm,較佳為0.1~20μm,進而較佳為0.5~6μm。 The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose or application, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.
作為基板,可使用石英玻璃、硼矽酸玻璃、鋁矽酸鹽玻璃、表面塗佈有二氧化矽之鈉鈣玻璃等玻璃板,聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等樹脂板,矽,於上述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。亦可於該等基板上形成另一彩色濾光片層、樹脂層、電晶體、電路等。 As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass coated with silicon dioxide can be used. Polycarbonate, polymethyl methacrylate, and polyterephthalic acid can be used. Resin plates, such as ethylene glycol, and silicon, are formed on the substrate with aluminum, silver, silver / copper / palladium alloy films, or the like. Another color filter layer, resin layer, transistor, circuit, etc. can also be formed on these substrates.
利用光微影法之各色像素之形成可以公知或慣用之裝置或條件進行。例如,可以如下方式製作。 The formation of the pixels of each color by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows.
首先,將著色硬化性樹脂組合物塗佈於基板上,藉由加熱乾燥(預烘烤)及/或減壓乾燥去除溶劑等揮發成分使其乾燥,而獲得平滑之著色組合物層。 First, a colored curable resin composition is coated on a substrate, and volatile components such as solvents are removed by drying under heat (pre-baking) and / or reduced pressure to dry, thereby obtaining a smooth colored composition layer.
作為塗佈方法,可列舉:旋轉塗佈法、狹縫式塗佈法、狹縫及 旋轉塗佈法等。 Examples of the coating method include a spin coating method, a slit coating method, a slit and Spin coating method and the like.
進行加熱乾燥之情形之溫度較佳為30~120℃,更佳為50~110℃。又,加熱時間較佳為10秒鐘~60分鐘,更佳為30秒鐘~30分鐘。 In the case of heating and drying, the temperature is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
於進行減壓乾燥之情形時,較佳為於50~150Pa之壓力下,在20~25℃之溫度範圍內進行。 In the case of drying under reduced pressure, it is preferably carried out under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.
著色組合物層之膜厚並無特別限定,只要根據目標之彩色濾光片之膜厚而適當選擇即可。 The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.
繼而,著色組合物層經由用以形成目標之著色圖案之光罩而曝光。該光罩上之圖案並無特別限定,可使用對應目標用途之圖案。 Then, the coloring composition layer is exposed through a mask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used.
作為用於曝光之光源,較佳為產生波長250~450nm之光之光源。例如亦可將未達350nm之光使用截止該波長區域之濾光片截止,或將436nm附近、408nm附近、365nm附近之光使用取出該等波長區域之帶通濾波器(band-pass filter)而選擇性地取出。具體而言,可列舉:水銀燈、發光二極體、金屬鹵化物燈、鹵素燈等。 As a light source for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferred. For example, light below 350 nm can be cut off with a filter that cuts off that wavelength region, or light near 436 nm, 408 nm, and 365 nm can be cut by a band-pass filter that takes out those wavelength regions. Selectively remove. Specific examples include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.
為了可對曝光面整體均勻地照射平行光線,或進行光罩與形成有著色組合物層之基板之正確之位置對準,較佳為使用光罩對準曝光機(mask aligner)及步進式曝光機(stepper)等曝光裝置。 In order to uniformly radiate parallel light to the entire exposure surface, or to align the mask with the correct position of the substrate on which the coloring composition layer is formed, it is preferable to use a mask aligner and stepping method. Exposure equipment such as an exposure machine (stepper).
藉由使曝光後之著色組合物層與顯影液接觸進行顯影,而於基板上形成著色圖案。藉由顯影可使著色組合物層之未曝光部溶解於顯影液中而去除。作為顯影液,例如較佳為氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物之水溶液。該等鹼性化合物於水溶液中之濃度較佳為0.01~10質量%,更佳為0.02~5質量%,進而更佳為0.03~5質量%。進而,顯影液亦可含有界面活性劑。 A coloring pattern is formed on a substrate by developing the coloring composition layer after exposure with a developing solution. The unexposed portion of the coloring composition layer can be dissolved in a developing solution and removed by development. The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, and the like. The concentration of the basic compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, and even more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain a surfactant.
顯影方法可為覆液法(puddle method)、浸漬法(dipping method)及噴霧法等中之任一方法。進而,於顯影時亦可使基板傾斜為任意角 度。 The developing method may be any one of a puddle method, a dipping method, a spray method, and the like. Furthermore, the substrate can be tilted to an arbitrary angle during development. degree.
於顯影後,較佳為進行水洗。 After development, washing with water is preferred.
進而,較佳為對所獲得之著色圖案進行後烘烤。後烘烤溫度較佳為150~250℃,更佳為160~235℃。後烘烤時間較佳為1~120分鐘,更佳為10~60分鐘。 Furthermore, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 150 to 250 ° C, and more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.
根據本發明之著色硬化性樹脂組合物,可製造著色劑之昇華得以抑制,亮度特別高之彩色濾光片。該彩色濾光片作為顯示裝置(例如,液晶顯示裝置、有機EL(Electroluminescence,電致發光)裝置、電子紙等)及固體攝像元件中所使用之彩色濾光片而有用。 According to the colored curable resin composition of the present invention, it is possible to produce a color filter with a sublimation of a colorant and a particularly high brightness. This color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL (Electroluminescence) device, an electronic paper, etc.) and a solid-state imaging element.
繼而,列舉實施例等對本發明進一步進行具體說明。 Next, the present invention will be further specifically described with examples and the like.
於實施例及比較例中,表示含量或使用量之%及份只要無特別記載,則為質量基準。 In the examples and comparative examples, the percentages and parts indicating the content or the amount used are the basis of quality unless otherwise specified.
於以下之實施例中,化合物之結構係以NMR(Nuclear Magnetic Resource,核磁共振)(JMM-ECA-500;日本電子股份有限公司製造)或質譜分析(LC;Agilent製造之1200型、MASS;Agilent製造之LC/MSD6130型)而確認。 In the following examples, the structure of the compound is analyzed by NMR (Nuclear Magnetic Resource, nuclear magnetic resonance) (JMM-ECA-500; manufactured by Japan Electronics Co., Ltd.) or mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; Agilent Manufactured LC / MSD6130).
樹脂之聚苯乙烯換算之重量平均分子量(Mw)及數量平均分子量(Mn)之測定係藉由GPC(Gel Permeation Chromatography,凝膠滲透層析)法,以如下條件進行。 The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC (Gel Permeation Chromatography, gel permeation chromatography) method under the following conditions.
裝置:HLC-8120GPC(Tosoh股份有限公司製造) Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)
管柱:TSK-GEL G2000HXL Column: TSK-GEL G2000HXL
管柱溫度:40℃ Column temperature: 40 ℃
溶劑:THF(tetrahydrofuran,四氫呋喃) Solvent: THF (tetrahydrofuran)
流速:1.0mL/min Flow rate: 1.0mL / min
受檢液固形物成分濃度:0.001~0.01質量% Concentration of solid content of test liquid: 0.001 ~ 0.01% by mass
注入量:50μL Injection volume: 50 μL
檢測器:RI(Refractive Index,折射率) Detector: RI (Refractive Index, refractive index)
校正用標準物質:TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(Tosoh股份有限公司製造) Calibration reference materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
將上述獲得之聚苯乙烯換算之重量平均分子量及數量平均分子量之比(Mw/Mn)設為分子量分佈。 The ratio of the weight-average molecular weight and the number-average molecular weight (Mw / Mn) in terms of polystyrene obtained in the above was defined as the molecular weight distribution.
將4-胺基-3-羥基苯甲酸(東京化成工業股份有限公司製造)10.0份、4-(二乙基胺基)柳醛(東京化成工業股份有限公司製造)12.8份、苯甲酸(東京化成工業股份有限公司製造)2.73份、1-戊醇(東京化成工業股份有限公司製造)157份及氰基乙酸乙酯(東京化成工業股份有限公司製造)7.43份加以混合,於120℃下攪拌3小時。添加氰基乙酸乙酯(東京化成工業股份有限公司製造)7.46份、苯甲酸(東京化成工業股份有限公司製造)2.79份、1-戊醇(東京化成工業股份有限公司製造)49.8份及4-(二乙基胺基)柳醛(東京化成工業股份有限公司製造)12.7份,於120℃下攪拌14小時。添加氰基乙酸乙酯(東京化成工業股份有限公司製造)3.76份、苯甲酸(東京化成工業股份有限公司製造)1.41份、1-戊醇(東京化成工業股份有限公司製造)52.5份及4-(二乙基胺基)柳醛(東京化成工業股份有限公司製造)6.35份,於120℃下攪拌8小時。將上述反應液冷卻至室溫後,以抽氣過濾之殘渣獲得析出之結晶。於該殘渣中添加四氫呋喃140份,於70℃下攪拌1小時後,以抽氣過濾之殘渣獲得不溶物。於該殘渣中添加四氫呋喃120份,於70℃下攪拌1小時後,以抽氣過濾之殘渣獲得不溶物。於該殘渣中添加N,N-二甲基甲醯胺340份,加熱至90℃而使其溶解後,於0℃~5℃下靜置。以抽氣過濾之殘渣獲得析出之結晶。將該殘渣於60℃下進行減壓乾燥,而獲得 式(1-1)所表示之化合物5.69份。藉由1H-NMR確認結構。 10.0 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 12.8 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and benzoic acid (Tokyo 2.73 parts of Chemical Industry Co., Ltd., 157 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.43 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. 3 hours. Added 7.46 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.79 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 49.8 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4- 12.7 parts of (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 14 hours. Add 3.76 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.41 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 52.5 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4- (Diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.35 parts, and stirred at 120 ° C for 8 hours. After the reaction solution was cooled to room temperature, the residue was filtered by suction to obtain precipitated crystals. To this residue was added 140 parts of tetrahydrofuran, and the mixture was stirred at 70 ° C. for 1 hour, and then the residue was filtered by suction to obtain an insoluble matter. 120 parts of tetrahydrofuran was added to the residue, and the mixture was stirred at 70 ° C. for 1 hour, and then the residue was filtered by suction to obtain an insoluble matter. To this residue was added 340 parts of N, N-dimethylformamide, and the mixture was heated to 90 ° C to dissolve it, and then allowed to stand at 0 ° C to 5 ° C. Precipitated crystals were obtained by suction filtration of the residue. This residue was dried under reduced pressure at 60 ° C to obtain 5.69 parts of a compound represented by formula (1-1). The structure was confirmed by 1 H-NMR.
1H-NMR(500MHz,DMSO-d6):1.14(6H,t),3.47(4H,q),6.57(1H,d),6.78(1H,dd),7.68(1H,d),7.79(1H,d),7.96(1H,dd),8.15(1H,d),8.80(1H,s),13.11(1H,s)。 1 H-NMR (500MHz, DMSO-d6): 1.14 (6H, t), 3.47 (4H, q), 6.57 (1H, d), 6.78 (1H, dd), 7.68 (1H, d), 7.79 (1H , d), 7.96 (1H, dd), 8.15 (1H, d), 8.80 (1H, s), 13.11 (1H, s).
將4-(二丁基胺基)柳醛(東京化成工業股份有限公司製造)24.8份、4-胺基-3-羥基苯甲酸(東京化成工業股份有限公司製造)15.3份、苯甲酸(東京化成工業股份有限公司製造)4.20份、1-戊醇(東京化成工業股份有限公司製造)242份及氰基乙酸乙酯(東京化成工業股份有限公司製造)11.3份加以混合,於120℃下攪拌5小時。添加氰基乙酸乙酯(東京化成工業股份有限公司製造)4.61份、苯甲酸(東京化成工業股份有限公司製造)1.70份、4-(二丁基胺基)柳醛(東京化成工業股份有限公司製造)10.1份及1-戊醇(東京化成工業股份有限公司製造)10.0份,於120℃下攪拌3小時。添加氰基乙酸乙酯(東京化成工業股份有限公司製造)4.60份、苯甲酸(東京化成工業股份有限公司製造)1.70份、4-(二丁基胺基)柳醛(東京化成工業股份有限公司製造)10.2份及1-戊醇(東京化成工業股份有限公司製造)10.0份,於120℃下攪拌3小時。添加氰基乙酸乙酯(東京化成工業股份有限公司製造)4.61份、苯甲酸(東京化 成工業股份有限公司製造)1.71份及4-(二丁基胺基)柳醛(東京化成工業股份有限公司製造)10.3份,於120℃下攪拌18小時。將上述反應液冷卻至室溫後,添加至己烷1900份中並進行攪拌。以抽氣過濾之殘渣獲得析出之結晶。於該殘渣中添加四氫呋喃328份,於60℃下進行再結晶。以抽氣過濾之殘渣獲得析出之結晶。於該殘渣中添加四氫呋喃160份並進行攪拌,以抽氣過濾之殘渣獲得不溶物。將該殘渣於60℃下進行減壓乾燥,而獲得式(1-3)所表示之化合物18.9份。藉由1H-NMR確認結構。 24.8 parts of 4- (dibutylamino) salixaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.3 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and benzoic acid (Tokyo 4.20 parts of Chemical Industry Co., Ltd., 242 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 11.3 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. 5 hours. Added 4.61 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.70 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4- (dibutylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) (Manufactured) 10.1 parts and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 3 hours. Added 4.60 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.70 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4- (dibutylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) (Manufactured) 10.2 parts and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 3 hours. Added 4.61 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.71 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4- (dibutylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) (Manufactured) 10.3 parts, and stirred at 120 ° C for 18 hours. The reaction solution was cooled to room temperature, and then added to 1900 parts of hexane and stirred. Precipitated crystals were obtained by suction filtration of the residue. 328 parts of tetrahydrofuran was added to the residue, and recrystallization was performed at 60 ° C. Precipitated crystals were obtained by suction filtration of the residue. To this residue, 160 parts of tetrahydrofuran was added and stirred, and the residue was filtered by suction to obtain an insoluble matter. This residue was dried under reduced pressure at 60 ° C to obtain 18.9 parts of a compound represented by formula (1-3). The structure was confirmed by 1 H-NMR.
1H-NMR(500MHz,DMSO-d6):0.92(6H,t),1.34(4H,qt),1.54(4H,tt),3.41(4H,t),6.56(1H,d),6.78(1H,dd),7.69(1H,d),7.80(1H,d),7.98(1H,dd),8.17(1H,d),8.82(1H,s),13.11(1H,s)。 1 H-NMR (500MHz, DMSO-d6): 0.92 (6H, t), 1.34 (4H, qt), 1.54 (4H, tt), 3.41 (4H, t), 6.56 (1H, d), 6.78 (1H , dd), 7.69 (1H, d), 7.80 (1H, d), 7.98 (1H, dd), 8.17 (1H, d), 8.82 (1H, s), 13.11 (1H, s).
將4-胺基-3-羥基苯甲酸(東京化成工業股份有限公司製造)4.32份、4-(雙(2-乙基己基)胺基)柳醛(依據日本專利特表2007-508275中記載之方法而合成)10.2份、苯甲酸(東京化成工業股份有限公司製造)1.18份、1-戊醇(東京化成工業股份有限公司製造)68.0份及氰基乙酸乙酯(東京化成工業股份有限公司製造)3.19份加以混合,於120℃下攪拌3小時。於該反應溶液中添加4-(雙(2-乙基己基)胺基)柳醛(依據日 本專利特表2007-508275中記載之方法而合成)15.3份、苯甲酸(東京化成工業股份有限公司製造)1.80份、1-戊醇(東京化成工業股份有限公司製造)10.0份及氰基乙酸乙酯(東京化成工業股份有限公司製造)4.80份,於120℃下攪拌12小時。將上述反應液冷卻至室溫後,利用旋轉蒸發器將溶劑蒸餾去除,而獲得殘渣。將該殘渣利用管柱層析法進行精製,而獲得式(1-15)所表示之化合物6.32份。 4.32 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4- (bis (2-ethylhexyl) amino) salicaldehyde (according to Japanese Patent Publication No. 2007-508275) 10.2 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.18 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (Production) 3.19 parts were mixed and stirred at 120 ° C for 3 hours. To this reaction solution was added 4- (bis (2-ethylhexyl) amino) salixaldehyde (depending on day (Synthesized by the method described in this patent special table 2007-508275) 15.3 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.80 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts and cyanoacetic acid 4.80 parts of ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 12 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off by a rotary evaporator to obtain a residue. This residue was purified by column chromatography to obtain 6.32 parts of a compound represented by formula (1-15).
(質譜分析)離子化模式=ESI+:m/z=[M+H]+ 547.3 (Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 547.3
精確分子量(Exact Mass):546.3 Exact Mass: 546.3
將間苯二酚(東京化成工業股份有限公司製造)275份與正己基胺(東京化成工業股份有限公司製造)101份加以混合,一面於150~155℃下將生成之水去除一面攪拌20小時。放冷後,使反應混合物溶解於甲苯433份中,將該甲苯溶液以水1000份清洗3次。於該甲苯溶液中添加無水硫酸鎂50份並進行攪拌,然後進行過濾。將濾液之溶劑蒸餾去除而獲得粗產物。使該粗產物溶解於甲苯234份中,於0℃以下進行攪拌,濾集晶析物。將該晶析物於50℃下進行減壓乾燥,而獲得式(pt1)所表示之化合物95.7份。 275 parts of resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 101 parts of n-hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the generated water was removed at 150 to 155 ° C and stirred for 20 hours. . After allowing to cool, the reaction mixture was dissolved in 433 parts of toluene, and the toluene solution was washed three times with 1,000 parts of water. To this toluene solution, 50 parts of anhydrous magnesium sulfate was added and stirred, and then filtered. The solvent of the filtrate was distilled off to obtain a crude product. This crude product was dissolved in 234 parts of toluene, and stirred at 0 ° C or lower, and the crystallized product was collected by filtration. This crystallized product was dried under reduced pressure at 50 ° C to obtain 95.7 parts of a compound represented by formula (pt1).
(質譜分析)離子化模式=ESI+:m/z=[M+H]+ 194.2 (Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 194.2
精確分子量:193.2 Exact molecular weight: 193.2
將式(pt1)所表示之化合物95.3份與水48.0份加以混合,於80℃下進行攪拌。繼而,一面添加1-溴-2-乙基己烷(東京化成工業股份有限公司製造)107份,一面於80℃下攪拌3小時後,添加48%氫氧化鈉水溶液22.4份。將該混合物於110℃下攪拌18小時。放冷後,使用10%氫氧化鈉水溶液將反應混合物之pH值調整為5,添加甲苯130份並進行攪拌,萃取甲苯層。將甲苯萃取液以水500份清洗2次,添加無水硫酸鎂25.0份進行攪拌,並進行過濾。將濾液之溶劑蒸餾去除,而獲得包含式(pt2)所表示之化合物作為主成分之殘渣154份。 95.3 parts of the compound represented by formula (pt1) and 48.0 parts of water were mixed and stirred at 80 ° C. Next, 107 parts of 1-bromo-2-ethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and after stirring at 80 ° C for 3 hours, 22.4 parts of a 48% sodium hydroxide aqueous solution was added. The mixture was stirred at 110 ° C for 18 hours. After allowing to cool, the pH of the reaction mixture was adjusted to 5 using a 10% sodium hydroxide aqueous solution, 130 parts of toluene was added and stirred, and the toluene layer was extracted. The toluene extract was washed twice with 500 parts of water, 25.0 parts of anhydrous magnesium sulfate was added, stirred, and filtered. The solvent of the filtrate was distilled off to obtain 154 parts of a residue containing a compound represented by the formula (pt2) as a main component.
(質譜分析)離子化模式=ESI+:m/z=[M+H]+ 306.3 (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 306.3
精確分子量:305.3 Exact molecular weight: 305.3
將所獲得之包含式(pt2)所表示之化合物作為主成分之殘渣154份 與N,N-二甲基甲醯胺597份加以混合,於-6℃~3℃下進行攪拌。一面將液溫保持於-6℃~3℃一面向其中添加磷醯氯(和光純藥工業股份有限公司製造)258份。將該混合物於室溫下攪拌1小時後,於60℃下攪拌4小時。放冷後,將反應混合物添加至冰1500份中,使用48%氫氧化鈉水溶液進行中和。於其中添加甲苯867份,萃取甲苯層。將該甲苯萃取液以15%氯化鈉水溶液1200份清洗2次。於該甲苯萃取液中添加無水硫酸鎂60.0份並進行攪拌後,進行過濾。將濾液之溶劑蒸餾去除而獲得殘渣。將該殘渣利用管柱層析法進行精製,而獲得式(pt3)所表示之化合物94.4份。 154 parts of the residue containing the obtained compound represented by the formula (pt2) as a main component It was mixed with 597 parts of N, N-dimethylformamidine and stirred at -6 ° C to 3 ° C. While maintaining the liquid temperature at -6 ° C to 3 ° C, 258 parts of phosphatidyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto. After the mixture was stirred at room temperature for 1 hour, it was stirred at 60 ° C for 4 hours. After allowing to cool, the reaction mixture was added to 1500 parts of ice, and neutralized with a 48% sodium hydroxide aqueous solution. 867 parts of toluene was added thereto, and the toluene layer was extracted. This toluene extract was washed twice with 1,200 parts of a 15% sodium chloride aqueous solution. After adding 60.0 parts of anhydrous magnesium sulfate to this toluene extract, the mixture was stirred, and then filtered. The solvent of the filtrate was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 94.4 parts of a compound represented by formula (pt3).
(質譜分析)離子化模式=ESI+:m/z=[M+H]+ 334.3 (Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 334.3
精確分子量:333.3 Exact molecular weight: 333.3
將4-胺基-3-羥基苯甲酸(東京化成工業股份有限公司製造)6.89份、式(pt3)所表示之化合物15.0份、苯甲酸(東京化成工業股份有限公司製造)1.87份、1-戊醇(東京化成工業股份有限公司製造)110份及氰基乙酸乙酯(東京化成工業股份有限公司製造)5.09份加以混合,於120℃下攪拌3小時。於該反應溶液中混合式(pt3)所表示之化合物22.5份、苯甲酸(東京化成工業股份有限公司製造)2.85份、1-戊醇(東京化成工業股份有限公司製造)10.0份及氰基乙酸乙酯(東京化成工業股份有限公司製造)7.66份,於120℃下攪拌12小時。將上述反應液冷卻至 室溫後,蒸餾去除溶劑,而獲得殘渣。將該殘渣利用管柱層析法進行精製,而獲得式(1-17)所表示之化合物8.86份。 6.89 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.0 parts of a compound represented by formula (pt3), 1.87 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1- 110 parts of amyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.09 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C for 3 hours. In this reaction solution, 22.5 parts of a compound represented by formula (pt3), 2.85 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and cyanoacetic acid were mixed. 7.66 parts of ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 12 hours. Cool the reaction solution to After room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 8.86 parts of a compound represented by formula (1-17).
(質譜分析)離子化模式=ESI+:m/z=[M+H]+ 519.3 (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 519.3
精確分子量:518.3 Exact molecular weight: 518.3
於間苯二酚138份中添加2-乙基己基胺64.5份,一面於150℃~155℃下去除生成之水一面將該混合物攪拌18小時。放冷後,於反應混合物中添加甲苯250份,以水500份清洗3次。於該甲苯溶液中添加無水硫酸鎂20.0份並進行攪拌後,進行過濾。將濾液之溶劑蒸餾去除,而獲得包含式(pt4)所表示之化合物作為主成分之殘渣113份。 64.5 parts of 2-ethylhexylamine was added to 138 parts of resorcinol, and the mixture was stirred for 18 hours while removing the generated water at 150 ° C to 155 ° C. After allowing to cool, 250 parts of toluene was added to the reaction mixture, and the reaction mixture was washed three times with 500 parts of water. 20.0 parts of anhydrous magnesium sulfate was added to this toluene solution, and after stirring, it filtered. The solvent of the filtrate was distilled off to obtain 113 parts of a residue containing a compound represented by the formula (pt4) as a main component.
(質譜分析)離子化模式=ESI+:m/z=[M+H]+ 222.2 (Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 222.2
精確分子量:221.2 Exact molecular weight: 221.2
於所獲得之包含式(pt4)所表示之化合物作為主成分之殘渣58.5份中添加水23.0份,一面攪拌一面使液溫成為60℃。於該溫度下一面添 加硫酸二乙酯39.3份與48%氫氧化鈉水溶液10.6份一面攪拌9小時。其後,於60℃下攪拌5小時。放冷後,利用10%氫氧化鈉水溶液中和反應混合物,添加甲苯300份。將該甲苯溶液以水500份清洗3次。於該甲苯溶液中添加無水硫酸鎂20.0份並進行攪拌後,進行過濾。將濾液之溶劑蒸餾去除,而獲得包含式(pt5)所表示之化合物作為主成分之殘渣67.5份。 23.0 parts of water was added to 58.5 parts of the residue containing the compound represented by formula (pt4) as a main component, and the liquid temperature was 60 ° C. while stirring. Add at this temperature Add 39.3 parts of diethyl sulfate and 10.6 parts of a 48% aqueous sodium hydroxide solution and stir for 9 hours. Then, it stirred at 60 degreeC for 5 hours. After allowing to cool, the reaction mixture was neutralized with a 10% sodium hydroxide aqueous solution, and 300 parts of toluene was added. This toluene solution was washed three times with 500 parts of water. 20.0 parts of anhydrous magnesium sulfate was added to this toluene solution, and after stirring, it filtered. The solvent of the filtrate was distilled off to obtain 67.5 parts of a residue containing a compound represented by the formula (pt5) as a main component.
(質譜分析)離子化模式=ESI+:m/z=[M+H]+ 250.2 (Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 250.2
精確分子量:249.2 Exact molecular weight: 249.2
於所獲得之包含式(pt5)所表示之化合物作為主成分之殘渣67.5份中添加N,N-二甲基甲醯胺323份。一面將該混合溶液之溫度保持於-6℃~4℃一面添加***105份。使該反應液之溫度恢復至室溫並攪拌1小時後,使反應液之溫度上升至60℃並攪拌3小時。放冷後,將反應混合物添加至冰水1500份中,一面攪拌一面添加48%氫氧化鈉水溶液進行中和。於其中添加甲苯500份,萃取甲苯層。將該甲苯溶液以水1000份進行清洗。繼而,將該甲苯溶液以飽和氯化鈉水溶液1500份進行清洗。於該甲苯溶液中添加無水硫酸鎂25.0份並進行攪拌後,進行過濾。將濾液之溶劑蒸餾去除而獲得殘渣。將該殘渣利用管柱層析法進行精製,而獲得式(pt6)所表示之化合物36.7份。 323 parts of N, N-dimethylformamide was added to 67.5 parts of the obtained residue containing the compound represented by formula (pt5) as a main component. While maintaining the temperature of the mixed solution at -6 ° C to 4 ° C, 105 parts of phosphorus oxychloride was added. After the temperature of the reaction solution was returned to room temperature and stirred for 1 hour, the temperature of the reaction solution was raised to 60 ° C and stirred for 3 hours. After allowing to cool, the reaction mixture was added to 1,500 parts of ice water, and a 48% sodium hydroxide aqueous solution was added while stirring to neutralize. 500 parts of toluene was added thereto, and the toluene layer was extracted. This toluene solution was washed with 1,000 parts of water. Then, this toluene solution was washed with 1500 parts of a saturated sodium chloride aqueous solution. 25.0 parts of anhydrous magnesium sulfate was added to this toluene solution, and after stirring, it filtered. The solvent of the filtrate was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 36.7 parts of a compound represented by formula (pt6).
(質譜分析)離子化模式=ESI+:m/z=[M+H]+ 278.2 (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 278.2
精確分子量:277.2 Exact molecular weight: 277.2
將4-胺基-3-羥基苯甲酸(東京化成工業股份有限公司製造)8.28份、式(pt6)所表示之化合物15.0份、苯甲酸(東京化成工業股份有限公司製造)2.25份、1-戊醇(東京化成工業股份有限公司製造)130份及氰基乙酸乙酯(東京化成工業股份有限公司製造)6.12份加以混合,於120℃下攪拌3小時。於該反應溶液中混合式(pt6)所表示之化合物22.5份、苯甲酸(東京化成工業股份有限公司製造)3.40份、1-戊醇(東京化成工業股份有限公司製造)10.0份及氰基乙酸乙酯(東京化成工業股份有限公司製造)9.20份,於120℃下攪拌12小時。將上述反應液冷卻至室溫後,蒸餾去除溶劑,而獲得殘渣。將該殘渣利用管柱層析法進行精製,而獲得式(1-19)所表示之化合物8.75份。 8.28 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.0 parts of the compound represented by formula (pt6), 2.25 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1- 130 parts of amyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.12 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C for 3 hours. In the reaction solution, 22.5 parts of a compound represented by formula (pt6), 3.40 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and cyanoacetic acid were mixed. 9.20 parts of ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 12 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 8.75 parts of a compound represented by formula (1-19).
(質譜分析)離子化模式=ESI+:m/z=[M+H]+ 463.2 (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 463.2
精確分子量:462.2 Exact molecular weight: 462.2
將4-胺基-3-羥基苯甲酸(東京化成工業股份有限公司製造)8.01份、2-羥基-4-(吡咯啶-1-基)苯甲醛(依據Chem.Commun.2011,47,2435.而合成)10.0份、苯甲酸(東京化成工業股份有限公司製造)2.18 份、1-戊醇(東京化成工業股份有限公司製造)127份及氰基乙酸乙酯(東京化成工業股份有限公司製造)5.91份加以混合,於120℃下攪拌3小時。於該反應溶液中混合2-羥基-4-(吡咯啶-1-基)苯甲醛(依據Chem.Commun.2011,47,2435.而合成)15.0份、苯甲酸(東京化成工業股份有限公司製造)3.30份、1-戊醇(東京化成工業股份有限公司製造)10.0份及氰基乙酸乙酯(東京化成工業股份有限公司製造)8.90份,於120℃下攪拌12小時。將上述反應液冷卻至室溫後,蒸餾去除溶劑,而獲得殘渣。將該殘渣利用管柱層析法進行精製,而獲得式(1-39)所表示之化合物6.50份。 8.01 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-hydroxy-4- (pyrrolidin-1-yl) benzaldehyde (according to Chem. Commun. 2011, 47, 2435) (Synthesis) 10.0 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.18 Parts, 127 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.91 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C for 3 hours. To this reaction solution were mixed 15.0 parts of 2-hydroxy-4- (pyrrolidin-1-yl) benzaldehyde (synthesized according to Chem. Commun. 2011, 47, 2435.), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.30 parts, 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.90 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C. for 12 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 6.50 parts of a compound represented by formula (1-39).
(質譜分析)離子化模式=ESI+:m/z=[M+H]+ 377.1 (Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 377.1
精確分子量:376.1 Exact molecular weight: 376.1
將4-胺基-3-羥基苯甲酸(東京化成工業股份有限公司製造)9.21份、8-羥基咯啶-9-羧醛(8-Hydroxyjulolidine-9-carboxaldehyde)(東京化成工業股份有限公司製造)13.1份、苯甲酸(東京化成工業股份有限公司製造)2.51份、1-戊醇(東京化成工業股份有限公司製造)145份及氰基乙酸乙酯(東京化成工業股份有限公司製造)6.80份加以混合,於120℃下攪拌3小時。添加氰基乙酸乙酯(東京化成工業股份有限公司製造)10.2份、苯甲酸(東京化成工業股份有限公司製造)3.80份、8- 羥基咯啶-9-羧醛(東京化成工業股份有限公司製造)19.6份及1-戊醇(東京化成工業股份有限公司製造)10.0份,於120℃下攪拌12小時。將上述反應液冷卻至室溫後,利用旋轉蒸發器將溶劑蒸餾去除,而獲得殘渣。將該殘渣利用管柱層析法進行精製,而獲得式(1-5)所表示之化合物。 9.21 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 8-hydroxy 13.1 parts of 8-Hydroxyjulolidine-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.51 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 145 parts of Co., Ltd.) and 6.80 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C for 3 hours. Added 10.2 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.80 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 8-hydroxyl 19.6 parts of pyridin-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C. for 12 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off by a rotary evaporator to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (1-5).
將4-胺基-3-羥基苯甲酸(東京化成工業股份有限公司製造)9.21份、8-羥基-1,1,7,7-四甲基咯啶-9-羧醛(東京化成工業股份有限公司製造)16.4份、苯甲酸(東京化成工業股份有限公司製造)2.51份、1-戊醇(東京化成工業股份有限公司製造)145份及氰基乙酸乙酯(東京化成工業股份有限公司製造)6.80份加以混合,於120℃下攪拌3小時。添加氰基乙酸乙酯(東京化成工業股份有限公司製造)10.2份、苯甲酸(東京化成工業股份有限公司製造)3.80份、8-羥基-1,1,7,7-四甲基咯啶-9-羧醛(東京化成工業股份有限公司製造)24.7份及1-戊醇(東京化成工業股份有限公司製造)10.0份,於120℃下攪拌12小時。將上述反應液冷卻至室溫後,利用旋轉蒸發器將溶劑蒸餾去除,而獲得殘渣。將該殘渣利用管柱層析法進行精製,而獲得式(1-7)所表示之化合物。 9.21 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 8-hydroxy-1,1,7,7-tetramethyl 16.4 parts of pyridin-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.51 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 145 parts of 1-pentanol (made by Tokyo Chemical Industry Co., Ltd.) 6.80 parts of ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C for 3 hours. Added 10.2 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.80 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 8-hydroxy-1,1,7,7-tetramethyl 24.7 parts of pyridin-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 12 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off by a rotary evaporator to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (1-7).
於具備回流冷卻器、滴液漏斗及攪拌機之燒瓶內通入適量氮氣而形成氮氣環境,添加丙二醇單甲醚乙酸酯100份,一面攪拌一面加熱至85℃。繼而,使用滴加泵歷時約5小時向該燒瓶內滴加使甲基丙烯酸19份、丙烯酸3,4-環氧三環[5.2.1.02.6]癸烷-8-酯及丙烯酸3,4-環氧三環[5.2.1.02.6]癸烷-9-酯之混合物(含有比以莫耳比計為50:50)171份溶解於丙二醇單甲醚乙酸酯40份中而成之溶液。另一方面,使用另一滴加泵歷時約5小時向燒瓶內滴加使聚合起始劑2,2'-偶氮雙(2,4-二甲基戊腈)26份溶解於丙二醇單甲醚乙酸酯120份中而成之溶液。於聚合起始劑之滴加結束後,於該溫度下保持約3小時,其後冷卻至室溫,而獲得固形物成分43.5%之共聚物(樹脂B1)之溶液。所獲得之樹脂B1之重量平均分子量為8000,分子量分佈為1.98,固形物成分換算之酸值為53mgKOH/g。 Pass a proper amount of nitrogen into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to form a nitrogen atmosphere. Add 100 parts of propylene glycol monomethyl ether acetate, and heat to 85 ° C while stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 2.6 ] decane-8-ester, and 3,4-acrylic acid were added dropwise to the flask using a dropping pump over about 5 hours. An epoxy tricyclo [5.2.1.0 2.6 ] decane-9-ester mixture (containing a molar ratio of 50:50) 171 parts was dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, 26 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl ether dropwise into the flask using another drop pump over about 5 hours. A solution of 120 parts of acetate. After the dropwise addition of the polymerization initiator was completed, it was kept at this temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B1) having a solid content of 43.5%. The weight average molecular weight of the obtained resin B1 was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mgKOH / g.
將著色劑(A):C.I.顏料綠7(顏料) 27份、丙烯酸系顏料分散劑 12份、樹脂(B):樹脂B1(固形物成分換算) 9.5份、及溶劑(E):丙二醇單甲醚乙酸酯 180份加以混合,使用球磨機使顏料充分分散而獲得顏料分散液;將著色劑(A):式(1-15)所表示之化合物 3.0份、樹脂(B):樹脂B1(固形物成分換算) 40份、聚合性化合物(C):二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA;日本化藥股份有限公司製造) 49份、聚合起始劑(D):N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01;BASF公司製造;O-醯基肟化合物) 9.8份、溶劑(E):丙二醇單甲醚乙酸酯 670份、及調平劑(F):聚醚改性聚矽氧油(Toray Silicone SH8400;Dow Corning Toray股份有限公司製造) 0.15份 Colorant (A): 27 parts of CI Pigment Green 7 (pigment), 12 parts of acrylic pigment dispersant, resin (B): 9.5 parts of resin B1 (solid content conversion), and solvent (E): propylene glycol monomethyl 180 parts of ether acetate were mixed, and the pigment was sufficiently dispersed using a ball mill to obtain a pigment dispersion liquid; colorant (A): 3.0 parts of the compound represented by formula (1-15), resin (B): resin B1 (solid form 40 parts, polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts, polymerization initiator (D): N-benzyl Ethoxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 9.8 parts Solvent (E): 670 parts of propylene glycol monomethyl ether acetate, and Leveling agent (F): Polyether-modified polysiloxane (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.15 parts
加以混合,而獲得著色硬化性樹脂組合物。 These were mixed to obtain a colored curable resin composition.
除將著色劑(A)之C.I.顏料綠7(顏料)取代為C.I.顏料綠36(顏料)以外,與實施例1同樣地獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained in the same manner as in Example 1 except that C.I. Pigment Green 7 (pigment) of the colorant (A) was replaced with C.I. Pigment Green 36 (pigment).
除將著色劑(A)之C.I.顏料綠7(顏料)取代為C.I.顏料綠58(顏料)以外,與實施例1同樣地獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained in the same manner as in Example 1 except that C.I. Pigment Green 7 (pigment) of the colorant (A) was replaced with C.I. Pigment Green 58 (pigment).
關於膜厚,使用日本真空技術股份有限公司製造之DEKTAK3測定膜厚。 As for the film thickness, the film thickness was measured using DEKTAK3 manufactured by Japan Vacuum Technology Co., Ltd.
將樹脂:甲基丙烯酸/甲基丙烯酸苄酯(莫耳比:30/70)共聚物(田岡化學工業股份有限公司製造,平均分子量10700,酸值70mgKOH/g)33.8%丙二醇單甲醚乙酸酯溶液 40.2份、聚合性化合物:二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA;日本化藥股份有限公司製造) 5.8份、聚合起始劑:N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE01;BASF日本公司製造) 0.58份、調平劑:聚醚改性聚矽氧(Toray Silicone SH8400;Dow Corning Toray股份有限公司製造) 0.01份、溶劑:丙二醇單甲醚 46.6份、及溶劑:丙二醇單甲醚乙酸酯 6.8份 Resin: methacrylic acid / benzyl methacrylate (mol ratio: 30/70) copolymer (manufactured by Taoka Chemical Industry Co., Ltd., average molecular weight 10700, acid value 70mgKOH / g) 33.8% propylene glycol monomethyl ether acetic acid 40.2 parts of an ester solution, polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts, polymerization initiator: N-benzyloxy-1- (4 -Phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Japan) 0.58 part, leveling agent: polyether modified polysiloxane (Toray Silicone SH8400 ; Manufactured by Dow Corning Toray Co., Ltd.) 0.01 parts, solvent: 46.6 parts of propylene glycol monomethyl ether, and solvent: 6.8 parts of propylene glycol monomethyl ether acetate
加以混合,而獲得昇華性試驗用樹脂組合物(SJS)。 These were mixed to obtain a resin composition (SJS) for a sublimation test.
於2英吋見方之玻璃基板(Eagle XG;Corning公司製造)上,利用旋轉塗佈法塗佈上述獲得之昇華性試驗用樹脂組合物(SJS),於100℃下以3分鐘使揮發成分揮發。冷卻後,使用曝光機(TME-150RSK;TOPCON股份有限公司製造),於大氣環境下以150mJ/cm2之曝光量(以365nm為基準)進行光照射。於烘箱中以220℃加熱2小時,而形成昇華性試驗用樹脂塗佈膜(SJSM)(膜厚2.2μm)。 On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), the above-obtained sublimation test resin composition (SJS) was applied by a spin coating method, and the volatile components were volatilized at 100 ° C for 3 minutes. . After cooling, light exposure was performed using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) at an exposure amount of 150 mJ / cm 2 (based on 365 nm) in an atmospheric environment. It heated at 220 degreeC in the oven for 2 hours, and formed the resin coating film (SJSM) for sublimation test (film thickness 2.2 micrometers).
於2英吋見方之玻璃基板(Eagle XG;Corning公司製造)上,利用旋轉塗佈法塗佈實施例1中獲得之著色硬化性樹脂組合物後,於100℃下進行3分鐘之預烘烤,而形成著色組合物層。冷卻後,將形成有著色組合物層之基板與石英玻璃製光罩之間隔設為200μm,使用曝光機(TME-150RSK;TOPCON股份有限公司製造),於大氣環境下以80 mJ/cm2之曝光量(以365nm為基準)進行曝光。再者,作為光罩,使用形成有100μm之線與間隙圖案者。於25℃下,將曝光後之著色組合物層於含有非離子系界面活性劑0.12%與氫氧化鉀0.04%之水溶液中浸漬70秒鐘而顯影,然後進行水洗。測定膜厚。將結果示於表1中。 The colored hardening resin composition obtained in Example 1 was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by a spin coating method, and then pre-baked at 100 ° C for 3 minutes. To form a coloring composition layer. After cooling, the substrate is formed of a colored composition layer and the spacer photomask made of quartz glass is set to 200 m, using an exposure machine (TME-150RSK; TOPCON Co., Ltd.), under the atmosphere at 80 mJ / cm 2 of The exposure was performed (based on 365 nm). In addition, as the photomask, a 100 μm line and gap pattern was used. The coloring composition layer after exposure was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for 70 seconds for development, and then washed with water. The film thickness was measured. The results are shown in Table 1.
使該著色塗佈膜與上述獲得之昇華性試驗用樹脂塗佈膜(SJSM)以空出70μm之間隔之狀態相對向,於220℃下進行40分鐘之後烘烤,藉此獲得著色圖案。使用測色機(OSP-SP-200;OLYMPUS公司製造)測定昇華性試驗用樹脂塗佈膜(SJSM)於加熱前後之色差(△Eab*)。若色差(△Eab*)為5.0以上,則表示著色劑具有昇華性。將結果示於表1中。於表1中,於各實施例中,○表示著色劑不具有昇華性,×表示著色劑具有昇華性。 This colored coating film and the resin coating film (SJSM) for sublimation test obtained above were opposed to each other with a gap of 70 μm, and then baked at 220 ° C. for 40 minutes to obtain a colored pattern. The color difference (ΔEab *) of the resin coating film (SJSM) for sublimation test before and after heating was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). A color difference (ΔEab *) of 5.0 or more indicates that the colorant has sublimability. The results are shown in Table 1. In Table 1, in each of the examples, ○ indicates that the colorant does not have sublimability, and X indicates that the colorant has sublimability.
除將實施例1中獲得之著色硬化性樹脂組合物取代為實施例QQQ中獲得之著色硬化性樹脂組合物以外,與實施例4同樣地獲得著色圖案。又,進行昇華性評價。將結果示於表1中。上述實施例QQQ分別表示表1所示之實施例QQQ。 A colored pattern was obtained in the same manner as in Example 4 except that the colored curable resin composition obtained in Example 1 was replaced with the colored curable resin composition obtained in Example QQ. In addition, sublimation evaluation was performed. The results are shown in Table 1. The above-mentioned embodiments QQQ respectively represent the embodiments QQQ shown in Table 1.
將著色劑(A):香豆素6 3.6份、樹脂(B):樹脂(B1)(固形物成分換算) 180份、溶劑(E):丙二醇單甲醚乙酸酯 230份、 溶劑(E):N,N-二甲基甲醯胺 590份、及調平劑(F):聚醚改性聚矽氧油(Toray Silicone SH8400;Dow Corning Toray股份有限公司製造) 0.063份 Colorant (A): Coumarin 6 3.6 parts, Resin (B): Resin (B1) (solid content conversion) 180 parts, Solvent (E): Propylene glycol monomethyl ether acetate 230 parts, Solvent (E): 590 parts of N, N-dimethylformamide, and leveling agent (F): polyether-modified polysiloxane (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.063 parts
加以混合,而獲得著色樹脂組合物。 They were mixed to obtain a colored resin composition.
於2英吋見方之玻璃基板(Eagle XG;Corning公司製造)上,利用旋轉塗佈法塗佈比較例1中獲得之著色樹脂組合物後,於100℃下進行3分鐘之預烘烤,而形成著色組合物層。對於膜厚,使用日本真空技術股份有限公司製造之DEKTAK3測定膜厚,結果為1.9μm。使該著色塗佈膜與上述獲得之昇華性試驗用樹脂塗佈膜(SJSM)以空出70μm之間隔之狀態相對向,於220℃下進行40分鐘之後烘烤。使用測色機(OSP-SP-200;OLYMPUS公司製造)測定昇華性試驗用樹脂塗佈膜(SJSM)於加熱前後之色差(△Eab*)。其結果,色差(△Eab*)為5.0以上。若色差(△Eab*)為5.0以上,則表示著色劑具有昇華性。 On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), the colored resin composition obtained in Comparative Example 1 was applied by a spin coating method, and then pre-baked at 100 ° C for 3 minutes, and A colored composition layer is formed. The film thickness was measured using DEKTAK3 manufactured by Japan Vacuum Technology Co., Ltd., and it was 1.9 μm. The colored coating film and the resin coating film for sublimation test (SJSM) obtained as described above were opposed to each other with a gap of 70 μm, and the baking was performed at 220 ° C. for 40 minutes. The color difference (ΔEab *) of the resin coating film (SJSM) for sublimation test before and after heating was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). As a result, the color difference (ΔEab *) was 5.0 or more. A color difference (ΔEab *) of 5.0 or more indicates that the colorant has sublimability.
由上述結果可確認,根據本發明,可提供一種著色劑不昇華而形成彩色濾光片之著色硬化性樹脂組合物。 From the above results, it was confirmed that the present invention can provide a coloring curable resin composition which forms a color filter without sublimation.
根據本發明,可提供一種著色劑不昇華而形成彩色濾光片之著色硬化性樹脂組合物,該彩色濾光片可較佳地用於液晶顯示裝置等顯示裝置。 According to the present invention, it is possible to provide a coloring curable resin composition that forms a color filter without sublimation of the colorant, and the color filter can be preferably used for display devices such as a liquid crystal display device.
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JP2006154740A (en) * | 2004-07-14 | 2006-06-15 | Fuji Photo Film Co Ltd | Photosensitive composition, pattern forming material, photosensitive laminate, pattern forming apparatus and method of pattern formation |
JP2006045314A (en) * | 2004-08-03 | 2006-02-16 | Fuji Electric Holdings Co Ltd | Salt composed of fluorescent anion and fluorescent cation and color conversion membrane using the same |
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