TWI604271B - Colored curable resin composition - Google Patents
Colored curable resin composition Download PDFInfo
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- TWI604271B TWI604271B TW101136863A TW101136863A TWI604271B TW I604271 B TWI604271 B TW I604271B TW 101136863 A TW101136863 A TW 101136863A TW 101136863 A TW101136863 A TW 101136863A TW I604271 B TWI604271 B TW I604271B
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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
- 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
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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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
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
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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
-
- 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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- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本發明,係關於一種著色硬化性樹脂組成物。 The present invention relates to a coloring curable resin composition.
著色硬化性樹脂組成物,係使用在液晶顯示面板、電激發光面板及電漿顯示面板等顯示裝置中所使用的濾色器之製造上。此類著色硬化性樹脂組成物,目前已知有含有作為其溶劑之環己酮、丙二醇單甲醚乙酸酯、丙二醇單甲醚及乳酸乙酯之著色硬化性樹脂組成物(JP2010-211198-A)。 The colored curable resin composition is used for the production of a color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. A colored curable resin composition containing cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and ethyl lactate as a solvent thereof is known as a coloring curable resin composition (JP2010-211198- A).
同時,在大型尺寸之基板方面,作為著色硬化性樹脂組成物之塗布裝置而使用細縫噴嘴塗布機。在使用細縫噴嘴塗布機塗布著色硬化性樹脂組成物時,已知該著色硬化性樹脂組成物在黏度越低時越可提高其塗布速度,因此可使產出間隔時間(Takt time)縮短(「濾色器之最新技術動向~構成材料‧製造‧評估‧海外動向~」,情報機構股份有限公司,2005年5月,p.159)。 Meanwhile, in the case of a large-sized substrate, a slit nozzle coater is used as a coating device for a colored curable resin composition. When the colored curable resin composition is applied by using a slit nozzle coater, it is known that the colored curable resin composition can increase the coating speed as the viscosity is lower, so that the interval time (Takt time) can be shortened ( "The latest technology trends in color filters - constituting materials ‧ manufacturing ‧ assessment ‧ overseas trends ~", Intelligence Agency, Inc., May 2005, p. 159).
然先前以來所知之上述著色硬化性樹脂組成物,仍有黏度未必可完全滿意之情形。 However, the above-mentioned colored curable resin composition known to the prior art may still be completely satisfactory in viscosity.
本發明包含以下之發明。 The invention includes the following invention.
[1]一種著色硬化性樹脂組成物,係包含著色劑、樹脂、聚合性化合物、聚合起始劑及溶劑,且著色劑包含染料及顏料,溶劑包含環酮及丙二醇單甲醚乙酸酯,環酮之含量相對於溶劑之總量為25質量%以上75質量%以下,丙二醇單甲醚乙酸酯之含量相對於溶劑之總量為25質量%以上75質量%以下,溶劑之含量相對於著色硬化性樹脂組成物之總量為80質量%以上90質量%以下。 [1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent, wherein the colorant comprises a dye and a pigment, and the solvent comprises a cyclic ketone and a propylene glycol monomethyl ether acetate. The content of the cyclic ketone is 25% by mass or more and 75% by mass or less based on the total amount of the solvent, and the content of the propylene glycol monomethyl ether acetate is 25% by mass or more and 75% by mass or less based on the total amount of the solvent, and the content of the solvent is relative to The total amount of the colored curable resin composition is 80% by mass or more and 90% by mass or less.
[2]如[1]項中所載之著色硬化性樹脂組成物,其中,環酮及丙二醇單甲醚乙酸酯之合計量相對於溶劑之總量為80質量%以上100質量%以下。 [2] The colored curable resin composition according to [1], wherein the total amount of the cyclic ketone and the propylene glycol monomethyl ether acetate is 80% by mass or more and 100% by mass or less based on the total amount of the solvent.
[3]如[1]項或[2]項中所載之著色硬化性樹脂組成物,其中,環酮係由環己酮及環戊酮所形成之群中所選擇之至少1種。 [3] The colored curable resin composition according to [1] or [2], wherein the cyclic ketone is at least one selected from the group consisting of cyclohexanone and cyclopentanone.
[4]一種濾色器,係由如[1]項至[3]項中任意一項所載之著色硬化性樹脂組成物所形成者。 [4] A color filter formed by the colored curable resin composition as set forth in any one of [1] to [3].
[5]一種顯示裝置,係包含如[4]項中所載之濾色器。本發明之著色硬化性樹脂組成物,係具有低黏度。 [5] A display device comprising the color filter as set forth in [4]. The colored curable resin composition of the present invention has a low viscosity.
本發明之著色硬化性樹脂組成物,係包含:著色劑(A)、樹脂(B)、聚合性化合物(C)、聚合起始劑(D)及溶劑(E)。 The colored curable resin composition of the present invention comprises a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).
著色劑(A)係包含:染料(A1)及顏料(A2)。 The colorant (A) contains a dye (A1) and a pigment (A2).
溶劑(E)係包含:環酮及丙二醇單甲醚乙酸酯,且環酮之含量相對於溶劑(E)之總量為25質量%以上75質量%以下,丙二醇單甲醚乙酸酯之含量相對於溶劑(E)之總量為25質量%以上75質量%以下,溶劑(E)之含量相對於著色硬化性樹脂組成物之總量為80質量%以上90質量%以下。 The solvent (E) includes a cyclic ketone and a propylene glycol monomethyl ether acetate, and the content of the cyclic ketone is 25% by mass or more and 75% by mass or less based on the total amount of the solvent (E), and propylene glycol monomethyl ether acetate The content of the solvent (E) is from 80% by mass to 90% by mass based on the total amount of the colored curable resin composition.
此外,本發明之著色硬化性樹脂組成物,依照其需要,亦可再包含由聚合起始助劑(D1)及界面活性劑(F)所形成之群中所選擇之至少1種。 Further, the colored curable resin composition of the present invention may further contain at least one selected from the group consisting of a polymerization starting aid (D1) and a surfactant (F).
同時,各成分並無特別之限定,可以單獨使用1種,惟亦可以2種以上併用。 In addition, each component is not particularly limited, and one type may be used alone, but two or more types may be used in combination.
著色劑(A),可例舉如:染料(A1)及顏料(A2)。 The coloring agent (A) may, for example, be a dye (A1) or a pigment (A2).
染料(A1)並無特別之限定,可使用一般所知之染料,可例舉如:溶劑染料、酸性染料、直接染料、媒染染料等,而以可溶解於有機溶劑之染料為佳。 The dye (A1) is not particularly limited, and generally known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mord dyes, and the like, and those which are soluble in an organic solvent are preferred.
染料(A1),可例舉如:在比色指數(The Society of Dyers and Colourists公司出版)中分類為染料之化合物、及在染色筆記(色染公司)中所載之一般已知之染料。又,依照化學結構,可例舉如:偶氮染料、花青染料、三苯基甲烷染料、酞花青染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基染料、偶氮次甲基染料、方酸菁(squarylium)染料、吖啶染料、苯乙烯染料、香豆素染料、喹啉染料及硝基染料等。此等之中,以有機溶劑可溶性染料較佳。 The dye (A1) may, for example, be a compound classified as a dye in a colorimetric index (published by The Society of Dyers and Colourists), and a generally known dye contained in a dyeing note (color dyeing company). Further, according to the chemical structure, for example, an azo dye, a cyanine dye, a triphenylmethane dye, a phthalocyanine dye, an anthraquinone dye, a naphthoquinone dye, a quinone imine dye, a methine dye, an azo A methine dye, a squarylium dye, an acridine dye, a styrene dye, a coumarin dye, a quinoline dye, and a nitro dye. Among these, an organic solvent-soluble dye is preferred.
具體上可例舉如:C.I.溶劑黃4號、(以下,省略C.I.溶劑黃之記載,只記載其編號)14號、15號、23號、24號、38號、62號、63號、68號、82號、94號、98號、99號、117號、162號、163號、167號、189號;C.I.溶劑紅45號、49號、111號、125號、130號、143號、145號、146號、150號、151號、155號、168號、169號、172號、175號、181號、207號、218號、222號、227號、230號、245號、247號;C.I.溶劑橙2號、7號、11號、15號、26號、56號、77號、86號;C.I.溶劑紫11號、13號、14號、26號、31號、36號、37號、38號、45號、47號、48號、51號、59號、60號;C.I.溶劑藍4號、5號、14號、18號、35號、36號、37號、45號、58號、59號、59:1號、63號、67號、68號、69號、70號、78號、79號、83號、90號、94號、97號、98號、100號、101號、102號、104號、105號、111號、112號、122號、128號、132號、136號、139號;C.I.溶劑綠1號、3號、4號、5號、7號、28號、29號、32號、33號、34號、35號、等C.I.溶劑染料;C.I.酸性黃1號、3號、7號、9號、11號、17號、23號、25號、29號、34號、36號、38號、40號、42號、54號、65號、72號、73號、76號、79號、98號、99號、111號、112號、113號、114號、116號、119號、123號、128 號、134號、135號、138號、139號、140號、144號、150號、155號、157號、160號、161號、163號、168號、169號、172號、177號、178號、179號、184號、190號、193號、196號、197號、199號、202號、203號、204號、205號、207號、212號、214號、220號、221號、228號、230號、232號、235號、238號、240號、242號、243號、251號;C.I.酸性紅1號、4號、8號、14號、17號、18號、26號、27號、29號、31號、33號、34號、35號、37號、40號、42號、44號、50號、51號、52號、57號、66號、73號、76號、80號、87號、88號、91號、92號、94號、95號、97號、98號、103號、106號、111號、114號、129號、133號、134號、138號、143號、145號、150號、151號、155號、158號、160號、172號、176號、182號、183號、195號、198號、206號、211號、215號、216號、217號、227號、228號、249號、252號、257號、258號、260號、261號、266號、268號、270號、274號、277號、280號、281號、289號、308號、312號、315號、316號、339號、341號、345號、346號、349號、382號、383號、388號、394號、401號、412號、417號、418號、422號、426號;C.I.酸性橙6號、7號、8號、10號、12號、26號、50號、51號、52號、56號、62號、63號、64號、74號、75號、94號、95號、107號、108號、169號、173號; C.I.酸性紫6B號、7號、9號、17號、19號、30號、34號、102號;C.I.酸性藍1號、7號、9號、15號、18號、22號、23號、25號、27號、29號、40號、41號、42號、43號、45號、51號、54號、59號、60號、62號、70號、72號、74號、78號、80號、82號、83號、86號、87號、90號、92號、93號、96號、100號、102號、103號、104號、112號、113號、117號、120號、126號、127號、129號、130號、131號、138號、140號、142號、143號、147號、150號、151號、154號、158號、161號、166號、167號、168號、170號、171號、175號、182號、183號、184號、187號、192號、199號、203號、204號、205號、210號、229號、234號、236號、242號、243號、256號、259號、267號、278號、280號、285號、290號、296號、315號、324:1號、335號、340號;C.I.酸性綠1號、3號、5號、9號、16號、25號、27號、28號、41號、50號、58號、63號、65號、80號、104號、105號、106號、109號等C.I.酸性染料;C.I.直接黃2號、33號、34號、35號、38號、39號、43號、47號、50號、54號、58號、68號、69號、70號、71號、86號、93號、94號、95號、98號、102號、108號、109號、129號、136號、138號、141號;C.I.直接紅79號、82號、83號、84號、91號、92號、96號、97號、98號、99號、105號、106號、107號、172 號、173號、176號、177號、179號、181號、182號、184號、204號、207號、211號、213號、218號、220號、221號、222號、232號、233號、234號、241號、243號、246號、250號;C.I.直接橙26號、34號、39號、41號、46號、50號、52號、56號、57號、61號、64號、65號、68號、70號、96號、97號、106號、107號;C.I.直接紫47號、52號、54號、59號、60號、65號、66號、79號、80號、81號、82號、84號、89號、90號、93號、95號、96號、103號、104號;C.I.直接藍1號、2號、6號、8號、15號、22號、25號、40號、41號、57號、71號、76號、77號、78號、80號、81號、84號、85號、86號、90號、93號、94號、95號、97號、98號、99號、100號、101號、106號、107號、108號、109號、113號、114號、115號、117號、119號、120號、137號、149號、150號、153號、155號、156號、158號、159號、160號、161號、162號、163號、164號、165號、166號、167號、168號、170號、171號、172號、173號、188號、189號、190號、192號、193號、194號、195號、196號、198號、199號、200號、201號、202號、203號、207號、209號、210號、212號、213號、214號、222號、225號、226號、228號、229號、236號、237號、238號、242號、243號、244號、245號、246號、247號、248號、249號、250號、251號、252號、256號、257號、 259號、260號、268號、274號、275號、293號;C.I.直接綠25號、27號、31號、32號、34號、37號、63號、65號、66號、67號、68號、69號、72號、77號、79號、82號等C.I.直接染料;C.I.分散染料黃51號、54號、76號;C.I.分散染料紫26號、27號;C.I.分散染料藍1號、14號、56號、60號等分散染料;C.I.鹼性紅1號、10號;C.I.鹼性藍1號、3號、5號、7號、9號、19號、21號、22號、24號、25號、26號、28號、29號、40號、41號、45號、47號、54號、58號、59號、60號、64號、65號、66號、67號、68號;C.I.鹼性綠1號等C.I.鹼性染料;C.I.活性黃2號、76號、116號;C.I.活性橙16號;C.I.活性紅36號等C.I.活性染料;C.I.媒染黃5號、8號、10號、16號、20號、26號、30號、31號、33號、42號、43號、45號、56號、61號、62號、65號;C.I.媒染紅1號、2號、3號、4號、9號、11號、12號、14號、17號、18號、19號、22號、23號、24號、25號、26號、27號、30號、32號、33號、36號、37號、38號、39號、41號、43號、45號、46號、48號、53號、56號、63號、71號、74號、85號、86號、88號、90號、94 號、95號;C.I.媒染橙3號、4號、5號、8號、12號、13號、14號、20號、21號、23號、24號、28號、29號、32號、34號、35號、36號、37號、42號、43號、47號、48號;C.I.媒染紫1號、2號、4號、5號、7號、14號、22號、24號、30號、31號、32號、37號、40號、41號、44號、45號、47號、48號、53號、58號;C.I.媒染藍1號、2號、3號、7號、8號、9號、12號、13號、15號、16號、19號、20號、21號、22號、23號、24號、26號、30號、31號、32號、39號、40號、41號、43號、44號、48號、49號、53號、61號、74號、77號、83號、84號;C.I.媒染綠1號、3號、4號、5號、10號、15號、19號、26號、29號、33號、34號、35號、41號、43號、53號等C.I.媒染染料;C.I.甕染綠1號等C.I.甕染染料(vat dye)等。 Specifically, for example, CI Solvent Yellow No. 4 (hereinafter, the description of the CI solvent yellow is omitted, and only the number thereof is described), No. 14, No. 15, No. 23, No. 24, No. 38, No. 62, No. 63, No. 68, 68 No., 82, 94, 98, 99, 117, 162, 163, 167, 189; CI Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247 CI Solvent Orange 2, 7, 11, 15, 15, 26, 77, 86; CI Solvent Violet No. 11, 13, 14, 26, 31, 36, 37 No., No. 38, No. 45, No. 47, No. 48, No. 51, No. 59, No. 60; CI Solvent Blue No. 4, No. 5, No. 14, No. 18, No. 35, No. 36, No. 37, No. 45, No. 45, No. 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Solvent Green 1, 3, 4 , No. 5, No. 7, No. 28, No. 29, No. 32, No. 33, No. 34, No. 35, etc. CI solvent dyes; CI Acid Yellow No. 1, No. 3, No. 7, No. 9, No. 11, No. 17 , 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111 No., 112, 113, 114, 116, 119, 123, 128 No. 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221 , 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26 No., 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134 , 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215 No. 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394 , 401, 412, 417, 418, 422, 426; CI Acid Orange 6, No. 7, No. 8, No. 10, No. 12, No. 26, No. 50, No. 51, No. 52, 56 No. 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet No. 6B, No. 7, No. 9, No. 17, No. 19, No. 30, No. 34, No. 102; CI Acid Blue No. 1, No. 7, No. 9, No. 15, No. 18, No. 22, No. 23 , 25, 27, 29, 40, 41, 42, 43, 45, 51, 54, 59, 60, 62, 70, 72, 74, 78 No. 8, 80, 82, 83, 86, 87, 90, 92, 93, 96, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166 , 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 229, 234 No. 236, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335, 340; CI Acid Green 1, No. 3, No. 5, No. 9, No. 16, No. 25, No. 27, No. 28, No. 41, No. 50, No. 58, No. 63, No. 65, No. 80, No. 104, No. 105, No. 105, 106 CI, No. 109, etc. CI acid dye; CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69 , 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82 No., 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172 No. 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61 , 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Purple 47, 52, 54, 59, 60, 65, 66, 79 No. 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue No. 1, No. 2, No. 6, No. 8, No. 15, 22, 25, 40, 41, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93 , 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120 No. 1, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 1 68, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201 , 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242 No. 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67 , CI No. 68, No. 69, No. 72, No. 77, No. 79, No. 82, CI Direct Dye; CI Disperse Dye Yellow No. 51, No. 54, No. 76; CI Disperse Dye Violet No. 26, No. 27; CI Disperse Dye Blue Disperse dyes such as No. 1, No. 14, No. 56, No. 60; CI alkaline red No. 1, No. 10; CI alkaline blue No. 1, No. 3, No. 5, No. 7, No. 9, No. 19, No. 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66 , 67, 68; CI alkaline green 1 and other CI basic dyes; CI active yellow 2, 76, 116; CI active orange 16; CI active red 36 and other CI reactive dyes; CI mediated yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mord Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25 , 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63 No., 71, 74, 85, 86, 88, 90, 94 No. 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, No. 34, No. 35, No. 36, No. 37, No. 42, No. 43, No. 47, No. 48; CI MG, No. 1, No. 2, No. 4, No. 5, No. 7, No. 14, No. 22, No. 24 , 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58; CI mordant blue 1, 2, 3, 7 No. 8, No. 8, No. 9, No. 13, No. 15, No. 16, No. 19, No. 20, No. 21, No. 22, No. 23, No. 24, No. 26, No. 30, No. 31, No. 32, No. 32, No. 39, No. 40, No. 41, No. 43, No. 44, No. 48, No. 49, No. 53, No. 61, No. 74, No. 77, No. 83, No. 84; CI mord green No. 1, No. 3, No. 4 CI mordant dyes such as No. 5, No. 10, No. 15, No. 19, No. 26, No. 29, No. 33, No. 34, No. 35, No. 41, No. 43 and No. 53; CI 瓮 绿 Green No. 1 etc. Dyed dye (vat dye) and the like.
此等染料,可配合所預定之濾色器的分光光譜適當地選擇。 These dyes can be appropriately selected in accordance with the spectroscopic spectrum of the predetermined color filter.
染料(A1),以呫噸(xanthene)染料(Aa)為佳。 The dye (A1) is preferably a xanthene dye (Aa).
呫噸染料(Aa),係含有分子內具有呫噸骨架之化合物的染料。該呫噸染料(Aa)之例,可列舉如:C.I.酸性紅51號(以下,省略C.I.酸性紅之記載,只記載編號。其他亦相同)、52號、87號、92號、94號、289號、388號;C.I.酸性紫9號、30號、102號;C.I.鹼性紅1 號(玫瑰紅6G)、2號、3號、4號、8號;C.I.鹼性紅10號(玫瑰紅B)、11號;C.I.鹼性紫10號、11號、25號;C.I.溶劑紅218號;C.I.媒染紅27號;C.I.活性紅36號(孟加拉玫瑰紅B);磺酸基玫瑰紅G;JP2010-32999-A中所載之呫噸染料及JP4492760-B中所載之呫噸染料等。其中以在有機溶劑中溶解者為佳。 Xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (Aa) include CI Acid Red No. 51 (hereinafter, the description of CI acid red is omitted, only the number is described. Others are the same), No. 52, No. 87, No. 92, No. 94, No. 289, No. 388; CI Acid Violet No. 9, No. 30, No. 102; CI alkaline red 1 No. (Rose Red 6G), No. 2, No. 3, No. 4, No. 8; CI Alkaline Red No. 10 (Rose Red B), No. 11; CI Alkaline Violet No. 10, No. 11, No. 25; CI Solvent Red No. 218; CI mordant red No. 27; CI active red No. 36 (Bangladesh rose red B); sulfonate rose red G; JP2010-32999-A xanthene dye contained in JP2010-32999-A and xanthene contained in JP4492760-B Dyes, etc. Among them, those dissolved in an organic solvent are preferred.
此等之中,呫噸染料(Aa)方面,以含有式(1a)所示之化合物(以下,亦有稱為「化合物(1a)」之情形)之染料較佳。在使用化合物(1a)時,呫噸染料(Aa)中之化合物(1a)之含量以50質量%以上為佳,70質量%以上更佳,90質量%以上又更佳。特別是呫噸染料(Aa),以單獨使用化合物(1a)較佳。 Among these, in terms of the xanthene dye (Aa), a dye containing a compound represented by the formula (1a) (hereinafter also referred to as "the compound (1a)") is preferred. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. In particular, the xanthene dye (Aa) is preferably used singly as the compound (1a).
R5表示-OH、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2 -Z+、-CO2R8、-SO3R8或-SO2NR9R10。 R 5 represents -OH, -SO 3 - , -SO 3 H, -SO 3 - Z + , -CO 2 H, -CO 2 - Z + , -CO 2 R 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 .
R6及R7各別獨立地表示氫原子或碳數1至6之烷基。 R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m表示0至5之整數。m為2以上之整數時,複數個 之R5為相同或不同。惟在R5為-SO3 -時,m為1。 m represents an integer from 0 to 5. When m is an integer of 2 or more, a plurality of R 5 are the same or different. However, when R 5 is -SO 3 - , m is 1.
a表示0或1之整數。 a represents an integer of 0 or 1.
X表示鹵素原子。 X represents a halogen atom.
R8表示碳數1至20之1價飽和烴基,該飽和烴基中所含之氫原子可經由鹵素原子取代。 R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted via a halogen atom.
Z+表示+N(R11)4、Na+或K+。 Z + represents + N(R 11 ) 4 , Na + or K + .
R9及R10各別獨立地表示氫原子或碳數1至20之1價飽和烴基,R9及R10亦可互相鍵結而與氮原子共同形成3至10員環之含氮雜環。 R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R 9 and R 10 may be bonded to each other to form a nitrogen-containing heterocyclic ring having a ring of 3 to 10 members with a nitrogen atom. .
R11各別獨立地表示氫原子、碳數1至20之1價飽和烴基或碳數7至10之芳烷基]。 R 11 each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
R1至R4所表示之碳數6至10之1價芳烴基,可例舉如:苯基、甲苯甲醯基、二甲苯基、2,4,6-三甲苯基、丙苯基及丁苯基。 The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 1 to R 4 may, for example, be a phenyl group, a tolylmethyl group, a xylyl group, a 2,4,6-trimethylphenyl group or a propylphenyl group. Butyl phenyl.
R1至R4所表示之碳數6至10之1價芳烴基,該芳烴基中所含之氫原子亦可經下述者取代:鹵素原子、-R8、-OH、-OR8、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2R8、-SR8、-SO3R8或-SO2NR9R10。此等取代基中,以由-SO3 -、-SO3H、-SO3 -Z+及-SO2NR9R10所形成之群中所選擇之至少1種為佳,由-SO3 -Z+及-SO2NR9R10所形成之群中所選擇之至少1種更佳。在該情形時-SO3 -Z+,以-SO3 -+N(R11)4為佳。在R1至R4係該等基時,含有化合物(1a)之著色硬化性樹脂組成物,可形成異物之產生少,且耐熱性優異的濾色器。 a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 1 to R 4 , and a hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a halogen atom, -R 8 , -OH, -OR 8 , -SO 3 - , -SO 3 H, -SO 3 - Z + , -CO 2 H, -CO 2 R 8 , -SR 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 . Among these substituents, at least one selected from the group consisting of -SO 3 - , -SO 3 H, -SO 3 - Z + and -SO 2 NR 9 R 10 is preferred, and -SO 3 - at least one selected from the group consisting of Z + and -SO 2 NR 9 R 10 is more preferred. In this case, -SO 3 - Z + is preferably -SO 3 -+ N(R 11 ) 4 . When R 1 to R 4 are such a group, the colored curable resin composition containing the compound (1a) can form a color filter having less generation of foreign matter and excellent heat resistance.
R1及R2可與氮原子共同形成含氮原子之環;R3及R4 可與氮原子共同形成含氮原子之環。該含氮原子之環,可例舉如以下者。 R 1 and R 2 may form a ring containing a nitrogen atom together with a nitrogen atom; and R 3 and R 4 may form a ring containing a nitrogen atom together with a nitrogen atom. The ring containing a nitrogen atom may, for example, be the following.
R8至R11所表示之碳數1至20之1價飽和烴基,可例舉如:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二碳烷基、十六碳烷基、二十碳烷基等直鏈狀烷基;異丙基、異丁基、異戊基、新戊基、2-乙基己基等支鏈狀烷基;環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等碳數3至20之脂環式飽和烴基。 The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 8 to R 11 may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group or a decyl group. a linear alkyl group such as a decyl group, a dodecyl group, a hexadecyl group or an eicosyl group; a branch such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group or a 2-ethylhexyl group; A chain alkyl group; a cyclopropyl saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.
-OR8,可例舉如:甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、2-乙基己氧基及二十碳烷氧基。 -OR 8 , which may, for example, be methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and Decaalkoxy.
-CO2R8,可例舉如:甲氧羰基、乙氧羰基、丙氧羰基、第三丁氧羰基、己氧羰基及二十碳烷氧羰基。 -CO 2 R 8 may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group or an eicosyloxycarbonyl group.
-SR8,可例舉如:甲硫基、乙硫基、丁硫基、己硫基、癸硫基及二十碳烷硫基。 -SR 8 may, for example, be a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, an anthracenylthio group or an eicosylthio group.
-SO2R8,可例舉如:甲磺醯基、乙磺醯基、丁磺醯基、己磺醯基、癸磺醯基及二十碳烷磺醯基。 -SO 2 R 8 may, for example, be a methylsulfonyl group, an ethylsulfonyl group, a butasulfonyl group, a hexylsulfonyl group, a sulfonyl group or an eicosylsulfonyl group.
-SO3R8,可例舉如:甲氧磺醯基、乙氧磺醯基、丙氧磺醯基、第三丁氧磺醯基、己氧磺醯基及二十碳烷氧磺醯基。 -SO 3 R 8 , which may, for example, be methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, third butoxysulfonyl, hexoxasulfonyl and eicosyloxasulfonate base.
-SO2NR9R10,可例舉如:胺磺醯基;N-甲胺磺醯基、N-乙胺磺醯基、N-丙胺磺醯基、N-異丙胺磺醯基、N-丁胺 磺醯基、N-異丁胺磺醯基、N-第二丁胺磺醯基、N-第三丁胺磺醯基、N-戊胺磺醯基、N-(1-乙丙基)胺磺醯基、N-(1,1-二甲丙基)胺磺醯基、N-(1,2-二甲丙基)胺磺醯基、N-(2,2-二甲丙基)胺磺醯基、N-(1-甲丁基)胺磺醯基、N-(2-甲丁基)胺磺醯基、N-(3-甲丁基)胺磺醯基、N-環戊胺磺醯基、N-己胺磺醯基、N-(1,3-二甲丁基)胺磺醯基、N-(3,3-二甲丁基)胺磺醯基、N-庚胺磺醯基、N-(1-甲己基)胺磺醯基、N-(1,4-二甲戊基)胺磺醯基、N-辛胺磺醯基、N-(2-乙基己基)胺磺醯基、N-(1,5-二甲己基)胺磺醯基、N-(1,1,2,2-四甲丁基)胺磺醯基等N-1取代胺磺醯基;N,N-二甲胺磺醯基、N,N-乙甲胺磺醯基、N,N-二乙胺磺醯基、N,N-丙甲胺磺醯基、N,N-異丙甲胺磺醯基、N,N-第三丁甲胺磺醯基、N,N-丁乙胺磺醯基、N,N-雙(1-甲丙基)胺磺醯基、N,N-庚甲胺磺醯基等N,N-2取代胺磺醯基等。 -SO 2 NR 9 R 10 , which may, for example, be an amine sulfonyl group; N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N-isopropylamine sulfonyl group, N -butylamine sulfonyl, N-isobutylamine sulfonyl, N-second butyl sulfonyl, N-third butyl sulfonyl, N-pentyl sulfonyl, N-(1-B Propyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dipropylpropyl)aminesulfonyl, N-(2,2-di Methyl propyl) sulfonyl, N-(1-methylbutyl) sulfonyl, N-(2-methylbutyl) sulfonyl, N-(3-methylbutyl) sulfonyl , N-cyclopentylsulfonyl, N-hexylaminesulfonyl, N-(1,3-dimethylbutyl)sulfonyl, N-(3,3-dimethylbutyl)aminesulfonate , N-heptylsulfonyl, N-(1-methylhexyl)aminesulfonyl, N-(1,4-dimethylpentyl)aminesulfonyl, N-octylsulfonyl, N- (2-ethylhexyl)amine sulfonyl, N-(1,5-dimethylhexyl)amine sulfonyl, N-(1,1,2,2-tetramethylbutyl)sulfonyl, etc. -1 substituted amine sulfonyl; N,N-dimethylamine sulfonyl, N,N-ethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N-propylamine sulfonium Base, N,N-isopropylmethamine sulfonyl, N,N-t-butylammoniosulfonyl, N,N-butylethylamine sulfonate , N, N- bis (1-methylpropyl) amine sulfonamide acyl, N, N- methylamine sulfo-heptyl and the like acyl N, N-2-substituted amine sulfonamide acyl and the like.
同時,R9及R10所表示之碳數1至20的1價飽和烴基,該飽和烴基中所含之氫原子可經-OH或鹵素原子取代,該飽和烴基中所含之-CH2-可經-O-、-CO-、-NH-或-NR8-取代。 Meanwhile, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 9 and R 10 , and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with -OH or a halogen atom, and -CH 2 - contained in the saturated hydrocarbon group It may be substituted by -O-, -CO-, -NH- or -NR 8 -.
R9及R10亦可互相鍵結而與氮原子共同形成3至10員環之含氮雜環。該雜環,可例舉以下者。 R 9 and R 10 may also be bonded to each other to form a nitrogen-containing heterocyclic ring of 3 to 10 membered rings together with a nitrogen atom. The heterocyclic ring can be exemplified by the following.
R6及R7所表示之碳數1至6的烷基,可例舉上述所例舉之直鏈狀烷基及支鏈狀烷基之中,碳數為1至6者。 The alkyl group having 1 to 6 carbon atoms represented by R 6 and R 7 may, for example, be a linear alkyl group or a branched alkyl group exemplified above and having 1 to 6 carbon atoms.
R11所表示之碳數7至10的芳烷基,可例舉如:苯甲 基、苯乙基、苯丁基等。 The aralkyl group having 7 to 10 carbon atoms represented by R 11 may, for example, be a benzyl group, a phenethyl group or a phenylbutyl group.
Z+為+N(R11)4、Na+或K+,而以+N(R11)4為佳。 Z + is + N(R 11 ) 4 , Na + or K + , and + N(R 11 ) 4 is preferred.
前述之+N(R11)4,以4個R11中至少2個係碳數5至20之1價飽和烴基為佳。同時,4個R11合計之碳數以20至80為佳,20至60較佳。在R11係該等基時,含有化合物(1a)之著色硬化性樹脂組成物,可形成異物少之濾色器。 In the above-mentioned + N(R 11 ) 4 , it is preferred that at least two of the four R 11 are a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Meanwhile, the total number of carbons of the four R 11 is preferably from 20 to 80, and preferably from 20 to 60. When R 11 is such a group, the colored curable resin composition of the compound (1a) is contained, and a color filter having a small amount of foreign matter can be formed.
m以1至4為佳,1或2更佳。 m is preferably 1 to 4, and 1 or 2 is more preferred.
呫噸染料(Aa)方面,以含有式(2a)所示之化合物(以下亦有情形稱為「化合物(2a)」)的染料較佳。在使用化合物(2a)時,呫噸染料(Aa)中之化合物(2a)之含量以50質量%以上為佳,70質量%以上更佳,90質量%以上又更佳。 In the case of the xanthene dye (Aa), a dye containing a compound represented by the formula (2a) (hereinafter also referred to as "compound (2a)") is preferred. When the compound (2a) is used, the content of the compound (2a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.
R25表示-SO3 -、-SO3H、-SO3 -Z1+或-SO2NHR26。 R 25 represents -SO 3 - , -SO 3 H, -SO 3 - Z1 + or -SO 2 NHR 26 .
m1表示0至5之整數。m1為2以上之整數時,複數個之R25為相同或不同。惟在R25為-SO3 -時,m1為1。 M1 represents an integer from 0 to 5. When m1 is an integer of 2 or more, a plurality of R 25 are the same or different. However, when R 25 is -SO 3 - , m1 is 1.
a1表示0或1之整數。 A1 represents an integer of 0 or 1.
X1表示鹵素原子。 X1 represents a halogen atom.
R26表示碳數1至20之1價飽和烴基。 R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z1+表示+N(R27)4、Na+或K+。 Z1 + represents + N(R 27 ) 4 , Na + or K + .
R27各別獨立地表示碳數1至20之1價飽和烴基或苯甲基]。 R 27 each independently represents a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms.
R21至R24所表示之碳數6至10之1價芳烴基,可舉與前述R1至R4所舉之芳烴基的例子同樣之基。該芳烴基中所含之氫原子可經-SO3 -、-SO3H、-SO3 -Z1+、-SO3R26或-SO2NHR26取代。 The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 21 to R 24 may be the same as those exemplified as the above-mentioned aromatic hydrocarbon group represented by R 1 to R 4 . The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with -SO 3 - , -SO 3 H, -SO 3 - Z1 + , -SO 3 R 26 or -SO 2 NHR 26 .
R21至R24之組合,以R21及R23係氫原子,R22及R24係碳數6至10之1價芳烴基,且該芳烴基中所含之氫原子可經-SO3 -、-SO3H、-SO3 -Z1+、-SO3R26或-SO2NHR26取代者為佳。再更佳之組合,係R21及R23係氫原子,R22及R24係碳數6至10之1價芳烴基,且該芳烴基中所含之氫原子可經-SO3 -Z1+或-SO2NHR26取代者。 a combination of R 21 to R 24 such that R 21 and R 23 are a hydrogen atom, R 22 and R 24 are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group may pass through -SO 3 - , -SO 3 H, -SO 3 - Z1 + , -SO 3 R 26 or -SO 2 NHR 26 is preferred. Further preferably, R 21 and R 23 are hydrogen atoms, R 22 and R 24 are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be -SO 3 - Z1 + Or -SO 2 NHR 26 replacement.
同時,又以R21及R22與氮原子共同形成含氮原子之脂肪族雜環,且R23及R24與氮原子共同形成含氮原子之脂肪族雜環者為佳。 Meanwhile, it is preferred that R 21 and R 22 together with a nitrogen atom form an aliphatic heterocyclic ring containing a nitrogen atom, and R 23 and R 24 together with a nitrogen atom form an aliphatic heterocyclic ring containing a nitrogen atom.
在R21至R24係該等基時,含有化合物(2a)之著色硬化性樹脂組成物,可形成耐熱性優異之濾色器。 When R 21 to R 24 are such a group, the colored curable resin composition containing the compound (2a) can form a color filter excellent in heat resistance.
前述脂肪族雜環,可例舉如下述者。 The aliphatic heterocyclic ring may, for example, be as follows.
R26及R27所示之碳數1至20的1價飽和烴基,可例舉 與R8至R11中所例舉之飽和烴基的例子同樣之基。 The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 26 and R 27 may be the same as those exemplified as the saturated hydrocarbon group exemplified in R 8 to R 11 .
R21至R24中之-R26,各別獨立地以氫原子、甲基或乙基為佳。同時,-SO3R26及-SO2NHR26中之R26,以碳數3至20之支鏈狀烷基為佳,碳數6至12之支鏈狀烷基更佳,2-乙基己基又更佳。在R26係該等基時,含有化合物(2a)之著色硬化性樹脂組成物,可形成異物產生少的濾色器。 R 21 to R -R in the 2426, in order to individually independently a hydrogen atom, preferably methyl or ethyl. Meanwhile, -SO 3 R 26, and in the -SO 2 NHR 26 R 26, carbon atoms in a branched chain alkyl group having 3 to 20 preferably of a carbon number of 6 to 12 branched alkyl group more preferably, 2-ethyl The base is better. When R 26 is such a group, the colored curable resin composition containing the compound (2a) can form a color filter having little foreign matter.
Z1+係+N(R27)4、Na+或K+,而以+N(R27)4為佳。 Z1 + is + N(R 27 ) 4 , Na + or K + , and + N(R 27 ) 4 is preferred.
前述之+N(R27)4,以4個R27中至少2個係碳數5至20之1價飽和烴基為佳。同時,4個R27之合計碳數以20至80為佳,20至60更佳。含有R27係該等基之化合物(2a)的著色硬化性樹脂組成物,可形成異物產生少之濾色器。 In the above-mentioned + N(R 27 ) 4 , it is preferred that at least two of the four R 27 are a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Meanwhile, the total carbon number of the four R 27 is preferably from 20 to 80, more preferably from 20 to 60. The color-curable resin composition containing the compound (2a) having R 27 -based groups can form a color filter having little foreign matter.
m1以1至4為佳,1或2更佳。 M1 is preferably from 1 to 4, more preferably from 1 or 2.
化合物(2a),可例舉如:式(1-1)至式(1-25)所示之化合物。同時,式中,R26表示碳數1至20之1價飽和烴基,而以碳數6至12之支鏈狀烷基為佳,2-乙基己基又更佳。該等之中,以C.I.酸性紅289之磺醯胺化物、C.I.酸性紅289之4級銨鹽、C.I.酸性紫102之磺醯胺化物、或C.I.酸性紫102之4級銨鹽為佳。此類化合物,可例舉如:式(1-1)至式(1-8)、式(1-11)及式(1-12)所示之化合物等。 The compound (2a) may, for example, be a compound represented by the formula (1-1) to the formula (1-25). Meanwhile, in the formula, R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably 2-ethylhexyl group. Among these, a sulfonamide of CI Acid Red 289, a 4-grade ammonium salt of CI Acid Red 289, a sulfonamide of CI Acid Violet 102, or a 4-grade ammonium salt of CI Acid Violet 102 is preferred. Such a compound may, for example, be a compound represented by the formula (1-1) to the formula (1-8), the formula (1-11) and the formula (1-12).
此外,呫噸染料(Aa),係以含有式(3a)所示之化合物(以下亦有情形稱為「化合物(3a)」)的染料較佳。在使用化合物(3a)時,呫噸染料(Aa)中之化合物(3a)之含量以50質量%以上為佳,70質量%以上更佳,90質量%以上又更佳。 Further, the xanthene dye (Aa) is preferably a dye containing a compound represented by the formula (3a) (hereinafter also referred to as "compound (3a)"). When the compound (3a) is used, the content of the compound (3a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.
R33及R34各別獨立地表示碳數1至4之烷基、碳數1 至4之烷基硫基或碳數1至4之烷基磺醯基。 R 33 and R 34 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms.
R31及R33可與氮原子共同形成含氮原子之環;R32及R34可與氮原子共同形成含氮原子之環。 R 31 and R 33 may form a ring containing a nitrogen atom together with a nitrogen atom; R 32 and R 34 may form a ring containing a nitrogen atom together with a nitrogen atom.
p及q互相獨立地表示0至5之整數。p為2以上時,複數個之R33可相同亦可不同;q為2以上時,複數個之R34可相同亦可不同]。 p and q independently represent each other from 0 to 5. When p is 2 or more, a plurality of R 33 may be the same or different; and when q is 2 or more, a plurality of R 34 may be the same or different.
R31、R32、R33及R34所表示之碳數1至4之烷基,可例舉如:甲基、乙基、丙基、丁基、異丙基、異丁基、第二丁基、第三丁基等。 The alkyl group having 1 to 4 carbon atoms represented by R 31 , R 32 , R 33 and R 34 may, for example, be methyl, ethyl, propyl, butyl, isopropyl, isobutyl or the like. Butyl, tert-butyl, and the like.
R33及R34所表示之碳數1至4之烷基硫基,可例舉如:甲基硫基、乙基硫基、丙基硫基、丁基硫基、異丙基硫基等。 The alkylthio group having 1 to 4 carbon atoms represented by R 33 and R 34 may, for example, be a methylthio group, an ethylthio group, a propylthio group, a butylthio group or an isopropylthio group. .
R33及R34所表示之碳數1至4之烷基磺醯基,可例舉如:甲基磺醯基、乙基磺醯基、丙基磺醯基、丁基磺醯基、異丙基磺醯基等。 The alkylsulfonyl group having 1 to 4 carbon atoms represented by R 33 and R 34 may, for example, be methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl or the like. Propylsulfonyl and the like.
R31及R32係以互相獨立地表示甲基及乙基為佳。R33及R34以碳數1至4之烷基為佳,甲基更佳。 R 31 and R 32 are preferably each independently represent a methyl group and an ethyl group. R 33 and R 34 are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
m及n以0至2之整數為佳,0或1更佳。 m and n are preferably an integer of 0 to 2, and 0 or 1 is more preferable.
化合物(3a),可例舉如分別以式(1-26)至式(1-32)所示之化合物。其中,由對有機溶劑之溶解性較佳之觀點而言,以式(1-26)所示之化合物較佳。 The compound (3a) may, for example, be a compound represented by the formula (1-26) to the formula (1-32), respectively. Among them, a compound represented by the formula (1-26) is preferred from the viewpoint of better solubility in an organic solvent.
呫噸染料(Aa)方面,可使用市售之呫噸染料(例如中外化成股份有限公司製造之「Chugai Aminol Fast Pink R-H/C」、田岡化學工業股份有限公司製造之「Rhodamin 6G」)。此外,以市售之呫噸染料為起始原料,再參考JP2010-32999-A進行合成者亦可。 For the xanthene dye (Aa), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Sino-foreign Chemicals Co., Ltd., and "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd.) can be used. In addition, the commercially available xanthene dye is used as a starting material, and the synthesis may be carried out by referring to JP2010-32999-A.
顏料(A2),可例舉如依照比色指數(The Society of Dyers and Colourists出版)分類為顏料之化合物。 The pigment (A2) may, for example, be a compound classified as a pigment according to a colorimetric index (published by The Society of Dyers and Colourists).
顏料(A2),可例舉如:C.I.顏料黃1號、3號、12號、13號、14號、15號、 16號、17號、20號、24號、31號、53號、83號、86號、93號、94號、109號、110號、117號、125號、128號、137號、138號、139號、147號、148號、150號、153號、154號、166號、173號、180號、185號、194號、214號、219號等黃色顏料;C.I.顏料橙13號、31號、36號、38號、40號、42號、43號、51號、55號、59號、61號、64號、65號、71號、73號等橙色顏料;C.I.顏料紅9號、97號、105號、122號、123號、144號、149號、166號、168號、175號、176號、177號、180號、192號、209號、215號、216號、224號、242號、254號、255號、264號、265號等紅色顏料;C.I.顏料藍15號、15:3號、15:4號、15:6號、60號、80號等藍色顏料;C.I.顏料紫1號、19號、23號、29號、32號、36號、38號等紫色顏料;C.I.顏料綠7號、36號、58號等綠色顏料;C.I.顏料棕23號、25號等棕色顏料;C.I.顏料黑1號、7號等黑色顏料等。 The pigment (A2) may, for example, be C.I. Pigment Yellow No. 1, No. 3, No. 12, No. 13, No. 14, No. 15, No. 16, No. 17, No. 20, No. 31, No. 53, No. 83, No. 86, No. 93, No. 94, No. 109, No. 110, No. 117, No. 125, No. 128, No. 137, No. 138 , 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194, 214, 219 and other yellow pigments; CI Pigment Orange No. 13, 31 No. 36, No. 38, No. 40, No. 42, No. 43, No. 51, No. 55, No. 59, No. 61, No. 64, No. 65, No. 71, No. 73 and other orange pigments; CI Pigment Red No. 9, Nos. 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224 , red pigments such as No. 242, No. 254, No. 255, No. 264, No. 265; blue pigments such as CI Pigment Blue No. 15, No. 15, No.: No. 15, No.: No. 15, No.: No.: No.: No. 60, No. 80; CI Pigment Violet No. 1, No. 19, No. 23, No. 29, No. 32, No. 36, No. 38 and other purple pigments; CI Pigment Green No. 7, No. 36, No. 58 and other green pigments; CI Pigment Brown No. 23, No. 25 Such as brown pigment; CI pigment black, No. 1, No. 7 and other black pigments.
本發明之著色硬化性樹脂組成物在調配成藍色著色硬化性樹脂組成物時,顏料係以C.I.顏料藍15號、15:3號、15:4號、15:6號、60號等藍色顏料及C.I.顏料紫1號、19號、23號、29號、32號、36號、38號等紫色顏料為佳,C.I.顏料藍15:3號、15:6號及C.I.顏料紫23號更佳,C.I.顏料藍15:6號又更佳。 When the colored curable resin composition of the present invention is formulated into a blue colored curable resin composition, the pigments are CI Pigment Blue No. 15, No. 15, No.: No. 15, No.: No. 15, No.: No. 15, No.: No.: No. 60, No. 60, etc. Color pigments and CI Pigment Violet No. 1, No. 19, No. 23, No. 29, No. 32, No. 36, No. 38, etc. Purple pigments are preferred. CI Pigment Blue Nos. 15:3, 15:6 and CI Pigment Violet No.23 Better, CI Pigment Blue 15:6 is even better.
本發明之著色硬化性樹脂組成物在調配成綠色著色硬化性樹脂組成物時,顏料係以C.I.顏料綠7號、36號、58號等綠色顏料及C.I.顏料黃138號、139號、150號等黃色顏料為佳。 When the colored curable resin composition of the present invention is formulated into a green colored curable resin composition, the pigment is a green pigment such as CI Pigment Green No. 7, No. 36, No. 58, and CI Pigment Yellow No. 138, No. 139, No. 150 It is better to wait for yellow pigments.
本發明之著色硬化性樹脂組成物在調配成紅色著色硬化性樹脂組成物時,顏料係以C.I.顏料紅177號、209號、242號、254號、255號等紅色顏料、C.I.顏料橙38號、43號、71號等橙色顏料及C.I.顏料黃138號、139號、150號等黃色顏料為佳。 When the colored curable resin composition of the present invention is formulated into a red colored curable resin composition, the pigment is a red pigment such as CI Pigment Red No. 177, No. 209, No. 242, No. 254, No. 255, and CI Pigment Orange No. 38. Yellow pigments such as No. 43, No. 71 and the like, and yellow pigments such as No. 138, No. 139 and No. 150 of CI Pigment Yellow are preferred.
在含有前述顏料時,透射光譜之最適化容易,且濾色器之耐光性及耐藥品性更佳。 When the pigment is contained, the optimum of the transmission spectrum is easy, and the color resistance and chemical resistance of the color filter are better.
顏料(A2),可依照需要,再施行:松脂處理、使用導入酸性基或鹼性基之顏料衍生物等之表面處理、以高分子化合物等對顏料表面進行接枝(graft)處理、以硫酸微粒化法等進行之微粒化處理、或用以使不純物去除之由有機溶劑及水等進行之洗淨處理、離子性不純物之由離子交換法等進行之去除處理等。 The pigment (A2) can be further subjected to a rosin treatment, a surface treatment using a pigment derivative or the like, or a grafting treatment of a pigment surface with a polymer compound or the like, and a sulfuric acid treatment. The micronization treatment by a micronization method or the like, the cleaning treatment by an organic solvent or water for removing impurities, the removal treatment of an ionic impurity by an ion exchange method, or the like.
顏料(A2)以粒徑均勻者為佳。含有顏料分散劑而進行分散處理時,可得到顏料在溶液中形成均勻地分散之狀態的顏料分散液。 The pigment (A2) is preferably one having a uniform particle diameter. When the dispersion treatment is carried out by containing a pigment dispersant, a pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained.
前述顏料分散劑,可例舉如: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。此類顏料分散劑,可單獨亦可以2種以上組合使用。顏料分散劑,可例舉如商品名: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(味之素精技股份有限公司製造)、Disperbyk(BYK公司製造)等。 The pigment dispersant may, for example, be a cationic dispersant such as a cationic system, an anionic system, a nonionic system, an amphoteric acid, a polyester system, a polyamine system or an acrylic resin. These pigment dispersants may be used alone or in combination of two or more. The pigment dispersing agent can be exemplified by a trade name: KP (Shin-Etsu Chemical Industry Co., Ltd. has Limited company manufacturing), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), AJISPER (manufactured by Ajinomoto Co., Ltd.), Disperbyk (BYK) Manufacturing) and so on.
在使用顏料分散劑時,其使用量相對於顏料(A2),以1質量%以上100質量%以下為佳,5質量%以上50質量%以下更佳。顏料分散劑之使用量在前述範圍時,有得到均勻之分散狀態的顏料分散液之傾向。 When the pigment dispersant is used, the amount thereof is preferably 1% by mass or more and 100% by mass or less based on the pigment (A2), and more preferably 5% by mass or more and 50% by mass or less. When the amount of the pigment dispersant used is in the above range, there is a tendency to obtain a pigment dispersion liquid in a uniformly dispersed state.
染料(A1)及顏料(A2)之含量比例依質量基準係以1:99至99:1為佳,1:99至70:30更佳,2:98至50:50又更佳。藉由如此比例,使透射光譜之最適化容易,而有使所得之濾色器在對比、明度、耐熱性及耐藥品性方面更佳之傾向。 The content ratio of the dye (A1) and the pigment (A2) is preferably from 1:99 to 99:1, more preferably from 1:99 to 70:30, still more preferably from 2:98 to 50:50. By such a ratio, the optimization of the transmission spectrum is easy, and the obtained color filter tends to be better in comparison, brightness, heat resistance, and chemical resistance.
特別是,著色劑(A),以含有呫噸染料(Aa)及藍色顏料之著色劑為佳,含有呫噸染料(Aa)及C.I.顏料藍15:6號之著色劑更佳。呫噸染料(Aa)與藍色顏料之含量比例依質量基準係以1:99至70:30為佳,2:98至50:50更佳。 In particular, the coloring agent (A) is preferably a coloring agent containing a xanthene dye (Aa) and a blue pigment, and a coloring agent containing a xanthene dye (Aa) and a C.I. pigment blue 15:6 is more preferable. The content ratio of the xanthene dye (Aa) to the blue pigment is preferably from 1:99 to 70:30, more preferably from 2:98 to 50:50, depending on the mass basis.
著色劑(A)之含量,相對於固形份之總量,以5至60質量%為佳,8至50質量%更佳,10至40質量%又更佳。著色劑(A)之含量在前述範圍內時,在形成濾色器時之色濃度充分,且可使組成物中含有需要量之樹脂(B)及聚合性化合物(C),因此可形成機械強度完全之濾色器。 The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 50% by mass, still more preferably from 10 to 40% by mass, based on the total amount of the solid portion. When the content of the coloring agent (A) is within the above range, the color density at the time of forming the color filter is sufficient, and the required amount of the resin (B) and the polymerizable compound (C) can be contained in the composition, so that the machine can be formed. Full color filter.
其中,本說明書中所謂之「固形份之總量」,意指由著色硬化性樹脂組成物之總量去除溶劑含量的量。固形份之 總量及相對於固形份之總量之各成分之含量,可例如以液相層析或氣相層析等一般所知之分析手段加以測定。 Here, the "total amount of solid content" as used herein means the amount by which the solvent content is removed from the total amount of the colored curable resin composition. Solid part The total amount and the content of each component relative to the total amount of the solid fraction can be measured, for example, by a generally known analytical means such as liquid chromatography or gas chromatography.
樹脂(B)方面,並無特別之限定,惟以鹼可溶性樹脂為佳。樹脂(B)方面,可例舉如以下之樹脂[K1]至[K6]等。 The resin (B) is not particularly limited, and an alkali-soluble resin is preferred. The resin (B) may, for example, be the following resins [K1] to [K6].
樹脂[K1]係不飽和羧酸及不飽和羧酸酐所形成之群中所選擇之至少1種(a)(以下亦有稱之為「(a)」之情形)、與具有碳數2至4之環醚結構及乙烯性不飽和鍵之單體(b)(以下亦有稱之為「(b)」之情形)之共聚物;樹脂[K2]係(a)及(b)、與可與(a)共聚之單體(c)(惟(a)與(b)不同)(以下亦有稱之為「(c)」之情形)之共聚物;樹脂[K3]係(a)與(c)之共聚物;樹脂[K4]係(a)與(c)之共聚物再以(b)反應之樹脂;樹脂[K5]係(b)與(c)之共聚物再以(a)反應之樹脂;樹脂[K6]係(b)與(c)之共聚物再以(a)進行反應,並以羧酸酐反應之樹脂。 The resin [K1] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter also referred to as "(a)"), and has a carbon number of 2 to a copolymer of a cyclic ether structure of 4 and an ethylenically unsaturated bond (b) (hereinafter also referred to as "(b)"); a resin [K2] (a) and (b), and a copolymer which can be copolymerized with (a) monomer (c) (other than (a) and (b)) (hereinafter also referred to as "(c)"); resin [K3] (a) Copolymer with (c); resin [K4] is a copolymer of (a) and (c) and then reacted with (b); resin [K5] is a copolymer of (b) and (c) a) Resin of the reaction; resin [K6] is a resin obtained by reacting the copolymer of (b) and (c) with (a) and reacting with a carboxylic acid anhydride.
(a)方面,具體上可例舉如:丙烯酸、甲基丙烯酸、巴豆酸,鄰-、間-、對-乙烯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-乙烯鄰苯二甲酸、4-乙烯鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲四氫鄰苯二甲酸、1,4-環己烯二羧酸等不飽和二羧酸類;甲-5-降莰烯-2,3-二羧酸、5-羧雙環[2.2.1]庚-2-烯、5,6- 二羧雙環[2.2.1]庚-2-烯、5-羧-5-甲雙環[2.2.1]庚-2-烯、5-羧-5-乙雙環[2.2.1]庚-2-烯、5-羧-6-甲雙環[2.2.1]庚-2-烯、5-羧-6-乙雙環[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-乙烯鄰苯二甲酸酐、4-乙烯鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲四氫鄰苯二甲酸酐、去水5,6-二羧雙環[2.2.1]庚-2-烯等不飽和二羧酸酐類;琥珀酸單[2-(甲基)丙烯醯氧乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧乙基]酯等2元以上之多元羧酸的不飽和單[(甲基)丙烯醯氧烷基]酯類;如α-(羥甲基)丙烯酸之類,同一分子中含有羥基及羧基的不飽和丙烯酸酯類等。 (a), specifically, for example, acrylic acid, methacrylic acid, crotonic acid, ortho-, m-, p-vinylbenzoic acid and the like unsaturated monocarboxylic acid; maleic acid, fumaric acid , citraconic acid, mesaconic acid, itaconic acid, 3-ethylene phthalic acid, 4-ethylene phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3, Unsaturated dicarboxylic acids such as 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-northene-2,3-dicarboxylic acid 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6- Dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2- Alkene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds; Butic 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, dimethyltetrahydrophthalic anhydride, dehydrated 5,6-dicarboxybicyclo[2.2.1]hept-2-ene and other unsaturated dicarboxylic anhydrides; Unsaturated mono-carboxylic acid of 2 or more polyvalent carboxylic acids such as monosuccinic acid [2-(methyl) propylene oxiranyl] ester, phthalic acid mono [2-(methyl) propylene oxy oxyethyl] ester [ (Methyl) propylene sulfoxyalkyl esters; such as α-(hydroxymethyl)acrylic acid, unsaturated acrylates having a hydroxyl group and a carboxyl group in the same molecule.
此等之中,由共聚反應性之觀點及對鹼水溶液之溶解性之觀點而言,以丙烯酸、甲基丙烯酸、順丁烯二酸酐等為佳。 Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.
又,本說明書中,所謂「(甲基)丙烯醯基」,表示由丙烯醯基及甲基丙烯醯基所形成之群中所選擇之至少1種。「(甲基)丙烯酸」及「(甲基)丙烯酸酯」等表示亦有同樣之意。 In the present specification, the "(meth)acryl fluorenyl group" means at least one selected from the group consisting of an acryloyl group and a methacryl fluorenyl group. The meanings of "(meth)acrylic acid" and "(meth)acrylate" are also the same.
(b)可例舉如:具有碳數2至4之環醚結構(例如,由環氧乙烷環、環氧丙烷環及四氫呋喃環所形成之群中所選擇之至少1種)及乙烯性不飽和鍵之聚合性化合物。(b)以含碳數2至4之環醚結構及(甲基)丙烯醯氧基之單體較佳。 (b) may be, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, a propylene oxide ring, and a tetrahydrofuran ring) and ethylenicity. A polymerizable compound having an unsaturated bond. (b) It is preferred to use a monomer having a cyclic ether structure of 2 to 4 carbon atoms and a (meth)acryloxy group.
又,本說明書中,所謂「(甲基)丙烯酸」,係表示由丙烯酸及甲基丙烯酸所形成之群中所選擇之至少1種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等表示亦有同樣之意。 In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The meanings of "(meth)acrylonitrile" and "(meth)acrylate" are also the same.
(b)之例可舉如:具有環氧乙基及乙烯性不飽和鍵之單體(b1)(以下亦有稱之為「(b1)」之情形)、具有環氧丙基及乙烯性不飽和鍵之單體(b2)(以下亦有稱之為「(b2)」之情形)、具有四氫呋喃基及乙烯性不飽和鍵之單體(b3)(以下亦有稱之為「(b3)」之情形)等。 (b) Examples thereof include a monomer having an epoxyethyl group and an ethylenically unsaturated bond (b1) (hereinafter also referred to as "(b1)"), having an epoxy group and an ethyl group. Monomer of unsaturated bond (b2) (hereinafter also referred to as "(b2)"), monomer having tetrahydrofuranyl group and ethylenically unsaturated bond (b3) (hereinafter also referred to as "(b3) )) and so on.
(b1)可例舉如:具有直鏈狀或支鏈狀之不飽和脂防族烴經過環氧化之結構的單體(b1-1)(以下亦有稱之為「(b1-1)」之情形)及具有不飽和脂環式烴經過環氧化之結構的單體(b1-2)(以下亦有稱之為「(b1-2)」之情形)。 (b1), for example, a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter also referred to as "(b1-1)" In the case of the monomer (b1-2) having an epoxidized structure of an unsaturated alicyclic hydrocarbon (hereinafter also referred to as "(b1-2)").
(b1-1)可例舉如:(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸β-甲基環氧丙酯、(甲基)丙烯酸β-乙基環氧丙酯、環氧丙基乙烯醚、鄰乙烯苯甲基環氧丙醚、間乙烯苯甲基環氧丙醚、對乙烯苯甲基環氧丙醚、α-甲-鄰乙烯苯甲基環氧丙醚、α-甲-間乙烯苯甲基環氧丙醚、α-甲-對乙烯苯甲基環氧丙醚、2,3-雙(環氧丙氧基甲基)苯乙烯、2,4-雙(環氧丙氧基甲基)苯乙烯、2,5-雙(環氧丙氧基甲基)苯乙烯、2,6-雙(環氧丙氧基甲基)苯乙烯、2,3,4-三(環氧丙氧基甲基)苯乙烯、2,3,5-三(環氧丙氧基甲基)苯乙烯、2,3,6-三(環氧丙氧基甲基)苯乙烯、3,4,5-三(環氧丙氧基甲基)苯乙烯、2,4,6-三(環氧丙氧基甲基)苯乙烯等。 (b1-1) may, for example, be a glycidyl (meth)acrylate, a β-methylglycidyl (meth)acrylate, a β-ethylglycidyl (meth)acrylate, or an epoxy. Propyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-phenoxymethyl methacrylate, α -A-m-vinylbenzyloxypropyl ether, α-methyl-p-vinylbenzyloxypropyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-dual ( Glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4 -Tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)benzene Ethylene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.
(b1-2)可例舉如:單氧化乙烯環己烯、1,2-環氧-4-乙烯 環己烷(如Celloxide 2000;Daicel化學工業股份有限公司製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(如Cyclomer A400;Daicel化學工業股份有限公司製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(如Cyclomer M100;Daicel化學工業股份有限公司製造)、式(I)所示之化合物及式(II)所示之化合物等。 (b1-2) may, for example, be: ethylene oxide cyclohexene, 1,2-epoxy-4-ethylene Cyclohexane (such as Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (such as Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), (methyl) 3,4-epoxycyclohexylmethyl acrylate (such as Cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the formula (I), a compound represented by the formula (II), and the like.
Xb1及Xb2表示單鍵、-Rb3-、*-Rb3-O-、*-Rb3-S-或*-Rb3-NH-。 X b1 and X b2 represents a single bond, -R b3 -, * - R b3 -O -, * - R b3 -S- or * -R b3 -NH-.
Rb3表示碳數1至6之烷二基。 R b3 represents an alkanediyl group having 1 to 6 carbon atoms.
*表示與O之鍵結基]。 * indicates a bond with O].
碳數1至4之烷基,可例舉如:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。 The alkyl group having 1 to 4 carbon atoms may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl or t-butyl.
氫原子經羥基取代之烷基,可例舉如:羥甲基、1-羥乙基、2-羥乙基、1-羥丙基、2-羥丙基、3-羥丙基、1-羥-1-甲乙基、2-羥-1-甲乙基、1-羥丁基、2-羥丁基、3-羥丁基、4-羥丁基等。 The alkyl group in which the hydrogen atom is substituted with a hydroxyl group may, for example, be hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1- Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.
Rb1及Rb2,以氫原子、甲基、羥甲基、1-羥乙基或2-羥乙基為佳,以氫原子或甲基更佳。 R b1 and R b2 are preferably a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.
烷二基,可例舉如:亞甲基、伸乙基、丙-1,2-二基、丙-1,3-二基、丁-1,4-二基、戊-1,5-二基、己-1,6-二基等。 The alkanediyl group may, for example, be a methylene group, an ethylidene group, a propionyl-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group or a penta-1,5- Dibasic, hex-1,6-diyl, and the like.
Xb1及Xb2,以單鍵、亞甲基、伸乙基、*-CH2-O-或*-CH2CH2-O-為佳,以單鍵或*-CH2CH2-O-更佳(*表示與O之鍵結基)。 X b1 and X b2 are preferably a single bond, a methylene group, an ethylidene group, a *-CH 2 -O- or a *-CH 2 CH 2 -O- group, and a single bond or *-CH 2 CH 2 -O - Better (* indicates a bond with O).
如式(I)所示之化合物,可例舉如:式(I-1)至式(I-15)所示之任意之化合物等。其中,以式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)及式(I-11)至式(I-15)所示之任意之化合物為佳,以式(I-1)、式(I-7)、式(I-9)及式(I-15)所示之任意之化合物更佳。 The compound represented by the formula (I) may, for example, be any compound represented by the formula (I-1) to the formula (I-15). Wherein, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), and the formula (I-11) to the formula (I-15) Any of the compounds shown is preferred, and any of the compounds represented by the formula (I-1), the formula (I-7), the formula (I-9) and the formula (I-15) is more preferable.
式(II)所示之化合物,可例舉如式(II-1)至式(II-15)所示之任意之化合物等。其中,以式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)及式(II-11)至式(II-15)所示之任意之化合物為佳,以式(II-1)、式(II-7)、式(II-9)及式(II-15)所示之任意之化合物更佳。 The compound represented by the formula (II) may, for example, be any compound represented by the formula (II-1) to the formula (II-15). Wherein, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11) to formula (II-15) Any of the compounds shown is preferred, and any of the compounds represented by the formula (II-1), the formula (II-7), the formula (II-9) and the formula (II-15) is more preferable.
式(I)所示之化合物及式(II)所示之化合物,可分別單獨使用,亦可以任意之比例混合使用。在混合使用時,式(I)所示之化合物及式(II)所示之化合物的含有比例以莫耳基準,以5:95至95:5為佳,10:90至90:10更佳,20:80至80:20又更佳。 The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in any ratio. When used in combination, the compound represented by the formula (I) and the compound represented by the formula (II) are preferably used in a molar ratio of 5:95 to 95:5, preferably 10:90 to 90:10. 20:80 to 80:20 is even better.
具有環氧丙基及乙烯性不飽和鍵之單體(b2),以具有環氧丙基與(甲基)丙烯醯氧基之單體較佳。單體(b2)之例可舉如:3-甲-3-甲基丙烯醯氧基甲基環氧丙烷、3-甲-3-丙烯醯氧基甲基環氧丙烷、3-乙-3-甲基丙烯醯氧基甲基環氧丙烷、3-乙-3-丙烯醯氧基甲基環氧丙烷、3-甲-3-甲基丙烯醯氧基乙基環氧丙烷、3-甲-3-丙烯醯氧基乙基環氧丙烷、3-乙-3-甲基丙烯醯氧基乙基環氧丙烷、3-乙-3-丙烯醯氧基乙基環氧丙烷等。 The monomer (b2) having a glycidyl group and an ethylenically unsaturated bond is preferably a monomer having a glycidyl group and a (meth)acryloxy group. Examples of the monomer (b2) include 3-methyl-3-methylpropenyloxymethyl propylene oxide, 3-methyl-3-propenyloxymethyl propylene oxide, and 3-ethyl-3. -Methacryloxymethoxymethyl propylene oxide, 3-ethyl-3-propenyloxymethyl propylene oxide, 3-methyl-3-methylpropenyloxyethyl propylene oxide, 3-methyl 3-propenyloxyethyl propylene oxide, 3-ethyl-3-methylpropenyloxyethyl propylene oxide, 3-ethyl-3-propenyloxyethyl propylene oxide, and the like.
具有四氫呋喃基及乙烯性不飽和鍵之單體(b3),以具有四氫呋喃基與(甲基)丙烯醯氧基之單體較佳。(b3),具體上可例舉如:丙烯酸四氫呋喃甲酯(如Viscoat V#150,大阪有機化学工業股份有限公司製造)、甲基丙烯酸四氫呋喃甲酯等。 The monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group. (b3), specifically, for example, tetrahydrofuran methyl acrylate (such as Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran methyl methacrylate or the like can be exemplified.
由可使所得之濾色器之耐熱性、耐藥品性等信賴性更高之點而言,(b)以(b1)為佳。另外,在著色硬化性樹脂組成物之保存安定性較佳之點而言,係以(b1-2)較佳。 (b) It is preferable that (b) is (b1) because the heat resistance and chemical resistance of the obtained color filter can be made higher. Further, it is preferable that (b1-2) is preferable in that the storage stability of the colored curable resin composition is good.
(c)可例舉如:(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 二碳烷酯、(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(在該技術領域中,其慣用名稱為「(甲基)丙烯酸二環戊酯」。此外,亦有稱為「(甲基)丙烯酸三環癸酯」之情形)、(甲基)丙烯酸三環[5.2.1.02.6]癸烯-8-酯(在該技術領域中,其慣用名稱為「(甲基)丙烯酸二環戊烯酯」)、(甲基)丙烯酸二環戊氧乙酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸快丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苯甲酯等(甲基)丙烯酸酯類;(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、等含羥基之(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-甲雙環[2.2.1]庚-2-烯、5-乙雙環[2.2.1]庚-2-烯、5-羥雙環[2.2.1]庚-2-烯、5-羥甲雙環[2.2.1]庚-2-烯、5-(2’-羥乙基)雙環[2.2.1]庚-2-烯、5-甲氧雙環[2.2.1]庚-2-烯、5-乙氧雙環[2.2.1]庚-2-烯、5,6-二羥雙環[2.2.1]庚-2-烯、5,6-二(羥甲基)雙環[2.2.1]庚-2-烯、5,6-二(2’-羥乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧雙環[2.2.1]庚-2-烯、5,6-二乙氧雙環[2.2.1]庚-2-烯、5-羥-5-甲雙環[2.2.1]庚-2-烯、5-羥-5-乙雙環[2.2.1]庚-2-烯、5-羥甲-5-甲雙環[2.2.1]庚-2-烯、5-第三丁氧羰基雙環[2.2.1]庚-2-烯、5-環 己氧羰基雙環[2.2.1]庚-2-烯、5-苯氧羰基雙環[2.2.1]庚-2-烯、5,6-二(第三丁氧羰基)雙環[2.2.1]庚-2-烯、5,6-二(環己氧羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物類; (c) may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, or (meth)acrylic acid third Butyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopenta(meth)acrylate Ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2.6 ]decane-8-ester (in the technical field, The conventional name is "dicyclopentanyl (meth) acrylate." In addition, there is also a case called "tricyclodecyl (meth) acrylate), trimethyl (meth) acrylate [5.2.1.0 2.6 ] Terpene-8-ester (commonly known in the art as "dicyclopentenyl (meth)acrylate), dicyclopentyloxy (meth)acrylate, isophthalic acid (meth)acrylate Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth)acrylic acid (meth) acrylate such as benzyl ester; (meth) acrylate 2 - hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, and other hydroxyl-containing (meth) acrylates; diethyl maleate, diethyl fumarate, itaconic acid Dicarboxylic acid diester such as ethyl ester; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-dibicyclo[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]heptane- 2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]heptane- 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-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2. 1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5- Tributyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene , 5,6-di(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, etc. Saturated compound
N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺、3-順丁烯二醯亞胺苯甲酸N-琥珀醯亞胺酯、4-順丁烯二醯亞胺丁酸N-琥珀醯亞胺酯、6-順丁烯二醯亞胺己酸N-琥珀醯亞胺酯、3-順丁烯二醯亞胺丙酸N-琥珀醯亞胺酯、N-(9-吖啶基)順丁烯二醯亞胺等二羰基醯亞胺衍生物類; N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, 3-butenimide benzoic acid N- Amber sulphate, N-succinimide, 4-m-butylene imidate, N-succinimide, 6-maleimide hexanoate, 3-butene a dicarbonyl quinone imine derivative such as N-succinimide, N-(9-acridinyl) maleimide or the like;
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、氯化乙烯、氯化亞乙烯、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-1,3-丁二烯等。 Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, ethylene chloride, vinyl chloride, Acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.
此等之中,由共聚反應性及耐熱性之點而言,以苯乙烯、乙烯基甲苯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺等為佳。 Among these, styrene, vinyl toluene, N-phenyl maleimide, N-cyclohexyl maleimide, N are used in terms of copolymerization reactivity and heat resistance. - Benzyl maleimide or the like is preferred.
樹脂[K1]中,由各來源之結構單元的比例,以構成樹脂[K1]之全結構單元中,源自(a)之結構單元:2至60莫耳%源自(b)之結構單元:40至98莫耳%為佳,源自(a)之結構單元:10至50莫耳%源自(b)之結構單元:50至90莫耳%更佳。 In the resin [K1], the proportion of the structural unit of each source to constitute the structural unit of the resin [K1], the structural unit derived from (a): 2 to 60 mol% of the structural unit derived from (b) 40 to 98 mol% is preferred, structural unit derived from (a): 10 to 50 mol% derived from the structural unit of (b): 50 to 90 mol% is more preferable.
樹脂[K1]之結構單元的比例,在上述範圍時,有使著色硬化性樹脂組成物之保存安定性、著色圖樣化塗膜形成時之顯像性、及所得之著色圖樣化塗膜之耐溶劑性更佳之傾向。 When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the development property when the colored pattern coating film is formed, and the resistance of the obtained colored pattern coating film are obtained. A tendency to be more solvent.
樹脂[K1],可以例如以文獻「高分子合成之實驗法」(大津隆行著 發行人化學同人股份有限公司 第1版第1刷1972年3月1日發行)中所載之方法及該文獻中所載之引用文獻為參考而製造。 The resin [K1] can be, for example, the method described in the literature "Experimental Method for Polymer Synthesis" (Dazu Long, Issuer Chemicals Co., Ltd., 1st Edition, 1st Brush, March 1, 1972) and the literature. The citations contained in the references are manufactured for reference.
具體之操作,可例舉如:將(a)及(b)之預定量、聚合起始劑及溶劑等加入反應容器中,再例如以氮氣將氧氣取代而成為脫氧環境,在攪拌之同時,加熱及保溫之方法。又,其中所使用之聚合起始劑及溶劑等,並無特別之限定,可使用在該領域中一般使用之物品。例如,聚合起始劑方面,可例舉如:偶氮化合物(2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2,4-二甲戊腈)等)及有機過氧化物(過氧化苯甲醯等),溶劑方面,只要係可使各單體溶解者即可,著色硬化性樹脂組成物之溶劑方面可例舉如後述之溶劑(E)等。 Specific operations include, for example, adding a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like to a reaction vessel, and then, for example, replacing oxygen with nitrogen to form a deoxidizing environment, while stirring, Heating and insulation methods. Further, the polymerization initiator, solvent and the like used therein are not particularly limited, and articles generally used in the field can be used. For example, the polymerization initiator may, for example, be an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) In the case of the organic peroxide (such as benzamidine peroxide), the solvent may be used as long as the monomer is dissolved. The solvent of the colored curable resin composition may, for example, be a solvent (E) to be described later.
又,所得之共聚物,可以將反應後之溶液直接使用,亦可使用經過濃縮或稀釋之溶液,亦可使用以再沉澱等方法而取出之固體(粉體)。特別是,在該聚合時,可以使用後述之溶劑(E)作為溶劑,藉此可將反應後之溶液直接使用,因此可使製造步驟簡化。 Further, the obtained copolymer may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. In particular, at the time of the polymerization, the solvent (E) described later can be used as a solvent, whereby the solution after the reaction can be used as it is, so that the production steps can be simplified.
在樹脂[K2]中,由各來源之結構單元的比例,以構成樹脂[K2]之全結構單元中, 源自(a)之結構單元:2至45莫耳%源自(b)之結構單元:2至95莫耳%源自(c)之結構單元:1至65莫耳%為佳,源自(a)之結構單元:5至40莫耳%源自(b)之結構單元:5至80莫耳%源自(c)之結構單元:5至60莫耳%更佳。 In the resin [K2], the ratio of the structural units of each source is used to constitute the entire structural unit of the resin [K2], The structural unit derived from (a): 2 to 45 mol% of the structural unit derived from (b): 2 to 95 mol% of the structural unit derived from (c): preferably from 1 to 65 mol%, derived from The structural unit of (a): 5 to 40 mol% of the structural unit derived from (b): 5 to 80 mol% of the structural unit derived from (c): preferably 5 to 60 mol%.
樹脂[K2]之結構單元的比例,在上述範圍時,有使著色硬化性樹脂組成物之保存安定性、著色圖樣化塗膜形成時之顯像性、及所得之著色圖樣化塗膜之耐溶劑性、耐熱性及機械強度更佳之傾向。 When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the development property when the colored pattern coating film is formed, and the resistance of the obtained color pattern coating film are obtained. The solvent, heat resistance and mechanical strength tend to be better.
樹脂[K2],可以例如與樹脂[K1]之製造方法所載之方法同樣地製造。 The resin [K2] can be produced, for example, in the same manner as the method described in the method for producing the resin [K1].
樹脂[K3]中,由各來源之結構單元的比例,以構成樹脂[K3]之全結構單元中,源自(a)之結構單元:2至60莫耳%源自(c)之結構單元:40至98莫耳%為佳,源自(a)之結構單元:10至50莫耳%源自(c)之結構單元:50至90莫耳%更佳。 In the resin [K3], the proportion of the structural unit of each source to constitute the structural unit of the resin [K3], the structural unit derived from (a): 2 to 60 mol% of the structural unit derived from (c) 40 to 98 mol% is preferred, the structural unit derived from (a): 10 to 50 mol% derived from the structural unit of (c): preferably 50 to 90 mol%.
樹脂[K3],可以例如與樹脂[K1]之製造方法所載之方法同樣地製造。 The resin [K3] can be produced, for example, in the same manner as the method described in the method for producing the resin [K1].
樹脂[K4],可藉由得到(a)與(c)之共聚物,再以(b)所具有之碳數2至4之環醚加成在(a)所具有之羧酸及/或羧酸酐而製造。 The resin [K4] can be obtained by adding the copolymer of (a) and (c), and then adding the cyclic ether having a carbon number of 2 to 4 (b) to the carboxylic acid (a) and/or Manufactured by carboxylic anhydride.
首先,(a)與(c)之共聚物,可以例如與樹脂[K1]之製造方法所載之方法同樣地製造。該情形時,由各來源之結構單元的比例,以與在樹脂[K3]中所例舉者同樣之比例為佳。 First, the copolymer of (a) and (c) can be produced, for example, in the same manner as the method described in the method for producing the resin [K1]. In this case, the ratio of the structural unit of each source is preferably the same as that exemplified in the resin [K3].
其次,再使(b)所具有之碳數2至4之環醚對前述共聚物中之源自(a)之羧酸及/或羧酸酐之一部分進行反應。 Next, the cyclic ether having 2 to 4 carbon atoms which is contained in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer.
之後繼續(a)與(c)之共聚物之製造,將燒瓶內環境從氮氣取代為空氣,並將(b)、羧酸或羧酸酐及環醚之反應催化劑(如三(二甲基胺基甲基)酚等)及聚合抑制劑(如氫醌等)等加入燒瓶內,之後例如在60至130℃,進行反應1至10小時,即可製造得樹脂[K4]。 Thereafter, the manufacture of the copolymer of (a) and (c) is continued, the environment of the flask is replaced with nitrogen from air, and (b), a reaction catalyst of a carboxylic acid or a carboxylic anhydride and a cyclic ether (such as tris(dimethylamine) The resin [K4] can be produced by adding a reaction such as a methyl group phenol or the like and a polymerization inhibitor (such as hydroquinone) to the flask, followed by, for example, a reaction at 60 to 130 ° C for 1 to 10 hours.
(b)之使用量,相對於(a)100莫耳,以5至80莫耳為佳,10至75莫耳更佳。使其在該範圍時,而有使著色硬化性樹脂組成物之保存安定性、圖樣化塗膜形成時之顯像性、及所得之圖樣化塗膜之耐溶劑性、耐熱性、機械強度及感度之平衡更佳之傾向。因環醚之反應性高,未反應之(b)不易殘存,故樹脂[K4]所使用之(b)以(b1)為佳,(b1-1)更佳。 The amount of use of (b) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. When it is in this range, the storage stability of the colored curable resin composition, the development property in the formation of the patterned coating film, and the solvent resistance, heat resistance, and mechanical strength of the obtained patterned coating film and The tendency to balance the sensitivity is better. Since the reactivity of the cyclic ether is high and the unreacted (b) does not easily remain, the (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1).
前述反應催化劑之使用量,相對於(a)、(b)及(c)之合計量100質量份,以0.001至5質量份為佳。前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,以0.001至5質量份為佳。 The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).
加入之方法、反應溫度及時間等反應條件,可依照製 造設備及聚合由來之發熱量等加以考慮再適當地調整。同時,與聚合之條件同樣,亦可依照製造設備及聚合由來之發熱量等加以考慮,再將加入方法及反應溫度適當地調整。 The reaction conditions such as the method of addition, reaction temperature and time can be determined according to the system. The equipment and the heat generated by the polymerization are considered and appropriately adjusted. At the same time, in the same manner as the polymerization conditions, it can be considered in accordance with the heat generated by the production equipment and the polymerization, and the addition method and the reaction temperature are appropriately adjusted.
樹脂[K5],在第一階段,係與上述樹脂[K1]之製造方法同樣地操作,得到(b)與(c)之共聚物。之後與上述同樣地,所得之共聚物可直接使用反應後之溶液,亦可以使用經濃縮或稀釋之溶液,亦可使用以再沉澱等方法而取出之固體(粉體)。 In the first step, the resin [K5] is treated in the same manner as in the above-described method for producing the resin [K1] to obtain a copolymer of (b) and (c). Thereafter, in the same manner as above, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used.
源自(b)及(c)之結構單元的比例,相對於構成前述共聚物之全結構單元的合計莫耳數,以在以下之範圍為佳。 The ratio of the structural unit derived from (b) and (c) is preferably in the following range with respect to the total number of moles of the entire structural unit constituting the copolymer.
以源自(b)之結構單元:5至95莫耳%源自(c)之結構單元:5至95莫耳%為佳,源自(b)之結構單元:10至90莫耳%源自(c)之結構單元;10至90莫耳%更佳。 The structural unit derived from (b): 5 to 95 mol% of the structural unit derived from (c): preferably 5 to 95 mol%, and the structural unit derived from (b): 10 to 90 mol% of the source From the structural unit of (c); 10 to 90 mol% is more preferable.
同時,可藉由以與樹脂[K4]之製造方法同樣之條件,使(a)所具有之羧酸或羧酸酐對(b)與(c)之共聚物所具有之源自(b)的環醚反應,得到樹脂[K5]。 At the same time, the carboxylic acid or carboxylic anhydride having the (a) copolymer (b) and (c) may be derived from (b) by the same conditions as in the production method of the resin [K4]. The cyclic ether is reacted to obtain a resin [K5].
對前述共聚物反應之(a)之使用量,相對於(b)100莫耳,以5至80莫耳為佳。因環醚之反應性高,未反應之(b)殘存不易,故樹脂[K5]所使用之(b)以(b1)為佳,(b1-1)更佳。 The amount of (a) used for the reaction of the aforementioned copolymer is preferably from 5 to 80 moles per 100 moles of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) remains difficult, the (b) used in the resin [K5] is preferably (b1), and more preferably (b1-1).
樹脂[K6],係復使羧酸酐對樹脂[K5]進行反應之樹脂。使羧酸酐對藉由環醚與羧酸或羧酸酐進行之反應所產 生之羥基反應。 The resin [K6] is a resin which reacts a carboxylic anhydride with a resin [K5]. Producing a carboxylic anhydride by reacting a cyclic ether with a carboxylic acid or a carboxylic anhydride The hydroxy group reacts.
羧酸酐,可例舉如: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、二甲四氫鄰苯二甲酸酐、去水5,6-二羧雙環[2.2.1]戊-2-烯(納迪克酸酐(Himic anhydride))等。羧酸酐之使用量,相對於(a)之使用量1莫耳,以0.5至1莫耳為佳。 The carboxylic anhydride may, for example, be maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6- Tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methatetrahydrophthalic anhydride, dehydrated 5,6-dicarboxybicyclo[2.2.1]penta- 2-ene (Himic anhydride) or the like. The amount of the carboxylic anhydride to be used is preferably from 1 to 1 mol per mol of the amount of (a).
樹脂(B),具體地可例舉如:(甲基)丙烯酸3,4-環氧環己基甲酯/(甲基)丙烯酸共聚物、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)丙烯酸環氧丙酯/(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸環氧丙酯/苯乙烯/(甲基)丙烯酸共聚物、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、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/(甲基)丙烯酸二環戊烯酯共聚物、3-甲-3-(甲基)丙烯醯氧基甲基環氧丙烷/(甲基)丙烯酸/苯乙烯共聚物等樹脂[K2];(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物等樹脂[K3];將(甲基)丙烯酸環氧丙酯加成在(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物之樹脂、將(甲基)丙烯酸環氧丙酯加成在(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物之樹脂、將(甲基)丙烯酸環氧丙酯加成在(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物之樹脂等樹脂[K4];對(甲基)丙烯酸三環癸酯/(甲基)丙烯酸環氧丙 酯之共聚物以(甲基)丙烯酸反應之樹脂、對(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸環氧丙酯之共聚物以(甲基)丙烯酸反應之樹脂等樹脂[K5];對(甲基)丙烯酸三環癸酯/(甲基)丙烯酸環氧丙酯之共聚物以(甲基)丙烯酸反應之樹脂再以四氫鄰苯二甲酸酐反應之樹脂等樹脂[K6]等。 Resin (B), specifically, for example, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricycloacrylate [5.2.1.0 2.6 Resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer, (meth) acrylate ring propylene oxide / styrene / (meth) acrylic acid copolymers, epoxy acrylate, 3,4-tricyclo [5.2.1.0 2.6] decyl acrylate / (meth) acrylic acid / N- cyclohexyl maleate (PEI) Copolymer, 3,4-epoxytricyclo[?.1.0 2.6 ]decyl acrylate/(meth)acrylic acid/vinyltoluene/dicyclopentenyl (meth)acrylate copolymer, 3-methyl-3- Resin such as (meth) propylene methoxymethyl propylene oxide / (meth) acrylate / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylate copolymer, styrene / a resin such as a (meth)acrylic copolymer [K3]; a resin obtained by adding a glycidyl (meth)acrylate to a benzyl (meth)acrylate/(meth)acrylic copolymer, (meth) Addition of glycidyl acrylate to tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid a resin of a polymer and a resin such as a trimethyl decyl (meth) acrylate/(meth)acrylic acid methacrylate/(meth)acrylic acid copolymer resin [K4] a copolymer of trimethyl decyl (meth) acrylate / glycidyl (meth) acrylate with (meth)acrylic acid, tricyclodecyl (meth) acrylate / styrene / ( a copolymer of glycidyl methacrylate with a resin such as a (meth)acrylic acid-reactive resin [K5]; a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate; A resin such as a resin which reacts with (meth)acrylic acid and a resin [K6] which is reacted with tetrahydrophthalic anhydride.
其中,樹脂(B),以樹脂[K1]、樹脂[K2]及樹脂[K3]為佳。 Among them, the resin (B) is preferably a resin [K1], a resin [K2], and a resin [K3].
樹脂(B)換算聚苯乙烯之重量平均分子量,以3,000至100,000為佳,5,000至50,000更佳,5,000至30,000又更佳。分子量在前述範圍時,可使其有塗膜硬度增加、薄膜殘留率提高、未曝光部分對顯像液之溶解性良好,且解析度提高之傾向。 The weight average molecular weight of the resin (B) to polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the coating film hardness is increased, the film residual ratio is improved, the solubility of the unexposed portion to the developing solution is good, and the resolution tends to be improved.
樹脂(B)之分子量分布[重量平均分子量(Mw)/數量平均分子量(Mn)],以1.1至6為佳,1.2至4更佳。 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.
樹脂(B)之酸價,以50至170mg-KOH/g為佳,60至150mg-KOH/g更佳,70至135mg-KOH/g又更佳。其中之酸價係使樹脂1g中和所需的氫氧化鉀之量(mg)之測定值,可例如使用氫氧化鉀水溶液滴定而求得。 The acid value of the resin (B) is preferably from 50 to 170 mg-KOH/g, more preferably from 60 to 150 mg-KOH/g, still more preferably from 70 to 135 mg-KOH/g. The acid value thereof is a measured value of the amount (mg) of potassium hydroxide required for neutralizing 1 g of the resin, and can be obtained, for example, by titration with an aqueous potassium hydroxide solution.
樹脂(B)之含量,相對於固形份之總量,以7至65質量%為佳,13至60質量%更佳,17至55質量%又更佳。樹脂(B)之含量,在前述之範圍時,有著色圖樣化塗膜之解析度及著色圖樣化塗膜之薄膜殘留率提高之傾向。 The content of the resin (B) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid portion. When the content of the resin (B) is within the above range, the resolution of the colored pattern coating film and the film residual ratio of the colored pattern coating film tend to increase.
聚合性化合物(C),係可藉由熱、或聚合起始劑(D)所 產生之活性自由基及/或酸進行聚合的化合物,可例舉如:具有聚合性之乙烯性不飽和鍵的化合物等,而以(甲基)丙烯酸酯化合物為佳。 The polymerizable compound (C) can be obtained by heat or a polymerization initiator (D) The compound which is polymerized by the active radical and/or the acid to be produced may, for example, be a compound having a polymerizable ethylenically unsaturated bond, and preferably a (meth) acrylate compound.
其中,聚合性化合物(C),以具有3個以上乙烯性不飽和鍵的聚合性化合物較佳。此類聚合性化合物,可例舉如:三(甲基)丙烯酸三羥甲基丙烷酯、三(甲基)丙烯酸新戊四醇酯、四(甲基)丙烯酸新戊四醇酯、五(甲基)丙烯酸二新戊四醇酯、六(甲基)丙烯酸二新戊四醇酯、八(甲基)丙烯酸三新戊四醇酯、七(甲基)丙烯酸三新戊四醇酯、十(甲基)丙烯酸四新戊四醇酯、九(甲基)丙烯酸四新戊四醇酯、異三聚氰酸三(2-(甲基)丙烯醯氧基乙基)酯、乙二醇改質四(甲基)丙烯酸新戊四醇酯、乙二醇改質六(甲基)丙烯酸二新戊四醇酯、丙二醇改質四(甲基)丙烯酸新戊四醇酯、丙二醇改質六(甲基)丙烯酸二新戊四醇酯、己內酯改質四(甲基)丙烯酸新戊四醇酯、己內酯改質六(甲基)丙烯酸二新戊四醇酯等。光聚合性化合物(C),可單獨亦可以2種以上組合使用。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Such a polymerizable compound may, for example, be trimethylolpropane tris(meth)acrylate, neopentyl glycol tri(meth)acrylate, neopentyl glycol tetra(meth)acrylate, or five ( Dipentaerythritol methyl methacrylate, di pentaerythritol hexa (meth) acrylate, tricobalt octa (meth) acrylate, tri pentaerythritol hepta(meth) acrylate, Tetraneutradoxytetrakis(meth)acrylate, tetrapentaerythritol pent(meth)acrylate, tris(2-(methyl)propenyloxyethyl)isocyanate, ethylene Alcohol-modified neopentyl glycol (meth) acrylate, ethylene glycol modified hexaerythritol hexa(meth) acrylate, propylene glycol modified tetrakis (meth) acrylate pentaerythritol ester, propylene glycol Lithoctaerythritol hexa(meth)acrylate, caprolactone modified tetrapentaerythritol tetra(meth)acrylate, caprolactone modified hexa(penta)cyclopentaerythritol acetate, and the like. The photopolymerizable compound (C) may be used singly or in combination of two or more kinds.
其中,以五(甲基)丙烯酸二新戊四醇酯及六(甲基)丙烯酸二新戊四醇酯較佳。 Among them, dineopentaerythritol 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,以150以上2,900以下為佳,250至1,500以下更佳。 The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 to 1,500 or less.
聚合性化合物(C)之含量,相對於固形份之總量,以7至65質量%為佳,13至60質量%更佳,17至55質量%又更佳。聚合性化合物(C)之含量,在前述範圍時,有使著色圖樣化塗膜之薄膜殘留率及耐藥品性提高之傾向。 The content of the polymerizable compound (C) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid portion. When the content of the polymerizable compound (C) is in the above range, the film residual ratio and chemical resistance of the colored pattern coating film tend to be improved.
聚合起始劑(D),只要為可藉由光或熱之作用而產生活性自由基、酸等,並使聚合起始之化合物者即可並無特別之限定,可使用一般已知之聚合起始劑。 The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat, and the polymerization is started, and generally known polymerization can be used. Starting agent.
聚合起始劑(D),可例舉如:烷基苯酮(alkylphenone)化合物、三化合物、醯基氧化膦化合物、O-醯肟化合物及聯咪唑化合物等。 The polymerization initiator (D) may, for example, be an alkylphenone compound or three. a compound, a mercaptophosphine oxide compound, an O-quinone compound, a biimidazole compound, and the like.
O-醯肟化合物,係含有式(d1)所示之部分結構的化合物。以下,*係表示鍵結基。 The O-indole compound is a compound containing a partial structure represented by the formula (d1). Hereinafter, * indicates a bonding group.
O-醯肟化合物,可例舉如:N-苯甲醯氧-1-(4-苯基硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧-1-(4-苯基硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧-1-[9-乙-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧-1-[9-乙-6-{2-甲-4-(3,3-二甲-2,4-二氧雜環戊基甲氧)苯甲醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧-1-[9-乙-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-1-[9-乙-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。可使用Irgacure(註冊商標)OXE 01、OXE 02(以上,為BASF公司製造)、N-1919(ADEKA公司製造)等商品。 The O-indole compound may, for example, be N-benzhydryl-1-(4-phenylthiophenyl)butan-1-one-2-imine or N-benzidine-1 -(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylidene-1-(4-phenylthiophenyl)-3-cyclopentylpropane- 1-keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-a Amine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolmethoxy)benzhydryl} -9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methylbenzimidyl}-9H-carbazole-3 -yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2-methylbenzylidene)-9H-indazole-3- ]]-3-cyclopentylpropan-1-one-2-imine and the like. Products such as Irgacure (registered trademark) OXE 01, OXE 02 (above, manufactured by BASF Corporation), and N-1919 (manufactured by Adeka Co., Ltd.) can be used.
烷基苯酮化合物,係具有式(d2)所示之部分結構或式 (d3)所示之部分結構的化合物。此等部分結構中之苯環可具有取代基。 An alkyl phenone compound having a partial structure or formula represented by formula (d2) (d3) A compound of a partial structure shown. The benzene ring in these partial structures may have a substituent.
具有式(d2)所示之部分結構的化合物,可例舉如:2-甲-2-(N-嗎啉基)-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲胺-1-(4-(N-嗎啉基)苯基)-2-苯甲基丁烷-1-酮、2-(二甲胺基)-2-[(4-甲苯基)甲基]-1-[4-(4-嗎啉基)苯基]丁烷-1-酮等。可使用Irgacure(註冊商標)369、907及379(以上,為BASF公司製造)等商品。 The compound having a partial structure represented by the formula (d2) may, for example, be 2-methyl-2-(N-morpholinyl)-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamine-1-(4-(N-morpholinyl)phenyl)-2-benzylidenebutan-1-one, 2-(dimethylamino)-2-[(4-toluene) Methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can be used.
具有式(d3)所示之部分結構的化合物,可例舉如:2-羥-2-甲-1-苯基丙烷-1-酮、2-羥-2-甲-1-[4-(2-羥乙氧基)苯基]丙烷-1-酮、1-羥環己基苯基酮、2-羥-2-甲-1-(4-異丙烯基苯基)丙烷-1-酮之寡聚物、α,α-二乙氧基乙醯苯、苯甲基二甲縮酮等。 The compound having a partial structure represented by the formula (d3) may, for example, be 2-hydroxy-2-methyl-1-propan-1-one or 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Oligomer, α,α-diethoxyethyl benzene, benzyl dimethyl ketal, and the like.
在感度之觀點方面,烷基苯酮化合物,以具有式(d2)所示之部分結構的化合物為佳。 From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).
三化合物,可例舉如: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-胡椒基-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-(4-二乙胺-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。 three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamine-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.
醯基氧化膦化合物,可例舉如:2,4,6-三甲基苯甲醯基二苯基氧化膦等。可使用Irgacure(註冊商標)819(BASF公司製造)等商品。 The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like. A product such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can be used.
聯咪唑化合物,可例舉如: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(可參考如:JPH06-75372-A、JPH06-75373-A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(烷氧苯基)聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(二烷氧苯基)聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧苯基)聯咪唑(可參考如:JPS48-38403-B、JPS62-174204-A等)、4,4’,5,5’-位之苯基經烷氧羰基取代之咪唑化合物(可參考如:JPH07-10913-A等)等。 The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to, for example, JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkyloxyphenyl)biimidazole, 2,2'-bis(2-chlorobenzene) -4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, JPS48-38403-B, JPS62-174204-A, etc.), 4, 4', 5, 5 An imidazole compound in which the phenyl group of the '-position is substituted with an alkoxycarbonyl group (for example, JPH07-10913-A, etc.) and the like.
聚合起始劑(D),可例舉如:苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻異丁基醚等苯偶姻化合物;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-4’-甲二苯硫醚、3,3’,4,4’-四(過氧化第三丁基羰基)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-2-氯吖啶酮、二苯乙二酮(benzil)、苯基乙醛酸甲酯、二茂鈦化合物等。該等係以與後述之聚合起始助劑(D1)(特別是胺類)組合使用為佳。 The polymerization initiator (D) may, for example, be a benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether. a compound; benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3', 4,4' a benzophenone compound such as tetrakis(t-butylcarbonyl peroxide)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylhydrazine, Anthraquinone compound such as camphorquinone; 10-but-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.
酸產生劑之,可例舉如:對甲苯磺酸4-羥苯基二甲基鋶、六氟銻酸4-羥苯基二甲基鋶、對甲苯磺酸4-乙醯氧基苯基二甲基鋶、六氟銻酸4-乙醯氧基苯基/甲基/苯甲基鋶、對甲苯磺酸三苯基鋶、六氟銻酸三苯基鋶、對甲苯磺酸二苯基錪、六氟銻酸二苯基錪等鎓鹽類,及甲苯磺酸硝苯甲酯類、甲苯磺酸苯偶姻酯類等。 The acid generator may, for example, be 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylhydrazine hexafluoroantimonate or 4-ethyloxyphenylphenyl p-toluenesulfonate. Dimethyl hydrazine, hexafluoroantimonic acid 4-ethenyloxyphenyl/methyl/benzyl hydrazine, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl p-toluenesulfonate Anthracene salts such as sulfonium and diphenylphosphonium hexafluoroantimonate, and nifennyl toluenesulfonate and benzoin tosylate.
聚合起始劑(D),以含有由烷基苯酮化合物、三化合物、醯基氧化膦化合物、O-醯肟化合物及聯咪唑化合物所形成之群中所選擇之至少1種的聚合起始劑為佳,含O-醯肟化合物的聚合起始劑更佳,含O-醯肟化合物及烷基苯酮化合物的聚合起始劑又更佳。 Polymerization initiator (D) to contain an alkyl benzophenone compound, three A polymerization initiator which is at least one selected from the group consisting of a compound, a mercaptophosphine oxide compound, an O-quinone compound and a biimidazole compound, and a polymerization initiator containing an O-quinone compound is more preferable. Further, a polymerization initiator containing an O-tellurium compound and an alkylphenone compound is more preferable.
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,以0.1至40質量份為佳,5至35質量份更佳,10至30質量份再更佳。聚合起始劑(D)之含量,在前述範圍時,有高感度化而使曝光時間縮短之傾向因此使生產性更佳。 The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 5 to 35 parts by mass, even more preferably 10 to 30 parts by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). The quality is even better. When the content of the polymerization initiator (D) is in the above range, the sensitivity is high and the exposure time is shortened, so that productivity is further improved.
聚合起始劑(D),可同時再含聚合起始助劑(D1)。聚合起始助劑(D1),係用以促進藉由聚合起始劑而使聚合開始的光聚合性化合物之聚合所使用之化合物、或增感劑。 The polymerization initiator (D) may further contain a polymerization initiation aid (D1). The polymerization initiation aid (D1) is a compound or a sensitizer used to promote polymerization of a photopolymerizable compound which starts polymerization by a polymerization initiator.
聚合起始助劑(D1),可例舉如:胺化合物、烷氧基蒽化合物、噻噸酮(thioxanthone)化合物及羧酸化合物等。 The polymerization initiation aid (D1) may, for example, be an amine compound, an alkoxy fluorene compound, a thioxanthone compound or a carboxylic acid compound.
胺化合物,可例舉如:三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲胺苯甲酸甲酯、4-二甲胺苯甲酸乙酯、4-二甲胺苯甲酸異戊酯、苯甲酸2-二甲胺乙酯、4-二甲胺 苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲胺基)二苯甲酮(通稱為米其勒酮(Michler’s ketone))、4,4’-雙(二乙胺基)二苯甲酮、4,4’-雙(乙甲胺基)二苯甲酮等,其中以4,4’-雙(二乙胺基)二苯甲酮較佳。可使用EAB-F(保土谷化學工業股份有限公司製造)等商品。 The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminebenzoate, ethyl 4-dimethylaminebenzoate or 4-dimethylaminebenzoic acid. Amyl ester, 2-dimethylamine ethyl benzoate, 4-dimethylamine 2-ethylhexyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4 , 4'-bis(diethylamino)benzophenone, 4,4'-bis(methylamino)benzophenone, etc., among which 4,4'-bis(diethylamino)diphenyl Methyl ketone is preferred. Products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.
烷氧基蒽化合物,可例舉如:9,10-二甲氧蒽、2-乙-9,10-二甲氧蒽、9,10-二乙氧蒽、2-乙-9,10-二乙氧蒽、9,10-二丁氧蒽、2-乙-9,10-二丁氧蒽等。 The alkoxy oxime compound may, for example, be 9,10-dimethoxy oxime, 2-ethyl-9,10-dimethoxy oxime, 9,10-diethoxy oxime, 2-ethyl-9,10- Diethoxy hydrazine, 9,10-dibutoxy oxime, 2-ethyl-9,10-dibutoxy oxime, and the like.
噻噸酮化合物,可例舉如:2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、1-氯-4-丙氧基噻噸酮等。 The thioxanthone compound may, for example, be 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone or 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone and the like.
羧酸化合物,可例舉如:苯基硫基乙酸、甲基苯基硫基乙酸、乙基苯基硫基乙酸、甲乙基苯基硫基乙酸、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。 The carboxylic acid compound may, for example, be phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid or methoxy Phenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.
聚合起始助劑(D1),以噻噸酮化合物為佳。 The polymerization starting aid (D1) is preferably a thioxanthone compound.
在使用聚合起始助劑(D1)時,其使用量,相對於樹脂(B)及聚合性化合物(C)之合計量100質量份,以0.1至30質量份為佳,1至20質量份更佳。聚合起始助劑(D1)之量在該範圍時,可以更高之感度形成著色圖樣化塗膜,有使濾色器的生產性更佳之傾向。 When the polymerization initiator (D1) is used, the amount thereof is preferably 0.1 to 30 parts by mass, and 1 to 20 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Better. When the amount of the polymerization starting aid (D1) is in this range, the coloring pattern coating film can be formed with higher sensitivity, and the productivity of the color filter tends to be better.
溶劑(E),包含環酮及丙二醇單甲醚乙酸酯。 Solvent (E) comprising a cyclic ketone and propylene glycol monomethyl ether acetate.
環酮,可例舉如:環戊酮、環己酮、環辛酮、甲基環己酮、異佛酮等。 The cycloketone may, for example, be cyclopentanone, cyclohexanone, cyclooctanone, methylcyclohexanone or isophorone.
環酮之含量,相對於溶劑(E)之總量,以25質量%以上75質量%以下為佳,30質量%以上70質量%以下更佳。 The content of the cyclic ketone is preferably 25% by mass or more and 75% by mass or less based on the total amount of the solvent (E), and more preferably 30% by mass or more and 70% by mass or less.
丙二醇單甲醚乙酸酯之含量,相對於溶劑(E)之總量,以25質量%以上75質量%以下為佳,28質量%以上70質量%以下更佳。 The content of the propylene glycol monomethyl ether acetate is preferably 25% by mass or more and 75% by mass or less based on the total amount of the solvent (E), and more preferably 28% by mass or more and 70% by mass or less.
環酮及丙二醇單甲醚乙酸酯之合計量,相對於溶劑之總量,以80質量%以上100質量%以下為佳,88質量%以上100質量%以下更佳。 The total amount of the cyclic ketone and the propylene glycol monomethyl ether acetate is preferably 80% by mass or more and 100% by mass or less based on the total amount of the solvent, and more preferably 88% by mass or more and 100% by mass or less.
環酮及丙二醇單甲醚乙酸酯之含量在前述範圍內時,著色硬化性樹脂組成物之黏度降低,因此在使用細縫噴嘴塗布機將著色硬化性樹脂組成物塗布時,可使塗布速度提高。 When the content of the cyclic ketone and the propylene glycol monomethyl ether acetate is within the above range, the viscosity of the colored curable resin composition is lowered. Therefore, when the colored curable resin composition is applied by using a slit nozzle coater, the coating speed can be increased. improve.
溶劑(E),亦可再含環酮及丙二醇單甲醚乙酸酯之外之溶劑。該溶劑,並無特別之限定,可使用該領域通常使用之溶劑。可舉例如由酯溶劑(分子內含-COO-,不含-O-之溶劑)、醚溶劑(分子內含-O-,不含-COO-之溶劑)、醚酯溶劑(分子內含-COO-及-O-之溶劑)、酮溶劑(分子內含-CO-,不含-COO-之溶劑)、醇溶劑、芳烴溶劑、醯胺溶劑、二甲基亞碸等之中選擇而使用。 The solvent (E) may further contain a solvent other than the cyclic ketone and the propylene glycol monomethyl ether acetate. The solvent is not particularly limited, and a solvent which is usually used in the field can be used. For example, an ester solvent (a solvent containing -COO-, a solvent containing no -O-), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (molecular inclusion - A solvent of COO- and -O-), a ketone solvent (a solvent containing -CO-, a solvent containing no -COO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, and a dimethyl hydrazine are selected and used. .
酯溶劑,可例舉如:乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥異丁酸甲酯、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。 The ester solvent may, for example, be methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate or isobutyl acetate. Amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate Ethyl acetate, cyclohexanol acetate, γ-butyrolactone, and the like.
醚溶劑,可例舉如: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-1-丁醇、3-甲氧-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(anisole)、苯基***(phenetole)、甲基苯甲醚等。 The ether solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran , tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl Ethyl (phenetole), methyl anisole, and the like.
醚酯溶劑,可例舉如:甲氧乙酸甲酯、甲氧乙酸乙酯、甲氧乙酸丁酯、乙氧乙酸甲酯、乙氧乙酸乙酯、3-甲氧丙酸甲酯、3-甲氧丙酸乙酯、3-乙氧丙酸甲酯、3-乙氧丙酸乙酯、2-甲氧丙酸甲酯、2-甲氧丙酸乙酯、2-甲氧丙酸丙酯、2-乙氧丙酸甲酯、2-乙氧丙酸乙酯、2-甲氧-2-甲基丙酸甲酯、2-乙氧-2-甲基丙酸乙酯、乙酸3-甲氧丁酯、乙酸3-甲-3-甲氧丁酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、二丙二醇單甲醚乙酸酯、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等。 The ether ester solvent may, for example, be methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate or methyl 3-methoxypropionate, or 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, sodium 2-methoxypropionate Ester, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, acetic acid 3 - methoxybutyl ester, 3-methyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate Ester, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.
酮溶劑,可例舉如:4-羥-4-甲-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲-2-戊酮等。 The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2-pentyl Ketones, etc.
醇溶劑,可例舉如:甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、丙三醇等。 The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol or glycerin.
芳烴溶劑,可例舉如:苯、甲苯、二甲苯、1,3,5-三甲苯等。 The aromatic hydrocarbon solvent may, for example, be benzene, toluene, xylene or 1,3,5-trimethylbenzene.
醯胺溶劑,可例舉如:N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等。 The guanamine solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.
上述溶劑中,由塗布性之觀點而言,以在20℃之黏度為3.0mPa‧s以下之有機溶劑為佳,2.8mPa‧s以下之有機溶劑更佳。此類溶劑,以丙二醇單甲醚、乳酸乙酯、3-乙氧丙酸乙酯及乙二醇單甲醚及4-羥-4-甲-2-戊酮為佳,丙二醇單甲醚更佳。 Among the above solvents, from the viewpoint of coatability, an organic solvent having a viscosity at 20 ° C of 3.0 mPa ‧ s or less is preferable, and an organic solvent of 2.8 mPa ‧ or less is more preferable. Such solvents are preferably propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether and 4-hydroxy-4-methyl-2-pentanone, and propylene glycol monomethyl ether is more preferred. good.
溶劑(E)之含量,相對於著色硬化性樹脂組成物之總量為80質量%以上90質量%以下,以82質量%以上88質量%以下為佳。換言之,著色硬化性樹脂組成物之固形份為10質量%以上20質量%以下,以12質量%以上18質量%以下為佳。溶劑(E)之含量在前述之範圍內時,使著色硬化性樹脂組成物之黏度降低,在使用細縫噴嘴塗布機將著色硬化性樹脂組成物塗布時,可使塗布速度提高。 The content of the solvent (E) is preferably 80% by mass or more and 90% by mass or less based on the total amount of the colored curable resin composition, and is preferably 82% by mass or more and 88% by mass or less. In other words, the solid content of the colored curable resin composition is preferably 10% by mass or more and 20% by mass or less, and more preferably 12% by mass or more and 18% by mass or less. When the content of the solvent (E) is within the above range, the viscosity of the colored curable resin composition is lowered, and when the colored curable resin composition is applied by using a slit nozzle coater, the coating speed can be improved.
界面活性劑(F),可例舉如:聚矽氧系界面活性劑、氟系界面活性劑、及含氟原子之聚矽氧系界面活性劑等。該等可於側鏈含有聚合性基。 The surfactant (F) may, for example, be a polyfluorene-based surfactant, a fluorine-based surfactant, or a fluorine-containing atomic surfactant. These may contain a polymerizable group in the side chain.
聚矽氧系界面活性劑,可例舉如:分子內含矽氧烷鍵之界面活性劑等。具體地可例舉如:Toray Silicone DC3PA、 同系列SH7PA、同系列DC11PA、同系列SH21PA、同系列SH28PA、同系列SH29PA、同系列SH30PA、同系列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(Momentive Performance Materials聯合公司製造)等。 The polyoxo-based surfactant may, for example, be a surfactant containing a decane bond in a molecule. Specifically, for example, Toray Silicone DC3PA, Same series SH7PA, same series DC11PA, same series SH21PA, same series SH28PA, same series SH29PA, same series SH30PA, same series SH8400 (trade name; manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials).
前述之氟系界面活性劑,可例舉如:分子內具有氟碳鏈之界面活性劑等。具體地可例舉如:Fluorad(註冊商標)FC430、同系列FC431(住友3M股份有限公司製造),MEGAFAC(註冊商標)F142D、同系列F171、同系列F172、同系列F173、同系列F177、同系列F183、同系列F554、同系列R30、同系列RS-718-K(DIC股份有限公司製造),EFTOP(註冊商標)EF301、同系列EF303、同系列EF351、同系列EF352(Mitsubishi Materiale Electronic Chemicals股份有限公司製造),Surflon(註冊商標)S381、同系列S382、同系列SC101、同系列SC105(旭玻璃股份有限公司製造)及E5844(Daikin Fine Chemical研究所製造)等。 The fluorine-based surfactant described above may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, for example, Fluorad (registered trademark) FC430, the same series FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, the same series F171, the same series F172, the same series F173, the same series F177, the same Series F183, the same series F554, the same series R30, the same series RS-718-K (made by DIC Corporation), EFTOP (registered trademark) EF301, the same series EF303, the same series EF351, the same series EF352 (Mitsubishi Materiale Electronic Chemicals shares (manufactured by Ltd.), Surflon (registered trademark) S381, the same series S382, the same series SC101, the same series SC105 (made by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute).
前述含氟原子之聚矽氧系界面活性劑,可例舉如:分子內具有矽氧烷鍵及氟碳鏈之界面活性劑等。具體地可例舉如:MEGAFAC(註冊商標)R08、同系列BL20、同系列F475、同系列F477及同系列F443(DIC股份有限公司製造)等。 The polyfluorinated surfactant of the fluorine atom may, for example, be a surfactant having a siloxane chain and a fluorocarbon chain in the molecule. Specifically, for example, MEGAFAC (registered trademark) R08, the same series BL20, the same series F475, the same series F477, and the same series F443 (manufactured by DIC Corporation) can be exemplified.
界面活性劑(F)之含量,相對於著色硬化性樹脂組成物 之總量,以0.001質量%以上0.2質量%以下為佳,0.002質量%以上0.1質量%以下更佳,0.01質量%以上0.05質量%以下又更佳。又,該含量中,並不包含前述顏料分散劑之含量。界面活性劑(F)之含量在前述範圍時,可使濾色器之平坦性良好。 The content of the surfactant (F) relative to the coloring curable resin composition The total amount is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and still more preferably 0.01% by mass or more and 0.05% by mass or less. Further, the content of the pigment dispersant is not included in the content. When the content of the surfactant (F) is within the above range, the flatness of the color filter can be improved.
本發明之著色硬化性樹脂組成物,依照其需要,可含有填充劑、其他之高分子化合物、密接促進劑、抗氧化劑、光安定劑、鏈轉移劑等該技術領域中一般已知之添加劑。 The colored curable resin composition of the present invention may contain additives such as a filler, other polymer compounds, adhesion promoters, antioxidants, photosetters, and chain transfer agents, which are generally known in the art, as needed.
本發明之著色硬化性樹脂組成物,可藉由例如將染料(A1)、顏料(A2)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)、及依照其需要所使用之聚合起始助劑(D1)、界面活性劑(F)及其他之成分,與溶劑(E)混合而進行調製。 The colored curable resin composition of the present invention can be, for example, a dye (A1), a pigment (A2), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and according to the needs thereof. The polymerization initiation aid (D1), the surfactant (F), and other components used are mixed with the solvent (E) to prepare.
預先將顏料(A2)與溶劑(E)混合,直到使顏料之平均粒徑成為0.2μm以下程度為止,使用珠磨機等使其分散為佳。操作時,亦可依照其需要而調配前述顏料分散劑、樹脂(B)之一部分或全部。在所得之顏料分散液中,將樹脂(B)之其餘部分及聚合性化合物(C)、及依照其需要所使用之聚合起始劑(D)、溶劑(E)之其餘部分、界面活性劑(F)及其他之成分等,以使其形成預定之濃度之方式加以混合,即可調製成目的之著色硬化性樹脂組成物。 The pigment (A2) and the solvent (E) are mixed in advance until the average particle diameter of the pigment is about 0.2 μm or less, and it is preferably dispersed by using a bead mill or the like. In the operation, a part or all of the pigment dispersant or the resin (B) may be blended according to the needs thereof. In the obtained pigment dispersion, the remainder of the resin (B) and the polymerizable compound (C), and the polymerization initiator (D) used in accordance with the necessity, the remainder of the solvent (E), and the surfactant (F) and other components and the like are mixed so as to form a predetermined concentration, whereby the intended color-curable resin composition can be prepared.
染料(A1),以預先使其在溶劑(E)中溶解調製成溶液為佳。該溶液,以藉通過孔徑0.01至1μm程度之濾膜而過 濾為佳。 The dye (A1) is preferably prepared by dissolving it in a solvent (E) in advance to prepare a solution. The solution is passed through a filter having a pore size of 0.01 to 1 μm. Filtering is better.
以如上述之操作加以混合調製之著色硬化性樹脂組成物,以藉通過孔徑0.1至10μm程度之濾膜而過濾為佳。 The colored curable resin composition prepared by mixing as described above is preferably filtered by a filter having a pore diameter of about 0.1 to 10 μm.
由本發明之著色硬化性樹脂組成物進行濾色器之著色圖樣化塗膜(「著色圖樣化塗膜」亦有簡稱之為「著色圖樣」之情形)之製造方法,可舉如:光蝕刻法、噴墨法、印刷法等。其中,以光蝕刻法較佳。光蝕刻法,係藉由將前述著色硬化性樹脂組成物塗布在基板,將其乾燥形成組成物層,介光罩並使該組成物層曝光,使其顯像之方法。在光蝕刻法中,在曝光時不使用光罩、及/或不進行顯像,藉此可形成上述組成物層之硬化物的著色塗膜。 A method for producing a color-patterning coating film of a color filter of the present invention (the case where the "coloring pattern coating film" is also referred to as a "coloring pattern") is exemplified by photolithography. , inkjet method, printing method, etc. Among them, photolithography is preferred. The photo-etching method is a method in which the colored curable resin composition is applied onto a substrate, dried to form a composition layer, and a dielectric cover is exposed to expose the composition layer. In the photolithography method, a coloring coating film of a cured product of the above composition layer can be formed without using a photomask and/or without developing.
該製作之濾色器之膜厚,並無特別之限定,可依照目的及用途等而適當調整,例如0.1至30μm,以0.1至20μm為佳,0.5至6μm更佳。 The film thickness of the color filter to be produced is not particularly limited, and may be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm.
基板方面,可以使用:石英玻璃、硼矽酸玻璃、氧化鋁矽酸鹽玻璃、表面經過氧化矽塗布之鈉鈣玻璃等玻璃板,及聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等樹脂板,矽,於前述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。此等基板上,亦可再形成其他濾色器層、樹脂層、電晶體、電路等。 For the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate coated with yttria-coated soda lime glass, and polycarbonate, polymethyl methacrylate, and poly-p-phenylene can be used. A resin plate such as ethylene formate is formed on the substrate, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Further, other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.
藉光蝕刻法使各色畫素形成時,可以一般已知或慣用之裝置及條件操作。例如可以下述之操作製作。 When each color pixel is formed by photolithography, it can be operated by generally known or conventional devices and conditions. For example, it can be produced by the following operations.
首先,將著色硬化性樹脂組成物塗布在基板上,藉加 熱乾燥(預焙)及/或減壓乾燥以將溶劑等揮發成分去除並乾燥,得到平滑之組成物層。 First, the colored curable resin composition is coated on a substrate, and The mixture is thermally dried (prebaked) and/or dried under reduced pressure to remove volatile components such as a solvent and dried to obtain a smooth composition layer.
塗布方法,可例舉如:旋塗法、細縫塗布法、細縫-旋轉塗布法等。特別,本發明之著色硬化性樹脂組成物黏度低,因此有用於使用細縫塗布法、細縫-旋轉塗布法等具有細縫噴嘴之塗布機的塗布方法。 The coating method may, for example, be a spin coating method, a slit coating method, a slit-rotation coating method, or the like. In particular, since the colored curable resin composition of the present invention has a low viscosity, there is a coating method for using a coater having a slit nozzle such as a slit coating method or a slit-spin coating method.
進行加熱乾燥時其溫度,以30至120℃為佳,50至110℃更佳。加熱時間方面,以10秒至60分鐘為佳,30秒至30分鐘更佳。 The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.
進行減壓乾燥時,以在50至150Pa之壓力下、20至25℃之溫度範圍進行為佳。 When drying under reduced pressure, it is preferably carried out at a temperature of from 50 to 150 Pa at a temperature of from 20 to 25 °C.
組成物層之膜厚,並無特別之限定,可依照目的之濾色器的膜厚適當地選擇。 The film thickness of the composition layer is not particularly limited, and can be appropriately selected depending on the film thickness of the color filter.
其次,該組成物層介用以形成目的之著色圖樣化塗膜的光罩而進行曝光。該光罩上之圖樣並無特別之限定,可以依照其目的之用途使用圖樣。 Next, the composition layer is exposed by forming a mask for forming a color patterning coating for the purpose. The pattern on the reticle is not particularly limited, and the pattern can be used according to the purpose for which it is intended.
曝光所使用之光源方面,以產生250至450nm波長之光的光源為佳。例如,可將未達350nm之光使用濾除該波長區域之濾光器(filter)而濾除,使436nm附近、408nm附近、365nm附近之光使用使此等波長區域透過之帶通濾波器而選擇性地透過。具體地可例舉如:汞燈、發光二極體、金屬鹵素燈、鹵素燈等。 In terms of the light source used for the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferred. For example, a light of less than 350 nm can be filtered using a filter that filters out the wavelength region, so that light near 436 nm, near 408 nm, and around 365 nm is used as a band pass filter that transmits the wavelength regions. Selectively through. Specifically, for example, a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, or the like can be exemplified.
為了對曝光面全體均勻地以平行光線照射、可進行使光罩及基材正確地對準,以使用光罩對準曝光機(mask aligner)及步進機(stepper)等曝光裝置為佳。 In order to uniformly illuminate the entire exposed surface with parallel light, the reticle and the substrate can be properly aligned to use the reticle alignment machine (mask Exposure devices such as aligner and stepper are preferred.
藉由使曝光後之組成物層與顯像液接觸並顯像,而在基板上形成著色圖樣化塗膜。藉由顯像,使組成物層之未曝光部分在顯像液中溶解而去除。顯像液之較佳例,可例舉如:氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲銨等鹼性化合物之水溶液。此等鹼性化合物之水溶液中之濃度,以0.01至10質量%為佳,0.03至5質量%更佳。同時,顯像液中,可再含界面活性劑。 A colored pattern coating film is formed on the substrate by bringing the exposed composition layer into contact with the developing liquid and developing the image. The unexposed portion of the composition layer is removed by dissolution in a developing solution by development. As a preferable example of the developing liquid, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide can be mentioned. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. At the same time, the developer may be further included in the developing solution.
顯像之方法,覆液法(puddle method)、浸漬法及噴霧法等任意者均可。在顯像時基板亦可以任意之角度傾斜。 The method of development, any of the puddle method, the dipping method, and the spraying method can be used. The substrate can also be tilted at any angle during development.
顯像後,以進行水洗為佳。 After the development, it is better to wash it.
此外,以對所得之著色圖樣化塗膜進行後焙為佳。後焙之溫度,以150至250℃為佳,160至235℃更佳。後焙之時間,以0.5至10分鐘為佳,1至5分鐘更佳。 Further, it is preferred to carry out post-baking of the obtained coloring pattern coating film. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 0.5 to 10 minutes, more preferably from 1 to 5 minutes.
該所得到之著色圖樣化塗膜及著色塗膜,有用於作為濾色器。 The obtained coloring pattern coating film and coloring coating film are used as a color filter.
依據本發明之著色硬化性樹脂組成物,可以良好生產性製作高性能之濾色器而,因此該濾色器,有用於作為顯示裝置(例如液晶顯示裝置、有機EL裝置等)、電子紙、固態影像元件等中所用之濾色器。 According to the colored curable resin composition of the present invention, a high-performance color filter can be produced with good productivity. Therefore, the color filter is used as a display device (for example, a liquid crystal display device, an organic EL device, etc.), electronic paper, A color filter used in solid-state image elements and the like.
以下例舉實施例,更具體地說明本發明。在例中,含量或使用量所表示之%及份,只要無特別註明,即係質量基準。 The invention will be more specifically described below by way of examples. In the examples, the % and the parts expressed by the content or the amount used are the quality standards unless otherwise specified.
在具備冷卻管及攪拌裝置之燒瓶中,將式(A1-1a)所示之化合物及式(A1-1b)所示之化合物之混合物(商品名Chugai Aminol Fast Pink R;中外化成公司製造)15份、氯仿150份及N,N-二甲基甲醯胺8.9份投入,在攪拌下維持20℃以下同時將亞硫醯氯10.9份滴下添加。在滴下結束後,昇溫至50℃,並於同溫度維持5小時進行反應,之後冷卻至20℃。將冷卻後之反應溶液,在攪拌下維持於20℃以下同時將2-乙基己胺12.5份及三乙胺22.1份之混合液滴下添加。之後,於同溫度攪拌5小時進行反應。其次將所得之反應混合物以旋轉蒸發器將溶劑蒸餾去除之後,再將少量甲醇加入並激烈攪拌。將該混合物一面攪拌一面加入於離子交換水375份之混合液中,使結晶析出。將析出之結晶過濾分離,並以離子交換水仔細洗淨,再於60℃減壓乾燥,得到染料A1-1(式(A1-1-1)至式(A1-1-8)所示之化合物的混合物)11.3份。 In a flask equipped with a cooling tube and a stirring device, a mixture of a compound represented by the formula (A1-1a) and a compound represented by the formula (A1-1b) (trade name: Chugai Aminol Fast Pink R; manufactured by a Chinese company) 15 A portion, 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide were placed, and the mixture was kept at 20 ° C or lower while stirring, and 10.9 parts of sulfite chloride was added dropwise. After the completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was maintained at the same temperature for 5 hours, followed by cooling to 20 ° C. The cooled reaction solution was kept under stirring at 20 ° C while stirring, and a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Next, after the obtained reaction mixture was distilled off by a rotary evaporator, a small amount of methanol was added and vigorously stirred. The mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed carefully with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a dye A1-1 (formula (A1-1-1) to formula (A1-1-8)). A mixture of the compounds) 11.3 parts.
在具備攪拌機、溫度計、回流冷卻器、及滴下漏斗之燒瓶內將氮氣以0.02L/分鐘流通使其成為氮氣環境,再將丙二醇單甲醚乙酸酯259份加入,並於攪拌之同時加熱至70℃。其次,再將丙烯酸56份、乙烯基甲苯83份、丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯(式(I-1)所示之化合物及式(II-1)所示之化合物,以莫耳比50:50混合者)229份、及丙烯酸三環[5.2.1.02.6]癸烯-8-酯(式(c-1)所示之化合物及式(c-2)所示之化合物,以莫耳比50:50混合者)8份,在丙二醇單甲醚乙酸酯140份中溶解而調製成溶液,再將該溶 液,使用滴下漏斗花費4小時滴入至保溫為70℃之燒瓶內。 In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was circulated at 0.02 L/min to make a nitrogen atmosphere, and 259 parts of propylene glycol monomethyl ether acetate was added thereto, and heated while stirring. 70 ° C. Next, 56 parts of acrylic acid, 83 parts of vinyl toluene, 3,4-epoxytricyclo[5.2.1.0 2.6 ] decyl acrylate (the compound represented by the formula (I-1) and the formula (II-1) were further added. 229 parts of the compound shown in a molar ratio of 50:50, and a tricyclo[5.2.1.0 2.6 ]nonene-8-ester (compound of formula (c-1) and formula (c-2) The compound shown was dissolved in a mixture of 140 parts of propylene glycol monomethyl ether acetate in 8 parts of a molar ratio of 50:50 to prepare a solution, and the solution was added dropwise to the dropping funnel for 4 hours. The flask was kept at 70 ° C.
另一方面,再將使聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)30份溶解在丙二醇單甲醚乙酸酯225份中之溶液,使用另一滴下漏斗花費4小時滴入燒瓶內。在該聚合起始劑之溶液滴下結束後,於4小時、保持於70℃,之後將其冷卻至室溫,得到重量平均分子量Mw為1.00×104、固形份37.5%、固形份酸價107mg-KOH/g之共聚物(樹脂B1)溶液。該樹脂B1,具有以下之結構單元。 On the other hand, a solution of 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 225 parts of propylene glycol monomethyl ether acetate was used, and another drop was used. The lower funnel was dropped into the flask over 4 hours. After the completion of the dropwise addition of the solution of the polymerization initiator, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.00 × 10 4 , a solid content of 37.5%, and a solid acid value of 107 mg. - KOH / g copolymer (resin B1) solution. This resin B1 has the following structural unit.
先使具備攪拌機、溫度計、回流冷卻器、滴下漏斗及氮氣導入管之燒瓶內成為氮氣環境,再將丙二醇單甲醚乙酸酯210份加入,並於攪拌之同時使其昇溫至100℃。其次,再將甲基丙烯酸苯甲酯106份、丙烯酸22份及甲基丙烯酸二環戊酯(日立化成股份有限公司製造FA-513M)22份在丙二醇單甲醚乙酸酯215份中溶解,再將溶解2,2’-偶氮雙異丁腈3.6份所調製之溶液,滴入該燒瓶內,在100℃ 持續攪拌5小時,得到重量平均分子量Mw1.00×104、固形份34.1%、固形份酸價為109mg-KOH/g之共聚物(樹脂B2)溶液。該樹脂B2,具有以下之結構單元。 First, a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was placed in a nitrogen atmosphere, and then 210 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 100 ° C while stirring. Next, 22 parts of benzyl methacrylate, 22 parts of acryl and 22 parts of dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were dissolved in 215 parts of propylene glycol monomethyl ether acetate. Further, a solution prepared by dissolving 3.6 parts of 2,2'-azobisisobutyronitrile was dropped into the flask, and stirring was continued at 100 ° C for 5 hours to obtain a weight average molecular weight of Mw 1.00 × 10 4 and a solid content of 34.1%. A solution of a copolymer (resin B2) having a solid acid value of 109 mg-KOH/g. This resin B2 has the following structural unit.
先在具備回流冷卻器、滴下漏斗及攪拌機之燒瓶內將氮氣以0.02L/分鐘流通使其成為氮氣環境,再將乳酸乙酯220份加入,並於攪拌之同時加熱至70℃。其次,再將甲基丙烯酸84份、及丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯(式(I-1)所示之化合物及式(II-1)所示之化合物,以莫耳比50:50混合者)336份,在乳酸乙酯140份中溶解調製成溶液,再將該溶液,使用滴下漏斗花費4小時滴入保溫於70℃之燒瓶內。另一方面,再將使聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)30份溶解在乳酸乙酯95份中之溶液,使用另一滴下漏斗花費4小時滴入燒瓶內。在該聚合起始劑之溶液滴下結束後,4小時、保持於70℃,之後使其冷卻至室溫,得到重量平均分子量Mw為8.0×103、分子量分布為2.5、固形份48%、溶液酸價為50mg-KOH/g(換算固形份酸價為104mg-KOH/g)之共聚物(樹脂B3)溶液。該樹脂B3,具有以下之結構單元。 First, nitrogen gas was circulated at 0.02 L/min in a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, and then 220 parts of ethyl lactate was added, and the mixture was heated to 70 ° C while stirring. Next, 84 parts of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 2.6 ]decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II-1)) 336 parts of a molar ratio of 50:50, dissolved in 140 parts of ethyl lactate to prepare a solution, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel. On the other hand, a solution in which 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in 95 parts of ethyl lactate is used, and another dropping funnel is used. Drop into the flask every hour. After completion of the dropwise addition of the solution of the polymerization initiator, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 8.0 × 10 3 , a molecular weight distribution of 2.5, a solid content of 48%, and a solution. A copolymer (resin B3) solution having an acid value of 50 mg-KOH/g (in terms of solid content of 104 mg-KOH/g). This resin B3 has the following structural unit.
在合成例中所得到之樹脂的重量平均分子量(Mw)及數量平均分子量(Mn)之測定,係使用GPC法,再以以下之條件操作。 The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured by the GPC method under the following conditions.
裝置;K2479(島津製作所股份有限公司製造) Device; K2479 (made by Shimadzu Corporation)
管柱;SHIMADZU Shim-pack GPC-80M Pipe string; SHIMADZU Shim-pack GPC-80M
管柱溫度;40℃ Column temperature; 40 ° C
溶劑;THF(四氫呋喃) Solvent; THF (tetrahydrofuran)
流速;1.0mL/分鐘 Flow rate; 1.0 mL/min
檢測器;RI Detector; RI
校正用標準品;TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(東曹股份有限公司製造) Standard for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (made by Tosoh Corporation)
將上述中所得到之換算聚苯乙烯之重量平均分子量及數量平均分子量之比(Mw/Mn)作為分子量分布。 The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight of the converted polystyrene obtained above was defined as a molecular weight distribution.
以成為表1-1、表1-2所示之組成之方式將各成分混合而得到著色硬化性樹脂組成物。又,「(A2-1)」,係將丙烯酸系顏料分散劑及「溶劑(E)**」欄記載之溶劑混合,再使用珠磨機預先分散。「溶劑(E)*」欄,係表示各溶劑之合計含量。 The components were mixed so as to have the compositions shown in Table 1-1 and Table 1-2 to obtain a colored curable resin composition. Further, "(A2-1)" is obtained by mixing an acrylic pigment dispersant and a solvent described in the "solvent (E)**" column, and dispersing in advance using a bead mill. The column "Solvent (E)*" indicates the total content of each solvent.
又,表1-1、表1-2中,各成分表示如下者。表中之數值,表示份數。樹脂(B)之份數,表示換算固形份之份數。 In addition, in Table 1-1 and Table 1-2, each component shows the following. The value in the table indicates the number of copies. The number of parts of the resin (B) indicates the number of parts converted into solid parts.
著色劑(A);(A1-1);係染料A1-1 Colorant (A); (A1-1); dye A1-1
著色劑(A);(A1-2);係C.I.直接藍264號與十二碳烷 基苯磺酸之鹽(Orient化學工業股份有限公司製造)(染料) Colorant (A); (A1-2); is C.I. Direct Blue No. 264 and Dodecane Salt of benzenesulfonic acid (manufactured by Orient Chemical Industry Co., Ltd.) (dye)
著色劑(A);(A2-1);係C.I.顏料藍15:6號(顏料) Colorant (A); (A2-1); is C.I. Pigment Blue 15:6 (pigment)
樹脂(B);(B1);係樹脂B1 Resin (B); (B1); resin B1
樹脂(B);(B2);係樹脂B2 Resin (B); (B2); resin B2
樹脂(B);(B3);係樹脂B3 Resin (B); (B3); resin B3
聚合性化合物(C);係六丙烯酸二新戊四醇酯(KAYARAD(註冊商標)DPHA;日本化藥股份有限公司製造) Polymerizable compound (C); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
聚合起始劑(D);(D-1);係N-苯甲醯氧-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-醯肟化合物) Polymerization initiator (D); (D-1); N-benzylidene oxide-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) ) OXE 01; manufactured by BASF; O-醯肟 compound)
聚合起始劑(D);(D-2);係2-甲-2-(N-嗎啉基)-1-(4-甲基硫基苯基)丙烷-1-酮(Irgacure(註冊商標)907;BASF公司製造;烷基苯酮化合物) Polymerization initiator (D); (D-2); 2-methyl-2-(N-morpholinyl)-1-(4-methylthiophenyl)propan-1-one (Irgacure (registered) Trademark) 907; manufactured by BASF; alkyl benzophenone compound)
聚合起始助劑(D1);(D-1-1);係2,4-二乙基噻噸酮(KAYACURE(註冊商標)DETX-S;日本化藥股份有限公司製造;噻噸酮化合物) Polymerization initiation aid (D1); (D-1-1); 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.; thioxanthone compound )
溶劑(E);(E-1);係環己酮 Solvent (E); (E-1); cyclohexanone
溶劑(E);(E-2);係環戊酮 Solvent (E); (E-2); cyclopentanone
溶劑(E);(E-3);係丙二醇單甲醚乙酸酯 Solvent (E); (E-3); propylene glycol monomethyl ether acetate
溶劑(E);(E-4);係丙二醇單甲醚 Solvent (E); (E-4); propylene glycol monomethyl ether
溶劑(E);(E-5);係乳酸乙酯 Solvent (E); (E-5); ethyl lactate
界面活性劑(F);係聚醚改質聚矽氧油(Toray Silicone SH8400;Dow Corning Toray股份有限公司製造) Surfactant (F); polyether modified polyoxygenated oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.)
上述之著色硬化性樹脂組成物中之溶劑之所含比例及 固形份如表2所示。 The proportion of the solvent in the above-mentioned colored curable resin composition and The solid content is shown in Table 2.
所得到之著色硬化性樹脂組成物的黏度,使用黏度計(機種;VISCOMETER TV-30;東機產業股份有限公司製造;回轉速度100rpm;測定溫度23℃)測定。其結果如表3所示。 The viscosity of the obtained colored curable resin composition was measured using a viscometer (model: VISCOMETER TV-30; manufactured by Toki Sangyo Co., Ltd.; rotation speed: 100 rpm; measurement temperature: 23 ° C). The results are shown in Table 3.
先在2吋見方之玻璃基板(EAGLE XG;Corning公司製造)上,將著色感光性樹脂組成物以旋塗法塗布之後,再以100℃預焙3分鐘形成組成物層。在使其冷卻後,使形成有組成物層之基板與含圖樣之石英玻璃製光罩成為100μm之間隔,再使用曝光機(TME-150RSK;TOPCON股份有限公司製造),於大氣環境下,以150mJ/cm2之曝光量(365nm基準)照射光。又,光罩方面,係使用形成有100μm線/間距(line and space)圖樣之光罩。在光照射之後,於含非離子系界面活性劑0.12%及氫氧化鉀0.04%之水系顯像液中將曝光後之組成物層在23℃浸漬60秒使其顯像,經過水洗後,再於烘箱中,於230℃進行後焙20分鐘,得到著色圖樣化塗膜。 The composition of the colored photosensitive resin composition was applied by spin coating on a glass substrate (EAGLE XG; manufactured by Corning Co., Ltd.), and then prebaked at 100 ° C for 3 minutes to form a composition layer. After cooling, the substrate on which the composition layer was formed and the quartz glass mask containing the pattern were placed at intervals of 100 μm, and then exposed to an atmosphere (TME-150RSK; manufactured by TOPCON Co., Ltd.) in an atmosphere. The exposure amount (365 nm reference) of 150 mJ/cm 2 was irradiated with light. Further, in the case of the photomask, a photomask formed with a line pattern of 100 μm line and space was used. After the light irradiation, the exposed composition layer was immersed at 23 ° C for 60 seconds in a water-based developing solution containing a nonionic surfactant of 0.12% and potassium hydroxide 0.04%, and after washing with water, The film was post-baked at 230 ° C for 20 minutes in an oven to obtain a colored pattern coating film.
針對得到之著色圖樣化塗膜,使用膜厚測定裝置(DEKTAK3;日本真空技術股份有限公司製造)測定其膜厚。其結果如表3所示。 The film thickness of the obtained color-coded coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 3.
針對該得到之著色圖樣化塗膜,使用測色機(OSP-SP-200;Olympus股份有限公司製造)測定其分光,使用C光源之特性函數測定在CIE之XYZ表色系中之xy色度座標(x,y)及明度Y。其結果如表3所示。 For the obtained coloring pattern coating film, the color separation was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy color in the XYZ color system of CIE was measured using the characteristic function of the C light source. Coordinate (x, y) and lightness Y. The results are shown in Table 3.
在15cm見方玻璃基板上,將著色硬化性樹脂組成物, 分別使用細縫模具塗布機(卓Die-100,伊藤忠產機股份有限公司製造),以塗布速度70mm/秒,在調整塗布量及噴嘴與基板之距離等之同時,以使硬化後膜厚成為1.5μm之方式進行塗布。之後,再以減壓乾燥機(VCD Microtech股份有限公司製造),將其乾燥至減壓度到達0.5torr為止。再於加熱板上,以90℃預焙2分鐘進一步進行乾燥後,於230℃進行後焙40分鐘形成著色塗膜。將該得到之著色塗膜的表面再以鈉燈照射,並以目視由各種角度觀察塗膜表面,在塗膜表面確定無不均時判定塗布性良好為○,確定有不均時判定為×。其結果如表3所示。 On the 15 cm square glass substrate, the colored curable resin composition is colored, Using a slit die coater (Zoo Die-100, manufactured by Itochu Co., Ltd.) at a coating speed of 70 mm/sec, the coating amount and the distance between the nozzle and the substrate are adjusted, so that the film thickness after hardening becomes Coating was carried out in a manner of 1.5 μm. Thereafter, the mixture was dried under a reduced pressure dryer (manufactured by VCD Microtech Co., Ltd.) until the degree of pressure reduction reached 0.5 torr. Further, it was further pre-baked at 90 ° C for 2 minutes on a hot plate, and then post-baked at 230 ° C for 40 minutes to form a colored coating film. The surface of the obtained colored coating film was further irradiated with a sodium lamp, and the surface of the coating film was observed from various angles by visual observation. When the surface of the coating film was determined to have no unevenness, it was judged that the coating property was good as ○, and when it was determined that there was unevenness, it was judged as ×. The results are shown in Table 3.
實施例之著色硬化性樹脂組成物,確定為低黏度。由此可知,依據本發明之著色硬化性樹脂組成物,可以高生產性進行濾色器之製造。 The colored curable resin composition of the example was determined to have a low viscosity. From this, it is understood that the colored curable resin composition of the present invention can be used for the production of a color filter with high productivity.
本發明之著色硬化性樹脂組成物之黏度低。 The colored curable resin composition of the present invention has a low viscosity.
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