TW201321893A - Colored photosensitive resin composition - Google Patents

Colored photosensitive resin composition Download PDF

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TW201321893A
TW201321893A TW101137000A TW101137000A TW201321893A TW 201321893 A TW201321893 A TW 201321893A TW 101137000 A TW101137000 A TW 101137000A TW 101137000 A TW101137000 A TW 101137000A TW 201321893 A TW201321893 A TW 201321893A
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group
meth
structural unit
acrylate
photosensitive resin
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TW101137000A
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TWI610134B (en
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Kimiyuki Shirouchi
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Sumitomo Chemical Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033Blends of pigments; Mixtured crystals; Solid solutions
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00Diaryl- or thriarylmethane dyes
    • C09B11/04Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10Amino derivatives of triarylmethanes
    • C09B11/24Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007Filters, e.g. additive colour filters; Components for display devices
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)

Abstract

A colored photosensitive resin composition comprising (A), (B1), (B2), (C) and (D) is provided. (A) coloring matter; (B1) a resin comprising a structural unit derived from a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride and a structural unit derived from a monomer having a C2-4 cyclic ether structure and an ethylenic unsaturated bond; (B2) a resin comprising a structural unit derived from a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride and a structural unit derived from a monomer having an alicyclic hydrocarbon structure, provided that the structural unit derived from a monomer having a C2-4 cyclic ether structure and an ethylenic unsaturated bond is not contained; (C) a polymerizable compound; and (D) a polymerization initiator.

Description

著色感光性樹脂組合物 Colored photosensitive resin composition

本發明係關於一種著色感光性樹脂組合物。 The present invention relates to a colored photosensitive resin composition.

業界將著色感光性樹脂組合物用於製造液晶顯示面板、電致發光面板及電漿顯示面板等顯示裝置中所使用之彩色濾光片。作為此種著色感光性樹脂組合物,眾所周知有僅包含甲基丙烯酸與丙烯酸-3,4-環氧三環[5.2.1.02.6]癸酯之共聚物作為樹脂的著色感光性樹脂組合物(JP2010-211198-A)。 The coloring photosensitive resin composition is used in the industry to manufacture color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. As such a color-sensitive photosensitive resin composition, a color-sensitive photosensitive resin composition containing only a copolymer of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 2.6 ]decyl acrylate as a resin is known (JP2010) -211198-A).

利用光微影法形成圖案時,將著色感光性樹脂組合物塗敷於基板上且乾燥所形成之組合物層若在顯影時剝離而流出至顯影液中,則有其剝離片作為異物而附著於圖案上,或者堵塞顯影機內之顯影液廢液的配管之虞。先前以來眾所周知之上述著色感光性樹脂組合物存在如上所述般並無法充分滿足顯影性之情形。 When the pattern is formed by the photolithography method, the colored photosensitive resin composition is applied onto the substrate, and the composition layer formed by drying is peeled off during development to flow out into the developer, and the release sheet is attached as a foreign matter. On the pattern, or clogging the piping of the developer waste liquid in the developing machine. The coloring photosensitive resin composition which has been known in the prior art has a case where the developability cannot be sufficiently satisfied as described above.

本發明包括以下之發明。 The invention includes the following inventions.

[1]一種著色感光性樹脂組合物,其包含(A)、(B1)、(B2)、(C)及(D):(A)著色劑;(B1)包含源自選自由不飽和羧酸及不飽和羧酸酐所組成之群中的至少1種之結構單元、及源自具有碳數2~4之環狀醚結構及乙烯性不飽和鍵之單體之結構單元的樹脂; (B2)包含源自選自由不飽和羧酸及不飽和羧酸酐所組成之群中的至少1種之結構單元、及源自具有脂環式烴結構之單體之結構單元的樹脂(其中,不包含源自具有碳數2~4之環狀醚結構及乙烯性不飽和鍵之單體之結構單元);(C)聚合性化合物;及(D)聚合起始劑。 [1] A colored photosensitive resin composition comprising (A), (B1), (B2), (C), and (D): (A) a colorant; (B1) comprising a source selected from the group consisting of unsaturated carboxylic acids a structural unit of at least one of a group consisting of an acid and an unsaturated carboxylic anhydride; and a resin derived from a structural unit having a cyclic ether structure having a carbon number of 2 to 4 and a monomer having an ethylenically unsaturated bond; (B2) comprising a resin derived from at least one structural unit selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer having an alicyclic hydrocarbon structure (wherein The structural unit derived from a monomer having a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond; (C) a polymerizable compound; and (D) a polymerization initiator.

[2]如[1]之著色感光性樹脂組合物,其中(B2)進而包含源自具有芳香族烴基之單體之結構單元。 [2] The colored photosensitive resin composition according to [1], wherein (B2) further comprises a structural unit derived from a monomer having an aromatic hydrocarbon group.

[3]如[1]或[2]之著色感光性樹脂組合物,其中(B2)之含量相對於(B1)與(B2)之合計量為10~90質量%。 [3] The colored photosensitive resin composition according to [1] or [2], wherein the content of (B2) is from 10 to 90% by mass based on the total of (B1) and (B2).

[4]一種彩色濾光片,其係由如[1]至[3]中任一項之著色感光性樹脂組合物所形成。 [4] A color filter formed of the colored photosensitive resin composition according to any one of [1] to [3].

[5]一種顯示裝置,其包含如[4]之彩色濾光片。 [5] A display device comprising the color filter of [4].

根據本發明之著色感光性樹脂組合物,於顯影後之顯影液中,較少產生來自著色感光性樹脂組合物之剝離片。 According to the colored photosensitive resin composition of the present invention, a release sheet derived from the colored photosensitive resin composition is less likely to be produced in the developer after development.

本發明之著色感光性樹脂組合物包含以下之(A)、(B1)、(B2)、(C)及(D)。 The colored photosensitive resin composition of the present invention comprises the following (A), (B1), (B2), (C) and (D).

(A)著色劑;(B1)包含源自選自由不飽和羧酸及不飽和羧酸酐所組成之群中的至少1種之結構單元、及源自具有碳數2~4之環狀醚結構及乙烯性不飽和鍵之單體之結構單元的樹脂(以下,有時稱作「樹脂(B1)」);(B2)包含源自選自由不飽和羧酸及不飽和羧酸酐所組成 之群中的至少1種之結構單元、及源自具有脂環式烴結構之單體之結構單元的樹脂(其中,不包含源自具有碳數2~4之環狀醚結構及乙烯性不飽和鍵之單體之結構單元)(以下,有時稱作「樹脂(B2)」);(C)聚合性化合物;及(D)聚合起始劑。 (A) a colorant; (B1) comprising at least one structural unit derived from a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a cyclic ether structure derived from a carbon number of 2 to 4. And a resin of a structural unit of a monomer having an ethylenically unsaturated bond (hereinafter sometimes referred to as "resin (B1)"); (B2) comprises a material selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. a resin having at least one structural unit and a structural unit derived from a monomer having an alicyclic hydrocarbon structure (excluding a cyclic ether structure having a carbon number of 2 to 4 and ethylene) a structural unit of a monomer of a saturated bond (hereinafter, sometimes referred to as "resin (B2)"); (C) a polymerizable compound; and (D) a polymerization initiator.

本發明之著色感光性樹脂組合物較佳為進而包含溶劑(E)。 The colored photosensitive resin composition of the present invention preferably further contains a solvent (E).

又,本發明之著色感光性樹脂組合物亦可視需要包含選自由聚合起始助劑(D1)及界面活性劑(F)所組成之群中的至少1種。 Moreover, the colored photosensitive resin composition of the present invention may optionally contain at least one selected from the group consisting of a polymerization starting aid (D1) and a surfactant (F).

再者,只要未特別說明,則各成分可單獨使用1種,亦可將2種以上併用。 In addition, each component may be used alone or in combination of two or more, unless otherwise specified.

<著色劑(A)> <Colorant (A)>

作為著色劑(A),可列舉染料(A1)及顏料(A2)。 Examples of the colorant (A) include a dye (A1) and a pigment (A2).

染料(A1)並無特別限定,可使用眾所周知之染料,例如可列舉溶劑染料、酸性染料、直接染料、媒染染料等,較佳為可溶解於有機溶劑之染料。 The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mord dyes, and the like, and dyes which are soluble in an organic solvent are preferable.

作為染料(A1),例如可列舉於Colour Index(The Society of Dyers and Colourists出版)中分類為染料之化合物,或者染色筆記(Dyeing Note)(色染社)中記載的眾所周知之染料。又,根據化學結構,可列舉偶氮染料、花青染料、三苯甲烷染料、酞菁染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基染料、次甲基偶氮染料、方酸染料、吖啶染 料、苯乙烯染料、香豆素染料、喹啉染料、硝基染料等。該等之中,較佳為有機溶劑可溶性染料。 Examples of the dye (A1) include a compound classified as a dye in the Colour Index (published by The Society of Dyers and Colourists), or a well-known dye described in Dyeing Note (color dyeing company). Further, examples of the chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, and methine azo dyes. Squaric acid dye, acridine dye Materials, styrene dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like. Among these, an organic solvent-soluble dye is preferred.

具體而言,可列舉C.I.溶劑黃4(以下,省略C.I.溶劑黃之記載,僅記載編號)、14、15、23、24、38、62、63、68、82、94、98、99、117、162、163、167、189,C.I.溶劑紅45、49、111、125、130、143、145、146、150、151、155、168、169、172、175、181、207、218、222、227、230、245、247,C.I.溶劑橙2、7、11、15、26、56、77、86,C.I.溶劑紫11、13、14、26、31、36、37、38、45、47、48、51、59、60,C.I.溶劑藍4、5、14、18、35、36、37、45、58、59、59:1、63、67、68、69、70、78、79、83、90、94、97、98、100、101、102、104、105、111、112、122、128、132、136、139,C.I.溶劑綠1、3、4、5、7、28、29、32、33、34、35等C.I.溶劑染料;C.I.酸性黃1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251, C.I.酸性紅1、4、8、14、17、18、26、27、29、31、33、34、35、37、40、42、44、50、51、52、57、66、73、76、80、87、88、91、92、94、95、97、98、103、106、111、114、129、133、134、138、143、145、150、151、155、158、160、172、176、182、183、195、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、289、308、312、315、316、339、341、345、346、349、382、383、388、394、401、412、417、418、422、426,C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169、173,C.I.酸性紫6B、7、9、17、19、30、34、102,C.I.酸性藍1、7、9、15、18、22、23、25、27、29、40、41、42、43、45、51、54、59、60、62、70、72、74、78、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、236、242、243、256、259、267、278、280、285、290、296、315、324:1、335、340,C.I.酸性綠1、3、5、9、16、25、27、28、41、50、58、63、65、80、104、105、106、109等C.I.酸性染料;C.I.直接黃2、33、34、35、38、39、43、47、50、54、 58、68、69、70、71、86、93、94、95、98、102、108、109、129、136、138、141,C.I.直接紅79、82、83、84、91、92、96、97、98、99、105、106、107、172、173、176、177、179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250,C.I.直接橙26、34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107,C.I.直接紫47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104,C.I.直接藍1、2、6、8、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、137、149、150、153、155、156、158、159、160、161、162、163、164、165、166、167、168、170、171、172、173、188、189、190、192、193、194、195、196、198、199、200、201、202、203、207、209、210、212、213、214、222、225、226、228、229、236、237、238、242、243、244、245、246、247、248、249、250、251、252、256、257、259、260、268、274、275、293,C.I.直接綠25、27、31、32、34、37、63、65、66、67、68、69、72、77、79、82等C.I.直接染料;C.I.分散黃51、54、76, C.I.分散紫26、27,C.I.分散藍1、14、56、60等C.I.分散染料;C.I.鹼性紅1、10,C.I.鹼性藍1、3、5、7、9、19、21、22、24、25、26、28、29、40、41、45、47、54、58、59、60、64、65、66、67、68,C.I.鹼性綠1等C.I.鹼性染料;C.I.反應性黃2、76、116,C.I.反應性橙16,C.I.反應性紅36等C.I.反應性染料;C.I.媒染黃5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65,C.I.媒染紅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、71、74、85、86、88、90、94、95,C.I.媒染橙3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48,C.I.媒染紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53、58,C.I.媒染藍1、2、3、7、8、9、12、13、15、16、19、20、21、22、23、24、26、30、31、32、39、40、41、43、44、48、49、53、61、74、77、83、84,C.I.媒染綠1、3、4、5、10、15、19、26、29、33、34、35、41、43、53等C.I.媒染染料; C.I.還原綠1等C.I.還原染料等。 Specifically, CI solvent yellow 4 (hereinafter, the description of CI solvent yellow is omitted, only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 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, 26, 56, 77, 86, CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83 , 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other CI solvent dyes; CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73 , 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168 , 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76 , 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172 , 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281 , 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426, CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, CI Acid Violet 6B, 7, 9, 17, 19, 30 , 34, 102, CI Acid Blue 1, 7, 9, 15, 18, 22, 23, 25, 27, 29, 40, 41, 42, 43, 45, 51, 54, 59, 60, 62, 70, 72, 74, 78, 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, 236, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340, CI Acid Green 1, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58 CI acid dyes such as 63, 65, 80, 104, 105, 106, 109; 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, 83, 84, 91, 92, 96 , 97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234 , 241, 243, 246, 250, CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, CI directly Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, CI Direct Blue 1, 2, 6, 8, 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, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, CI directly CI direct dyes such as green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82; CI disperse yellow 51, 54, 76, CI disperse violet 26, 27, CI disperse blue 1, 14, 56, 60 and other CI disperse dyes; CI alkaline red 1, 10, CI alkaline blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, CI basic green 1 and other CI basic dyes; CI reactivity Yellow 2, 76, 116, CI Reactive Orange 16, CI Reactive Red 36 and other CI reactive dyes; CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45 , 56, 61, 62, 65, CI mordant 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, 71, 74, 85, 86, 88, 90, 94, 95, CI mordant orange 3, 4, 5 , 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13 , 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39 , 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, CI mord green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and other CI mordant dyes; C.I. Reduction of green 1, etc. C.I. vat dyes and the like.

該等染料只要根據所期望之彩色濾光片之分光光譜而適當選擇即可。 These dyes may be appropriately selected depending on the spectral spectrum of the desired color filter.

作為染料(A1),較佳為染料(Aa)。 As the dye (A1), it is preferably Dye (Aa).

染料(Aa)係包含分子內具有骨架之化合物之染料。作為染料(Aa),例如可列舉:C.I.酸性紅51(以下,省略C.I.酸性紅之記載,僅記載編號;其它亦相同)、52、87、92、94、289、388,C.I.酸性紫9、30、102,C.I.鹼性紅1(羅丹明6G)、2、3、4、8、C.I.鹼性紅10(羅丹明B)、11,C.I.鹼性紫10、11、25,C.I.溶劑紅218、C.I.媒染紅27、C.I.反應性紅36(孟加拉玫瑰紅B)、磺醯羅丹明G、JP2010-32999-A中記載之染料及JP4492760-B中記載之染料等。較佳為可溶解於有機溶劑者。 Dye (Aa) contains intramolecular A dye of a compound of the skeleton. As Examples of the dye (Aa) include CI Acid Red 51 (hereinafter, the description of CI Acid Red is omitted, only the number is described; the others are the same), 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30 , 102, CI alkaline red 1 (rhodamine 6G), 2, 3, 4, 8, CI alkaline red 10 (rhodamine B), 11, CI alkaline purple 10, 11, 25, CI solvent red 218, CI mordant red 27, CI reactive red 36 (Bengal rose red B), sulfonium rhodamine G, JP2010-32999-A Dyes and materials described in JP4492760-B Dyes, etc. It is preferably one which is soluble in an organic solvent.

該等之中,染料(Aa)較佳為包含由式(1a)所表示之化合物(以下,有時稱作「化合物(1a)」)之染料。於使用化合物(1a)之情形時,染料(Aa)中之化合物(1a)之含量較佳為50質量%以上,更佳為70質量%以上,進而較佳為90質量%以上。尤佳為僅使用化合物(1a)作為染料(Aa)。 Among these, The dye (Aa) is preferably a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as "compound (1a)"). In the case of using the compound (1a), The content of the compound (1a) in the 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. It is especially preferred to use only compound (1a) as Dye (Aa).

[於式(1a)中,R1~R4分別獨立地表示氫原子、-R8或亦可具有取代基之碳數6~10之一價芳香族烴基。R1及R2亦可與氮原子一起形成含有氮原子之環,R3及R4亦可與氮原子一起形成含有氮原子之環。R5表示-OH、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2 -Z+、-CO2R8、-SO3R8或-SO2NR9R10。R6及R7分別獨立地表示氫原子或碳數1~6之烷基。m表示0~5之整數。於m為2以上之整數之情形時,複數個R5既可相同亦可不同。其中,於R5為-SO3 -之情形時,m為1。a表示0或1之整數。X表示鹵素原子。R8表示碳數1~20之一價飽和烴基,該飽和烴基中所含之氫原子亦可經鹵素原子取代。Z+表示+N(R11)4、Na+或K+。R9及R10分別獨立地表示氫原子或碳數1~20之一價飽和烴基,R9及R10亦可相互鍵結而與氮原子一起形成3~10員環之含氮雜環。R11分別獨立地表示氫原子、碳數1~20之一價飽和烴基或碳數7~10之芳烷基]。 [In the formula (1a), R 1 to R 4 each independently represent a hydrogen atom, -R 8 or a C 6-10 monovalent aromatic hydrocarbon group which may have a substituent. 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. 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 . R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents an integer from 0 to 5. In the case where m is an integer of 2 or more, a plurality of R 5 may be the same or different. Wherein, when R 5 is -SO 3 - , m is 1. a represents an integer of 0 or 1. X represents a halogen atom. R 8 represents a one-valent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. Z + represents + N(R 11 ) 4 , Na + or K + . 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 3 to 10 member ring together with the nitrogen atom. 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.

作為表示R1~R4之碳數6~10之一價芳香族烴基,例如可列舉:苯基、甲苯甲醯基、二甲苯基、基、丙基苯基及丁基苯基。 Examples of the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms of R 1 to R 4 include a phenyl group, a tolylmethyl group, and a xylyl group. Base, propyl phenyl and butyl phenyl.

R1~R4之碳數6~10之一價芳香族烴基中,該芳香族烴基 所含之氫原子亦可經鹵素原子、-R8、-OH、-OR8、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2R8、-SR8、-SO3R8、-SO2NR9R10等取代。於該等取代基之中,較佳為選自由-SO3 -、-SO3H、-SO3 -Z+及-SO2NR9R10所組成之群中的至少1種,更佳為選自由-SO3 -Z+及-SO2NR9R10所組成之群中的至少1種。此時之-SO3 -Z+較佳為-SO3 -+N(R11)4。若R1~R4為該等基,則包含化合物(1a)之著色感光性樹脂組合物可形成較少產生異物,且耐熱性優異之彩色濾光片。 In the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms of R 1 to R 4 , the hydrogen atom contained in the aromatic hydrocarbon group may also pass through 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 , -SO 2 NR 9 R 10 , etc. Among the 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 more preferably At least one selected from the group consisting of -SO 3 - Z + and -SO 2 NR 9 R 10 is selected. At this time, -SO 3 - Z + is preferably -SO 3 -+ N(R 11 ) 4 . When R 1 to R 4 are such a group, the colored photosensitive resin composition containing the compound (1a) can form a color filter which is less likely to generate foreign matter and is excellent in heat resistance.

R1及R2亦可與氮原子一起形成含有氮原子之環,R3及R4亦可與氮原子一起形成含有氮原子之環。作為該含有氮原子之環,例如可列舉以下者。 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. Examples of the ring containing a nitrogen atom include the following.

作為表示R8~R11之碳數1~20之一價飽和烴基,可列舉:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十六烷基、二十基等碳數1~20之直鏈狀烷基;異丙基、異丁基、異戊基、新戊基、2-乙基己基等碳數3~20之支鏈狀烷基;環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等碳數3~20之脂環式飽和烴基。 Examples of the one-valent saturated hydrocarbon group having 1 to 20 carbon atoms of R 8 to R 11 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a decyl group. a linear alkyl group having 1 to 20 carbon atoms such as dodecyl, hexadecyl or icosyl; carbon such as isopropyl, isobutyl, isopentyl, neopentyl or 2-ethylhexyl a branched alkyl group of 3 to 20; an alicyclic 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.

作為-OR8,例如可列舉: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-乙基己氧基及二十烷氧基。 Examples of -OR 8 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and two. Decaconoxy.

作為-CO2R8,例如可列舉:甲氧基羰基、乙氧基羰基、丙氧基羰基、第三丁氧基羰基、己氧基羰基及二十烷氧基羰基。 Examples of the -CO 2 R 8 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

作為-SR8,例如可列舉:甲基硫烷基、乙基硫烷基、丁基硫烷基、己基硫烷基、癸基硫烷基及二十基硫烷基等。 Examples of -SR 8 include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a mercaptosulfanyl group, and a decylsulfanyl group.

作為-SO2R8,例如可列舉:甲基磺醯基、乙基磺醯基、丁基磺醯基、己基磺醯基、癸基磺醯基及二十基磺醯基。 Examples of -SO 2 R 8 include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and a decylsulfonyl group.

作為-SO3R8,例如可列舉:甲氧基磺醯基、乙氧基磺醯基、丙氧基磺醯基、第三丁氧基磺醯基、己氧基磺醯基及二十烷氧基磺醯基。 Examples of -SO 3 R 8 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a third butoxysulfonyl group, a hexyloxysulfonyl group, and Alkoxysulfonyl.

作為-SO2NR9R10,例如可列舉:胺磺醯基;N-甲基胺磺醯基、N-乙基胺磺醯基、N-丙基胺磺醯基、N-異丙基胺磺醯基、N-丁基胺磺醯基、N-異丁基胺磺醯基、N-第二丁基胺磺醯基、N-第三丁基胺磺醯基、N-戊基胺磺醯基、N-(1-乙基丙基)胺磺醯基、N-(1,1-二甲基丙基)胺磺醯基、N-(1,2-二甲基丙基)胺磺醯基、N-(2,2-二甲基丙基)胺磺醯基、N-(1-甲基丁基)胺磺醯基、N-(2-甲基丁基)胺磺醯基、N-(3-甲基丁基)胺磺醯基、N-環戊基胺磺醯基、N-己基胺磺醯基、N-(1,3-二甲基丁基)胺磺醯基、N-(3,3-二甲基丁基)胺磺醯基、N-庚基胺磺醯基、N-(1-甲基己基)胺磺醯基、N-(1,4-二甲基戊基)胺磺醯基、N-辛基胺磺醯基、N-(2-乙基己基)胺磺醯基、N-(1,5-二甲基)己基胺磺醯基、N-(1,1,2,2-四甲基丁基)胺磺醯基等N-1取代胺磺醯基; N,N-二甲基胺磺醯基、N,N-乙基甲基胺磺醯基、N,N-二乙基胺磺醯基、N,N-丙基甲基胺磺醯基、N,N-異丙基甲基胺磺醯基、N,N-第三丁基甲基胺磺醯基、N,N-丁基乙基胺磺醯基、N,N-雙(1-甲基丙基)胺磺醯基、N,N-庚基甲基胺磺醯基等N,N-2取代胺磺醯基等。 Examples of -SO 2 NR 9 R 10 include an aminesulfonyl group; N-methylaminesulfonyl group, N-ethylaminesulfonyl group, N-propylaminesulfonyl group, and N-isopropyl group; Aminesulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentyl Aminesulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl Aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)amine Sulfonyl, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl) Aminesulfonyl, N-(3,3-dimethylbutyl)aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N-(1 ,4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl)hexylamine N-1 substituted amine sulfonyl group such as sulfonyl, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl; N,N-dimethylamine sulfonyl, N,N -ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N- Propylmethylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-t-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N An N, N-2 substituted amine sulfonyl group such as N-bis(1-methylpropyl)amine sulfonyl group or N,N-heptylmethylamine sulfonyl group.

又,表示R9及R10之碳數1~20之一價飽和烴基中,該飽和烴基所含之氫原子亦可經-OH或鹵素原子取代,該飽和烴基所含之-CH2-亦可經-O-、-CO-、-NH-或-NR8-置換。 Further, in the one-valent saturated hydrocarbon group having 1 to 20 carbon atoms of R 9 and R 10 , the hydrogen atom contained in the saturated hydrocarbon group may be substituted by -OH or a halogen atom, and the -CH 2 - contained in the saturated hydrocarbon group is also It may be replaced by -O-, -CO-, -NH- or -NR 8 -.

R9及R10亦可相互鍵結而與氮原子一起形成3~10員環之含氮雜環。作為該雜環,例如可列舉以下者。 R 9 and R 10 may be bonded to each other to form a nitrogen-containing heterocyclic ring of 3 to 10 membered rings together with a nitrogen atom. Examples of the hetero ring include the following.

作為表示R6及R7之碳數1~6之烷基,可列舉上述中所列舉之直鏈狀烷基及支鏈狀烷基中的碳數1~6者。 Examples of the alkyl group having 1 to 6 carbon atoms of R 6 and R 7 include those having 1 to 6 carbon atoms in the linear alkyl group and the branched alkyl group described above.

作為表示R11之碳數7~10之芳烷基,可列舉苄基、苯基乙基、苯基丁基等。 Examples of the aralkyl group having 7 to 10 carbon atoms of R 11 include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z++N(R11)4、Na+或K+,較佳為+N(R11)4Z + is + N(R 11 ) 4 , Na + or K + , preferably + N(R 11 ) 4 .

作為上述+N(R11)4,較佳為4個R11中至少2個為碳數5~20之一價飽和烴基。又,4個R11之合計碳數較佳為20~80,更佳為20~60。若R11為該等基,則包含化合物(1a)之著色感光性樹脂組合物可形成異物較少之彩色濾光片。 As the above + N(R 11 ) 4 , at least two of the four R 11 are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R 11 is preferably from 20 to 80, more preferably from 20 to 60. When R 11 is such a group, the colored photosensitive resin composition containing the compound (1a) can form a color filter having less foreign matter.

m較佳為1~4,更佳為1或2。 m is preferably from 1 to 4, more preferably 1 or 2.

作為染料(Aa),更佳為包含由式(2a)所表示之化合物(以下,有時稱作「化合物(2a)」)之染料。於使用化合 物(2a)之情形時,染料(Aa)中之化合物(2a)之含量較佳為50質量%以上,更佳為70質量%以上,進而較佳為90質量%以上。 As The dye (Aa) is more preferably a dye containing a compound represented by the formula (2a) (hereinafter sometimes referred to as "compound (2a)"). In the case of using the compound (2a), The content of the compound (2a) in the 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.

[於式(2a)中,R21~R24分別獨立地表示氫原子、-R26或碳數6~10的一價之亦可具有取代基之芳香族烴基。R21及R22亦可與氮原子一起形成含有氮原子之環,R23及R24亦可與氮原子一起形成含有氮原子之環。R25表示-SO3 -、-SO3H、-SO3 -Z1+或-SO2NHR26。m1表示0~5之整數。於m1為2以上之整數之情形時,複數個R25既可相同亦可不同。其中,於R25為-SO3 -之情形時,m1為1。a1表示0或1之整數。X1表示鹵素原子。R26表示碳數1~20之一價飽和烴基。Z1+表示+N(R27)4、Na+或K+。R27分別獨立地表示碳數1~20之一價飽和烴基或苄基]。 [In the formula (2a), R 21 to R 24 each independently represent a hydrogen atom, -R 26 or a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10 which may have a substituent. R 21 and R 22 may form a ring containing a nitrogen atom together with a nitrogen atom, and R 23 and R 24 may form a ring containing a nitrogen atom together with a nitrogen atom. R 25 represents -SO 3 - , -SO 3 H, -SO 3 - Z1 + or -SO 2 NHR 26 . M1 represents an integer from 0 to 5. In the case where m1 is an integer of 2 or more, the plurality of R 25 may be the same or different. Wherein, in the case where R 25 is -SO 3 - , m1 is 1. A1 represents an integer of 0 or 1. X1 represents a halogen atom. R 26 represents a one-valent saturated hydrocarbon group having 1 to 20 carbon atoms. Z1 + represents + N(R 27 ) 4 , Na + or K + . R 27 independently represents a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms.

作為表示R21~R24之碳數6~10之一價芳香族烴基,可列舉與上述R1~R4中作為芳香族烴基所列舉者相同之基。該 芳香族烴基中所含之氫原子亦可經-SO3 -、-SO3H、-SO3 -Z1+、-SO3R26或-SO2NHR26取代。 Examples of the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms of R 21 to R 24 include the same groups as those exemplified as the aromatic hydrocarbon group in the above R 1 to R 4 . The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -SO 3 - , -SO 3 H, -SO 3 - Z1 + , -SO 3 R 26 or -SO 2 NHR 26 .

作為R21~R24之組合,較佳為R21及R23為氫原子,R22及R24為碳數6~10之一價芳香族烴基,且該芳香族烴基中所含之氫原子經-SO3 -、-SO3H、-SO3 -Z1+、-SO3R26或-SO2NHR26取代者。進而較佳之組合為R21及R23為氫原子,R22及R24為碳數6~10之一價芳香族烴基,且該芳香族烴基中所含之氫原子經-SO3 -Z1+或-SO2NHR26取代者。 As a combination of R 21 to R 24 , R 21 and R 23 are preferably a hydrogen atom, and 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. Substituted by -SO 3 - , -SO 3 H, -SO 3 - Z1 + , -SO 3 R 26 or -SO 2 NHR 26 . Further preferably, 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 is via -SO 3 - Z1 + Or -SO 2 NHR 26 replacement.

又,較佳為R21及R22與氮原子一起形成含有氮原子之脂肪族雜環,且R23及R24與氮原子一起形成含有氮原子之脂肪族雜環者。 Further, 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.

若R21~R24為該等基,則包含化合物(2a)之著色感光性樹脂組合物可形成耐熱性優異之彩色濾光片。 When R 21 to R 24 are these groups, the colored photosensitive resin composition containing the compound (2a) can form a color filter excellent in heat resistance.

作為上述脂肪族雜環,例如可列舉下述者。 Examples of the aliphatic heterocyclic ring include the following.

作為表示R26及R27之碳數1~20之一價飽和烴基,可列舉與R8~R11中作為飽和烴基所列舉者相同之基。 Examples of the one-valent saturated hydrocarbon group having 1 to 20 carbon atoms of R 26 and R 27 include the same groups as those exemplified as the saturated hydrocarbon group in R 8 to R 11 .

R21~R24中之-R26較佳為分別獨立地為氫原子、甲基或乙基。又,作為-SO3R26及-SO2NHR26中之R26,較佳為碳數3~20之支鏈狀烷基,更佳為碳數6~12之支鏈狀烷基,進而較佳為2-乙基己基。若R26為該等基,則包含化合物(2a)之著色感光性樹脂組合物可形成較少產生異物之彩色濾光 片。 R 21 ~ R -R is preferably in the 24 26 are each independently a hydrogen atom, methyl or ethyl. Further, and as -SO 3 R 26 in the -SO 2 NHR 26 R 26, preferred is a branched alkyl group having a carbon number of 3 to 20, more preferably 6 to 12 carbon atoms of the branched chain alkyl group, and further It is preferably 2-ethylhexyl. When R 26 is such a group, the colored photosensitive resin composition containing the compound (2a) can form a color filter which generates less foreign matter.

Z1++N(R27)4、Na+或K+,較佳為+N(R27)4Z1 + is + N(R 27 ) 4 , Na + or K + , preferably + N(R 27 ) 4 .

作為上述+N(R27)4,較佳為4個R27中至少2個為碳數5~20之一價飽和烴基。又,4個R27之合計碳數較佳為20~80,更佳為20~60。若R27為該等基,則包含化合物(2a)之著色感光性樹脂組合物可形成較少產生異物之彩色濾光片。 As the above + N(R 27 ) 4 , at least two of the four R 27 are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R 27 is preferably from 20 to 80, more preferably from 20 to 60. When R 27 is such a group, the colored photosensitive resin composition containing the compound (2a) can form a color filter which generates less foreign matter.

m1較佳為1~4,更佳為1或2。 M1 is preferably from 1 to 4, more preferably 1 or 2.

作為化合物(2a),例如可列舉由式(1-1)~式(1-25)所表示之化合物。再者,式中,R26表示碳數1~20之一價飽和烴基,較佳為碳數6~12之支鏈狀烷基,進而較佳為2-乙基己基。該等之中,較佳為C.I.酸性紅289之磺醯胺化物、C.I.酸性紅289之四級銨鹽、C.I.酸性紫102之磺醯胺化物或C.I.酸性紫102之四級銨鹽。作為此種化合物,例如可列舉由式(1-1)~式(1-8)、式(1-11)及式(1-12)所表示之化合物等。 The compound (2a) is, for example, a compound represented by the formula (1-1) to the formula (1-25). Further, 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, and further preferably 2-ethylhexyl group. Among these, a sulfonium amidate of CI Acid Red 289, a quaternary ammonium salt of CI Acid Red 289, a sulfonamide of CI Acid Violet 102, or a quaternary ammonium salt of CI Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12).

又,作為染料(Aa),包含由式(3a)所表示之化合物(以下,有時稱作「化合物(3a)」)之染料亦更佳。於使用化合物(3a)之情形時,染料(Aa)中之化合物(3a)之含量較佳為50質量%以上,更佳為70質量%以上,進而較佳為90質量%以上。 Again, as The dye (Aa), which contains a compound represented by the formula (3a) (hereinafter sometimes referred to as "compound (3a)"), is also more preferable. In the case of using the compound (3a), The content of the compound (3a) in the 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.

[於式(3a)中,R31及R32相互獨立地表示碳數1~4之烷基。R33及R34相互獨立地表示碳數1~4之烷基、碳數1~4之烷基硫烷基或碳數1~4之烷基磺醯基。R31及R33亦可與氮原子一起形成含有氮原子之環,R32及R34亦可與氮原子一起形成含有氮原子之環。p及q相互獨立地表示0~5之整數。於p為2以上之情形時,複數個R33既可相同亦可不同,於q為2以上之情形時,複數個R34既可相同亦可不同]。 [In the formula (3a), R 31 and R 32 each independently represent an alkyl group having 1 to 4 carbon atoms. R 33 and R 34 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms. R 31 and R 33 may form a ring containing a nitrogen atom together with a nitrogen atom, and R 32 and R 34 may form a ring containing a nitrogen atom together with a nitrogen atom. p and q independently represent an integer from 0 to 5. When p is 2 or more, the plurality of R 33 may be the same or different. When q is 2 or more, the plurality of R 34 may be the same or different.

作為表示R31、R32、R33及R34之碳數1~4之烷基,可列舉:甲基、乙基、丙基、丁基、異丙基、異丁基、第二丁 基、第三丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms of R 31 , R 32 , R 33 and R 34 include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and a second butyl group. , third butyl, and the like.

作為表示R33及R34之碳數1~4之烷基硫烷基,可列舉:甲基硫烷基、乙基硫烷基、丙基硫烷基、丁基硫烷基、異丙基硫烷基等。 Examples of the alkylsulfanyl group having 1 to 4 carbon atoms of R 33 and R 34 include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropyl group. Sulfuryl group and the like.

作為表示R33及R34之碳數1~4之烷基磺醯基,可列舉: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。 Examples of the alkylsulfonyl group having 1 to 4 carbon atoms of R 33 and R 34 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropyl group. Sulfonyl and the like.

R31及R32較佳為相互獨立地為甲基及乙基。R33及R34較佳為碳數1~4之烷基,更佳為甲基。 R 31 and R 32 are preferably each independently a methyl group and an ethyl group. R 33 and R 34 are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

m及n較佳為0~2之整數,更佳為0或1。 m and n are preferably an integer of 0 to 2, more preferably 0 or 1.

作為化合物(3a),例如可列舉分別由式(1-26)~式(1-32)所表示之化合物。其中,就對有機溶劑之溶解性優異之方面而言,較佳為由式(1-26)所表示之化合物。 The compound (3a) is, for example, a compound represented by the formula (1-26) to the formula (1-32). Among them, the compound represented by the formula (1-26) is preferred from the viewpoint of excellent solubility in an organic solvent.

染料(Aa)可使用市售之染料(例如,中外化成(股)製造之「Chugai Aminol Fast Pink R-H/C」,田岡化學工業(股)製造之「Rhodamin 6G」)。又,亦可以市售之染料為起始原料,參照JP2010-32999-A進行合成。 Dye (Aa) can be used commercially Dye (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Sino-foreign Chemical Co., Ltd., "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd.). Also, it is also available for sale. The dye was used as a starting material and synthesized by referring to JP2010-32999-A.

作為染料(A1),酞菁染料(Ab)亦較佳。酞菁染料(Ab)較佳為由式(4)所表示之化合物。 As the dye (A1), a phthalocyanine dye (Ab) is also preferred. The phthalocyanine dye (Ab) is preferably a compound represented by the formula (4).

[於式(4)中,G1表示碳數2~16之烷二基,該烷二基中所含之-CH2-亦可經-O-置換。J1表示氫原子、-NRaRb或-NRaRbH+Q-。Ra及Rb相互獨立地表示氫原子或碳數1~8之烷基。Q-表示鹵化物離子、BF4 -、PF6 -、ClO4 -、X-CO2 -或Y-SO3 -。X及Y分別獨立地表示一價有機基。p表示1~4之整數]。 [In the formula (4), G 1 represents an alkanediyl group having 2 to 16 carbon atoms, and -CH 2 - contained in the alkanediyl group may be substituted by -O-. J 1 represents a hydrogen atom, -NR a R b or -NR a R b H + Q - . R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Q - represents a halide ion, BF 4 - , PF 6 - , ClO 4 - , X-CO 2 - or Y-SO 3 - . X and Y each independently represent a monovalent organic group. p represents an integer from 1 to 4].

式(4)表示以式(4-0)所示之化合物中所含之p個氫原子經 -SO2-NH-G1-J1取代。於p為2以上之情形時,複數個-SO2-NH-G1-J1既可相互相同亦可不同。 Formula (4) represents that p hydrogen atoms contained in the compound represented by formula (4-0) are substituted with -SO 2 -NH-G 1 -J 1 . When p is 2 or more, a plurality of -SO 2 -NH-G 1 -J 1 may be the same or different from each other.

作為碳數2~12之烷二基,可列舉:亞甲基、伸乙基、丙二基、丁二基等。 Examples of the alkanediyl group having 2 to 12 carbon atoms include a methylene group, an ethylidene group, a propylenediyl group, and a butyldiyl group.

作為-CH2-經-O-置換之碳數2~12之烷二基,可列舉由式(G-1)所表示之基及由式(G-2)所表示之基。 Examples of the alkanediyl group having 2 to 12 carbon atoms which are substituted by -CH 2 -O-O are a group represented by the formula (G-1) and a group represented by the formula (G-2).

[於式(G-1)及式(G-2)中,G2~G5分別獨立地表示碳數1~8之烷二基。n1表示1~3之整數。n2表示0~3之整數。其中,由式(G-1)所表示之基中所含之碳原子及氧原子之合計數為3~12,由式(G-2)所表示之基中所含之碳原子及氧原子之合計數為2~12。*表示與-NH-之鍵結鍵]。 [In the formula (G-1) and the formula (G-2), G 2 to G 5 each independently represent an alkanediyl group having 1 to 8 carbon atoms. N1 represents an integer from 1 to 3. N2 represents an integer from 0 to 3. Wherein the total number of carbon atoms and oxygen atoms contained in the group represented by the formula (G-1) is 3 to 12, and the carbon atom and oxygen atom contained in the group represented by the formula (G-2) The total count is 2~12. * indicates a bond with -NH-].

作為碳數1~4之烷基,可列舉:甲基、乙基、丙基、丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.

作為-SO2-NH-G1-J1,例如可列舉由下述式所表示之基。 Examples of -SO 2 -NH-G 1 -J 1 include a group represented by the following formula.

於G1為由式(G-1)所表示之基之情形時,作為-SO2-NH-G1-J1,例如可列舉由下述式所表示之基。 In the case where G 1 is a group represented by the formula (G-1), examples of the -SO 2 -NH-G 1 -J 1 include a group represented by the following formula.

於G1為由式(G-2)所表示之基之情形時,作為-SO2-NH-G1-J1,例如可列舉由下述式所表示之基。 In the case where G 1 is a group represented by the formula (G-2), examples of the -SO 2 -NH-G 1 -J 1 include a group represented by the following formula.

於J1為-NRaRb之情形時,作為-SO2-NH-G1-J1,例如可列舉由下述式所表示之基。 In the case where J 1 is -NR a R b , examples of -SO 2 -NH-G 1 -J 1 include a group represented by the following formula.

於J1為-NRaRbH+Q-之情形時,作為-SO2-NH-G1-NRaRbH+,例如可列舉由下述式所表示之基。 In the case where J 1 is -NR a R b H + Q - , examples of -SO 2 -NH-G 1 -NR a R b H + include a group represented by the following formula.

Q-表示鹵化物離子、BF4 -、PF6 -、ClO4 -、X-CO2 -或Y-SO3 -Q - represents a halide ion, BF 4 - , PF 6 - , ClO 4 - , X-CO 2 - or Y-SO 3 - .

X及Y表示一價有機基。作為一價有機基,可列舉:碳數1~20之烷基、碳數3~20之環烷基、碳數6~20之芳基及組合有該等之基等。 X and Y represent a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a group in which these groups are combined.

作為碳數1~20之烷基,可列舉:甲基、乙基、丙基、丁基、己基、癸基等。 Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group.

作為碳數3~20之環烷基,可列舉:環丙基、環丁基、環戊基、環己基、環癸基等。 Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.

作為碳數6~20之芳基,可列舉:苯基、萘基、蒽基等。 Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthracenyl group.

X-CO2 -係含有CO2 -基之有機物陰離子,Y-SO3 -係含有 SO3 -基之有機物陰離子,例如可列舉由式(Q-1)~式(Q-4)所表示之陰離子。 X-CO 2 - is an organic anion containing a CO 2 - group, and Y-SO 3 - is an organic anion containing an SO 3 - group, and is represented by, for example, a formula (Q-1) to a formula (Q-4). Anion.

[Ry表示碳數1~20之烷基。 [R y represents an alkyl group having 1 to 20 carbon atoms.

n3表示0~5之整數]。 N3 represents an integer from 0 to 5.].

作為Q-,較佳為X-CO2 -及Y-SO3 -,更佳為由式(Q-4)所表示之陰離子。若為該等陰離子,則存在由式(2)所表示之化合物對溶劑之溶解性提高之傾向。 As Q - , X-CO 2 - and Y-SO 3 - are preferable, and an anion represented by the formula (Q-4) is more preferable. In the case of these anions, the solubility of the compound represented by the formula (2) in a solvent tends to be improved.

作為由式(4)所表示之化合物,例如可列舉JP2011-28236-A所揭示之化合物。其中,較佳為由式(4-1)~式(4-5)所表示之化合物,更佳為由式(4-2)所表示之化合物及由式(4-5)所表示之化合物。 The compound represented by the formula (4) is, for example, a compound disclosed in JP2011-28236-A. Among them, a compound represented by the formula (4-1) to the formula (4-5) is preferred, and a compound represented by the formula (4-2) and a compound represented by the formula (4-5) are more preferred. .

作為顏料(A2),例如可列舉於Colour Index(The Society of Dyers and Colourists出版)中分類為顏料之化合物。 As the pigment (A2), for example, a compound classified as a pigment in the Colour Index (published by The Society of Dyers and Colourists) can be cited.

作為顏料,例如可列舉C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、180、185、194、214、219等黃色顏料;C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料;C.I.顏料紅9、97、105、122、123、144、149、166、168、175、176、177、180、192、209、215、216、224、 242、254、255、264、265等紅色顏料;C.I.顏料藍15、15:3、15:4、15:6、60、80等藍色顏料;C.I.顏料紫1、19、23、29、32、36、38等紫色顏料;C.I.顏料綠7、36、58等綠色顏料;C.I.顏料棕23、25等棕色顏料;C.I.顏料黑1、7等黑色顏料等。 As the pigment, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 can be cited. Yellow pigments such as 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194, 214, 219; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43 , 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192 209, 215, 216, 224, Red pigments such as 242, 254, 255, 264, and 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, 80; CI Pigment Violet 1, 19, 23, 29, 32 , 36, 38 and other purple pigments; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7 and other black pigments.

將本發明之著色感光性樹脂組合物製備為藍色著色感光性樹脂組合物之情形時,作為顏料,較佳為C.I.顏料藍15、15:3、15:4、15:6、60等藍色顏料及C.I.顏料紫1、19、23、29、32、36、38等紫色顏料,更佳為C.I.顏料藍15:3、15:6及C.I.顏料紫23,進而較佳為C.I.顏料藍15:6。 When the colored photosensitive resin composition of the present invention is prepared as a blue colored photosensitive resin composition, it is preferably a pigment such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc. as a pigment. Color pigment and CI pigment purple, purple pigments such as 19, 23, 29, 32, 36, 38, etc., more preferably CI pigment blue 15:3, 15:6 and CI pigment violet 23, and further preferably CI pigment blue 15 :6.

將本發明之著色感光性樹脂組合物製備為綠色著色感光性樹脂組合物之情形時,顏料較佳為C.I.顏料綠7、36、58等綠色顏料及C.I.顏料黃138、139、150等黃色顏料。 When the colored photosensitive resin composition of the present invention is prepared as a green colored photosensitive resin composition, the pigment is preferably a green pigment such as CI Pigment Green 7, 36, and 58 and a yellow pigment such as CI Pigment Yellow 138, 139, and 150. .

將本發明之著色感光性樹脂組合物製備為紅色著色感光性樹脂組合物之情形時,顏料較佳為C.I.顏料紅177、209、242、254、255等紅色顏料,C.I.顏料橙38、43、71等橙色顏料及C.I.顏料黃138、139、150等黃色顏料。 When the colored photosensitive resin composition of the present invention is prepared as a red colored photosensitive resin composition, the pigment is preferably a red pigment such as CI Pigment Red 177, 209, 242, 254, 255, CI Pigment Orange 38, 43, 71 and other orange pigments and CI pigment yellow 138, 139, 150 and other yellow pigments.

藉由包含上述顏料,容易使透射光譜最佳化,彩色濾光片之耐光性及耐化學品性變得良好。 By including the above pigment, the transmission spectrum is easily optimized, and the light resistance and chemical resistance of the color filter are improved.

顏料(A2)亦可視需要實施以下處理:松香處理;使用導入有酸性基或鹼性基之顏料衍生物等的表面處理;利用高分子化合物等對顏料表面進行之接枝處理;利用硫酸微粒 化法等之微粒化處理;或者用以去除雜質之利用有機溶劑或水等之洗淨處理,利用離子交換法等去除離子性雜質之處理等。 The pigment (A2) may also be subjected to the following treatments as needed: rosin treatment; surface treatment using a pigment derivative or the like into which an acidic group or a basic group is introduced; graft treatment of a pigment surface by using a polymer compound or the like; A micronization treatment such as a chemical method, or a treatment for removing impurities, an organic solvent or water, or the like, and an ion exchange method or the like for removing ionic impurities.

顏料(A2)較佳為粒徑均勻。藉由含有顏料分散劑而進行分散處理,可獲得顏料在溶液中均勻分散之狀態的顏料分散液。 The pigment (A2) preferably has a uniform particle size. By performing a dispersion treatment by containing a pigment dispersant, a pigment dispersion liquid in a state in which the pigment is uniformly dispersed in a solution can be obtained.

作為上述顏料分散劑,例如可列舉:陽離子系、陰離子系、非離子系、兩性、聚酯系、多胺系、丙烯酸系等之顏料分散劑等。該等顏料分散劑可單獨使用,亦可組合2種以上而使用。作為顏料分散劑,可列舉商品名KP(信越化學工業(股)製造)、Flowlen(共榮社化學(股)製造)、Solsperse(Zeneca(股)製造)、EFKA(CIBA公司製造)、Ajisper(Ajinomoto Fine-Techno(股)製造)、Disperbyk(BYK-Chemie公司製造)等。 Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used singly or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA), and Ajisper ( Ajinomoto Fine-Techno Co., Ltd., Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

於使用顏料分散劑之情形時,其使用量相對於顏料(A2)較佳為1質量%以上100質量%以下,更佳為5質量%以上50質量%以下。若顏料分散劑之使用量在上述範圍內,則存在可獲得分散狀態均勻之顏料分散液之傾向。 In the case of using a pigment dispersant, the amount thereof to be used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less based on the pigment (A2). When the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid having a uniform dispersion state can be obtained.

著色劑(A)較佳為包含染料(A1)。藉由包含染料(A1),容易使透射光譜最佳化。 The colorant (A) preferably contains the dye (A1). The transmission spectrum is easily optimized by including the dye (A1).

又,著色劑(A)更佳為包含染料(A1)及顏料(A2)。於該情形時,染料(A1)與顏料(A2)之含量比率以質量基準計較佳為1:99~99:1,更佳為3:97~90:10。藉由設為此種比率,容易使透射光譜最佳化,所獲得之彩色濾光片存在 對比度、亮度、耐熱性及耐化學品性優異之傾向。 Further, the colorant (A) more preferably contains the dye (A1) and the pigment (A2). In this case, the content ratio of the dye (A1) to the pigment (A2) is preferably from 1:99 to 99:1, more preferably from 3:97 to 90:10, on a mass basis. By setting this ratio, it is easy to optimize the transmission spectrum, and the obtained color filter exists. The tendency to be excellent in contrast, brightness, heat resistance and chemical resistance.

染料(A1)較佳為包含染料(Aa)之染料,更佳為包含染料(Aa)與酞菁染料(Ab)之染料。於該情形時,染料(Aa)與酞菁染料(Ab)之含量比率以質量基準計較佳為5:95~95:5,更佳為20:80~80:20,進而較佳為40:60~65:35。 The dye (A1) preferably contains Dye (Aa) dye, more preferably Dye of dye (Aa) and phthalocyanine dye (Ab). In this case, The content ratio of the dye (Aa) to the phthalocyanine dye (Ab) is preferably 5:95 to 95:5, more preferably 20:80 to 80:20, and still more preferably 40:60 to 65:35 on a mass basis. .

尤其是,著色劑(A)較佳為包含染料(Aa)與藍色顏料之著色劑,更佳為包含染料(Aa)與C.I.顏料藍15:6之著色劑。染料(Aa)與藍色顏料之含量比率以質量基準計較佳為1:99~90:10,更佳為2:98~70:30,進而較佳為2:98~50:50。 In particular, the colorant (A) preferably comprises a coloring agent for dye (Aa) and blue pigment, preferably containing Dye (Aa) and CI Pigment Blue 15:6 colorant. The content ratio of the dye (Aa) to the blue pigment is preferably from 1:99 to 90:10, more preferably from 2:98 to 70:30, still more preferably from 2:98 to 50:50, on a mass basis.

著色劑(A)之含量相對於固形物成分之總量較佳為5~60質量%,更佳為8~50質量%,進而較佳為10~40質量%。若著色劑(A)之含量在上述範圍內,則製成彩色濾光片時之色濃度充分,且可使組合物中包含必要量之樹脂或聚合性化合物(C),因此可形成機械強度充分之彩色濾光片。 The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 50% by mass, even more preferably from 10 to 40% by mass, based on the total amount of the solid content component. When the content of the coloring agent (A) is within the above range, the color density when the color filter is formed is sufficient, and the necessary amount of the resin or the polymerizable compound (C) can be contained in the composition, so that mechanical strength can be formed. A full color filter.

此處,本說明書中之所謂「固形物成分之總量」,意指自本發明之著色感光性樹脂組合物的總量減去溶劑之含量後的量。固形物成分之總量及各成分相對於該總量之含量可利用例如液相層析法或氣相層析法等眾所周知之分析方法而進行測定。 Here, the term "the total amount of the solid content component" in the present specification means the amount obtained by subtracting the content of the solvent from the total amount of the colored photosensitive resin composition of the present invention. The total amount of the solid content component and the content of each component with respect to the total amount can be measured by a well-known analytical method such as liquid chromatography or gas chromatography.

<樹脂(B1)> <Resin (B1)>

樹脂(B1)係包含源自選自由不飽和羧酸及不飽和羧酸酐所組成之群中的至少1種(以下,有時稱作「(a)」)之結構 單元、及源自具有碳數2~4之環狀醚結構及乙烯性不飽和鍵之單體(以下,有時稱作「(b)」)之結構單元的樹脂。樹脂(B1)亦可進而具有源自與(a)及(b)不同,且可與該等共聚合之單體(以下,有時稱作「(c)」)之結構單元。 The resin (B1) contains a structure derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter, sometimes referred to as "(a)"). The unit and the resin derived from a structural unit having a monomer having a carbon number of 2 to 4 and a monomer having an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"). The resin (B1) may further have a structural unit derived from a monomer which is different from (a) and (b) and which is copolymerizable with the above (hereinafter, sometimes referred to as "(c)").

作為樹脂(B1),可列舉以下之樹脂[K1]及樹脂[K2]。 The resin (B1) is exemplified by the following resin [K1] and resin [K2].

樹脂[K1]:(a)及(b)之共聚物;樹脂[K2]:(a)、(b)及(c)之共聚物。 Resin [K1]: a copolymer of (a) and (b); a resin [K2]: a copolymer of (a), (b) and (c).

作為(a),具體而言,例如可列舉:丙烯酸、甲基丙烯酸、丁烯酸,鄰、間、對乙烯基苯甲酸等不飽和單羧酸類;順丁烯二酸、反丁烯二酸、甲基順丁烯二酸、甲基反丁烯二酸、伊康酸、3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲基四氫鄰苯二甲酸、1,4-環己烯二甲酸等不飽和二羧酸類;甲基-5-降烯-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯等含有羧基之雙環不飽和化合物類;順丁烯二酸酐、甲基順丁烯二酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯酐等不飽和二 羧酸類之酸酐;琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等二元以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯類;α-(羥基甲基)丙烯酸等同一分子中含有羥基及羧基之不飽和丙烯酸酯類等。 Specific examples of (a) include acrylic acid, methacrylic acid, crotonic acid, unsaturated monocarboxylic acids such as o-, m-, p-vinylbenzoic acid, and maleic acid and fumaric acid. , methyl maleic acid, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydroortene Unsaturated dicarboxylic acids such as phthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5- drop Alkene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-A Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2 - a bicyclic unsaturated compound containing a carboxyl group such as a olefin or a 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, and itaconic anhydride; 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic acid Acid anhydride, dimethyltetrahydrophthalic anhydride, acid anhydride of unsaturated dicarboxylic acid such as 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono[2-(methyl) Unsaturated mono[(methyl)acryloxyloxy group of divalent or higher polycarboxylic acid such as propylene methoxyethyl ester, phthalic acid mono [2-(methyl) propylene oxyethyl] ester An alkyl group ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid.

該等之中,就共聚合反應性之方面或對鹼水溶液之溶解性之方面而言,較佳為(甲基)丙烯酸及順丁烯二酸酐等,更佳為(甲基)丙烯酸。 Among these, in terms of copolymerization reactivity or solubility in an aqueous alkali solution, (meth)acrylic acid, maleic anhydride, etc. are preferable, and (meth)acrylic acid is more preferable.

再者,於本說明書中,所謂「(甲基)丙烯醯基」,表示選自由丙烯醯基及甲基丙烯醯基所組成之群中的至少1種。「(甲基)丙烯酸」及「(甲基)丙烯酸酯」等記法亦具有相同之含義。 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 group. The notation such as "(meth)acrylic acid" and "(meth)acrylate" has the same meaning.

(b)係指例如具有碳數2~4之環狀醚結構(例如,選自由環氧乙烷環、環氧丙烷環及四氫呋喃環所組成之群中的至少1種)與乙烯性不飽和鍵之聚合性化合物。(b)較佳為具有碳數2~4之環狀醚與(甲基)丙烯醯氧基之單體。 (b) means, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, a propylene oxide ring, and a tetrahydrofuran ring) and ethylenic unsaturation A polymerizable compound of a bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

作為(b),例如可列舉具有環氧乙烷基與乙烯性不飽和鍵之單體(b1)(以下,有時稱作「(b1)」)、具有環氧丙烷基與乙烯性不飽和鍵之單體(b2)(以下,有時稱作「(b2)」)、具有四氫呋喃基與乙烯性不飽和鍵之單體(b3)(以下,有時稱作「(b3)」)等。 (b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxypropylene group and an ethylenic unsaturated group The monomer (b2) of the bond (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b3)")) .

(b1)例如可列舉具有直鏈狀或支鏈狀之不飽和脂肪族烴經環氧化之結構的單體(b1-1)(以下,有時稱作「(b1- 1)」),以及具有不飽和脂環式烴經環氧化之結構的單體(b1-2)(以下,有時稱作「(b1-2)」)。 (b1), for example, a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b1-) 1)"), and a monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b1-2)").

作為(b1-1),可列舉:(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸-β-甲基縮水甘油酯、(甲基)丙烯酸-β-乙基縮水甘油酯、縮水甘油基乙烯醚、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、α-甲基-鄰乙烯基苄基縮水甘油醚、α-甲基-間乙烯基苄基縮水甘油醚、α-甲基-對乙烯基苄基縮水甘油醚、2,3-雙(縮水甘油氧基甲基)苯乙烯、2,4-雙(縮水甘油氧基甲基)苯乙烯、2,5-雙(縮水甘油氧基甲基)苯乙烯、2,6-雙(縮水甘油氧基甲基)苯乙烯、2,3,4-三(縮水甘油氧基甲基)苯乙烯、2,3,5-三(縮水甘油氧基甲基)苯乙烯、2,3,6-三(縮水甘油氧基甲基)苯乙烯、3,4,5-三(縮水甘油氧基甲基)苯乙烯及2,4,6-三(縮水甘油氧基甲基)苯乙烯等。 Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl group. Vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-inter Vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(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)styrene, 3,4,5-tris (glycidol) Oxymethyl)styrene and 2,4,6-tris(glycidoxymethyl)styrene.

作為(b1-2),可列舉:乙烯基環己烯單氧化物、1,2-環氧-4-乙烯基環己烷(例如,Celloxide 2000;Daicel Chemical Industries(股)製造)、(甲基)丙烯酸-3,4-環氧環己基甲酯(例如,Cyclomer A400;Daicel Chemical Industries(股)製造)、(甲基)丙烯酸-3,4-環氧環己基甲酯(例如,Cyclomer M100;Daicel Chemical Industries(股)製造)、由式(I)所表示之化合物、由式(II)所表示之化合物等。 (b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industries), (A) 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100) ; manufactured by Daicel Chemical Industries, a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[於式(I)及式(II)中,Rb1及Rb2表示氫原子或碳數1~4之烷基,該烷基中所含之氫原子亦可經羥基取代。 [In the formula (I) and the formula (II), R b1 and R b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

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1~6之烷二基。 R b3 represents an alkanediyl group having 1 to 6 carbon atoms.

*表示與O之鍵結鍵]。 * indicates the key with O.].

作為碳數1~4之烷基,可列舉:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

作為氫原子經羥基取代之烷基,可列舉:羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥基丁基、2-羥基丁基、3-羥基丁基、4-羥基丁基等。 Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

作為Rb1及Rb2,較佳可列舉氫原子、甲基、羥基甲基、1-羥基乙基及2-羥基乙基,更佳可列舉氫原子及甲基。 The R b1 and R b2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

作為烷二基,可列舉:亞甲基、伸乙基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基等。 Examples of the alkanediyl group include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. - Diyl, hexane-1,6-diyl and the like.

作為Xb1及Xb2,較佳可列舉單鍵、亞甲基、伸乙基、*-CH2-O-及*-CH2CH2-O-,更佳可列舉單鍵、*-CH2CH2-O-(*表示與O之鍵結鍵)。 Preferred examples of X b1 and X b2 include a single bond, a methylene group, an exoethyl group, *-CH 2 -O-, and *-CH 2 CH 2 -O-, and more preferably a single bond or *-CH. 2 CH 2 -O- (* indicates the bond with O).

作為由式(I)所表示之化合物,可列舉由式(I-1)~式(I-15)之任一個所表示之化合物等。其中,較佳為由式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)及式(I-11)~式(I-15)之任一個所表示之化合物,更佳為由式(I-1)、式(I-7)、式(I-9) 或式(I-15)所表示之化合物。 The compound represented by the formula (I) may, for example, be a compound represented by any one of the formulae (I-1) to (I-15). Among them, preferred are formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) and formula (I-11)-form ( The compound represented by any one of I-15) is more preferably of the formula (I-1), the formula (I-7), and the formula (I-9). Or a compound represented by the formula (I-15).

作為由式(II)所表示之化合物,可列舉由式(II-1)~式(II-15)之任一個所表示之化合物等。其中,較佳為由式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)及式(II-11)~式(II-15)之任一個所表示之化合物,更佳為由式(II-1)、式(II-7)、式(II-9)或式(II-15)所表示之化合物。 The compound represented by the formula (II) may, for example, be a compound represented by any one of the formulae (II-1) to (II-15). Among them, preferred are formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), and formula (II-11)-form ( The compound represented by any one of II-15) is more preferably a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

由式(I)所表示之化合物及由式(II)所表示之化合物可分別單獨使用,亦可以任意之比率混合使用。於混合使用之情形時,由式(I)所表示之化合物與由式(II)所表示之化合物之含有比率以莫耳基準計較佳為5:95~95:5,更佳為10:90~90:10,進而較佳為20:80~80:20。 The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in combination at any ratio. In the case of mixed use, the content ratio of the compound represented by the formula (I) to the compound represented by the formula (II) is preferably from 5:95 to 95:5, more preferably 10:90 on a molar basis. ~90:10, and further preferably 20:80~80:20.

作為具有環氧丙烷基與乙烯性不飽和鍵之單體(b2),更佳為具有環氧丙烷基與(甲基)丙烯醯氧基之單體。作為 (b2),可列舉:3-甲基-3-甲基丙烯醯氧基甲基環氧丙烷、3-甲基-3-丙烯醯氧基甲基環氧丙烷、3-乙基-3-甲基丙烯醯氧基甲基環氧丙烷、3-乙基-3-丙烯醯氧基甲基環氧丙烷、3-甲基-3-甲基丙烯醯氧基乙基環氧丙烷、3-甲基-3-丙烯醯氧基乙基環氧丙烷、3-乙基-3-甲基丙烯醯氧基乙基環氧丙烷、3-乙基-3-丙烯醯氧基乙基環氧丙烷等。 The monomer (b2) having an oxypropylene group and an ethylenically unsaturated bond is more preferably a monomer having an oxypropylene group and a (meth)acryloxy group. As (b2), exemplified by 3-methyl-3-methylpropenyloxymethyl propylene oxide, 3-methyl-3-propenyloxymethyl propylene oxide, 3-ethyl-3- Methyl propylene methoxymethyl propylene oxide, 3-ethyl-3-propenyl methoxymethyl propylene oxide, 3-methyl-3-methyl propylene methoxyethyl propylene oxide, 3- Methyl-3-propenyloxyethyl propylene oxide, 3-ethyl-3-methylpropenyloxyethyl propylene oxide, 3-ethyl-3-propenyloxyethyl propylene oxide Wait.

作為具有四氫呋喃基與乙烯性不飽和鍵之單體(b3),更佳為具有四氫呋喃基與(甲基)丙烯醯氧基之單體。 The monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group.

作為(b3),具體而言可列舉:丙烯酸四氫糠酯(例如,Viscoat V#150,大阪有機化學工業(股)製造)及甲基丙烯酸四氫糠酯等。 Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

作為(b),就可進一步提高所獲得之彩色濾光片之耐熱性、耐化學品性等可靠性方面而言,較佳為(b1)。進而,就著色感光性樹脂組合物之保存穩定性優異之方面而言,更佳為(b1-2)。 (b) is preferably (b1) in terms of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, in terms of excellent storage stability of the colored photosensitive resin composition, (b1-2) is more preferable.

作為(c),例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂基酯、(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-8-基酯(於該技術領域中,慣用名係稱作「(甲基)丙烯酸二環戊酯」。又,有時稱作「(甲基)丙烯酸三環癸酯」)、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-基酯 (於該技術領域中,慣用名係稱作「(甲基)丙烯酸二環戊烯酯」)、(甲基)丙烯酸二環戊基氧基乙酯、(甲基)丙烯酸異酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯類;(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯等含有羥基之(甲基)丙烯酸酯類;順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等二羧酸二酯;雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物類;N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N- 苄基順丁烯二醯亞胺、N-丁二醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-丁二醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-丁二醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順丁烯二醯亞胺等二羰基醯亞胺衍生物類;苯乙烯、α-甲基苯乙烯、鄰乙烯基甲苯、間乙烯基甲苯、對乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (methyl) Cyclopentyl acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] 癸-8-yl (meth) acrylate ( In the technical field, the conventional name is called "dicyclopentanyl (meth) acrylate." Further, it is sometimes called "tricyclodecyl (meth) acrylate"), tricyclo(meth) acrylate [ 5.2.1.0 2,6 ]decene-8-yl ester (in the technical field, the conventional name is called "dicyclopentenyl (meth) acrylate)", dicyclopentyloxy (meth) acrylate Ethyl ethyl ester, (meth)acrylic acid Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (methyl) a (meth) acrylate such as benzyl acrylate; a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl diacid, diethyl fumarate, diethyl iconate; bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [2.2.1] Hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]heptane- 2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[ 2.2.1] hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-di Ethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]g 2-ene, 5-hydroxymethyl- 5-methylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]g 2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5, a bicyclic unsaturated compound such as 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylbutylene Amine, N-benzyl maleimide, N-butylenediamine-3-butyleneimine benzoate, N-butylenediamine-4-cis Acetylimine butyrate, N-butylenediamine-6-methyleneimide hexanoate, N-butylenediamine-3-oxenimide Dicarbonyl ruthenium derivatives such as acid esters, N-(9-acridinyl) maleimide, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, Vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene Diene, 2,3-dimethyl-1,3-butadiene, and the like.

該等之中,就共聚合反應性及耐熱性之方面而言,較佳為苯乙烯、乙烯基甲苯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺及雙環[2.2.1]庚-2-烯。 Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenyl maleimide, N-cyclohexylbutylene oxide are preferred. Amine, N-benzyl maleimide and bicyclo [2.2.1] hept-2-ene.

於樹脂[K1]中,源自各單體之結構單元之比率相對於構成樹脂[K1]之全部結構單元較佳為:源自(a)之結構單元:2~60莫耳%源自(b)之結構單元:40~98莫耳%,更佳為:源自(a)之結構單元:10~50莫耳%源自(b)之結構單元:50~90莫耳%。 In the resin [K1], the ratio of the structural unit derived from each monomer is preferably relative to the entire structural unit constituting the resin [K1]: the structural unit derived from (a): 2 to 60 mol% is derived from ( b) The structural unit: 40 to 98 mol%, more preferably: the structural unit derived from (a): 10 to 50 mol% derived from the structural unit of (b): 50 to 90 mol%.

若構成樹脂[K1]之結構單元之比率在上述範圍內,則存在著色感光性樹脂組合物之保存穩定性、形成著色圖案時之顯影性以及所獲得之著色圖案之耐溶劑性優異的傾向。 When the ratio of the structural unit constituting the resin [K1] is within the above range, the storage stability of the colored photosensitive resin composition, the developability in forming a colored pattern, and the solvent resistance of the obtained colored pattern tend to be excellent.

樹脂[K1]例如可參照文獻「高分子合成之實驗法」(大津隆行著,化學同人(股)出版社,第1版第1次印刷,1972年3月1日出版)所揭示之方法及該文獻所揭示之引用文獻而製造。 For example, the resin [K1] can be referred to the "Experimental Method for Polymer Synthesis" (Dazu Takashi, Chemical Tongren (Public) Press, 1st Edition, 1st Printing, published on March 1, 1972). Manufactured by reference to the literature disclosed in this document.

具體而言,可列舉下述方法:將(a)及(b)之特定量、聚合起始劑及溶劑等放入至反應容器中,例如藉由用氮置換氧而形成脫氧環境,一面攪拌一面進行加熱及保溫。再者,此處所使用之聚合起始劑及溶劑等並無特別限定,可使用該領域內通常使用者。例如,作為聚合起始劑,可列舉偶氮化合物(2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)等)或有機過氧化物(過氧化苯甲醯等),作為溶劑,只要為可溶解各單體者即可,可列舉作為著色感光性樹脂組合物之溶劑而於後文中記載之溶劑(E)等。 Specifically, a method in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction container, for example, by dissolving oxygen with nitrogen to form a deoxidizing environment, stirring Heating and keeping warm on one side. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and a general user in the field can be used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic The oxide (such as benzamidine peroxide) may be used as a solvent, and the solvent (E) described later may be mentioned as a solvent for the colored photosensitive resin composition.

再者,所獲得之樹脂可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,亦可使用利用再沈澱等方法形成固體(粉體)而取出者。尤其是藉由於該聚合時使用後述溶劑(E)作為溶劑,可將反應後之溶液直接用於製造著色感光性樹脂組合物,故而可使著色感光性樹脂組合物之製造步驟簡略化。 Further, the obtained resin may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) may be formed by a method such as reprecipitation. In particular, since the solvent (E) described later is used as a solvent in the polymerization, the solution after the reaction can be directly used for producing a colored photosensitive resin composition, so that the production steps of the colored photosensitive resin composition can be simplified.

於樹脂[K2]中,源自各者之結構單元之比率於構成樹脂[K2]之全部結構單元中較佳為: In the resin [K2], the ratio of the structural units derived from each of them is preferably among all the structural units constituting the resin [K2]:

源自(a)之結構單元:2~45莫耳% Structural unit derived from (a): 2~45mol%

源自(b)之結構單元:2~95莫耳% Structural unit derived from (b): 2~95 mol%

源自(c)之結構單元:1~65莫耳%, Structural unit derived from (c): 1 to 65 mol%,

更佳為: More preferably:

源自(a)之結構單元:5~40莫耳% Structural unit derived from (a): 5~40 mol%

源自(b)之結構單元:5~80莫耳% Structural unit derived from (b): 5~80 mol%

源自(c)之結構單元:5~60莫耳%。 The structural unit derived from (c): 5 to 60 mol%.

若樹脂[K2]之結構單元之比率在上述範圍內,則存在著色感光性樹脂組合物之保存穩定性、形成著色圖案時之顯影性、以及所獲得之著色圖案之耐溶劑性、耐熱性及機械強度優異的傾向。 When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored photosensitive resin composition, the developability in forming a colored pattern, and the solvent resistance and heat resistance of the obtained colored pattern and The tendency to have excellent mechanical strength.

作為樹脂(B1),具體而言可列舉:樹脂[K1],(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[K2],(甲基)丙烯酸縮水甘油酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸縮水甘油酯/苯乙烯/(甲基)丙烯酸共聚物、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/乙烯基甲苯共聚物、3-甲基-3-(甲基)丙烯醯氧基甲基環氧丙烷/(甲基)丙烯酸/N-環己基順丁烯二醯亞胺共聚物等。 Specific examples of the resin (B1) include a resin [K1], a (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, and an acrylic-3,4-epoxy resin. Tricyclo [5.2.1.0 2.6 ] decyl ester / (meth)acrylic acid copolymer; resin [K2], glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer, (meth)acrylic acid glycidyl ester / styrene / (meth) acrylic acid copolymer, acrylic acid -3,4-epoxytricyclo[5.2.1.0 2.6 ] decyl ester / (meth)acrylic acid / N-cyclohexyl cis maleic copolymer (PEI), 3,4-epoxy acrylate, tricyclo [5.2.1.0 2.6] decyl acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (methyl Propylene methoxymethyl propylene oxide / (meth) acrylic acid / N-cyclohexyl maleimide copolymer.

樹脂[K2]例如可以與作為樹脂[K1]之製造方法所揭示之方法相同之方式而製造。 The resin [K2] can be produced, for example, in the same manner as the method disclosed in the method for producing the resin [K1].

樹脂(B1)之聚苯乙烯換算之重量平均分子量較佳為3,000~100,000,更佳為5,000~50,000,進而較佳為5,000~30,000。若分子量在上述範圍內,則存在彩色濾光片之硬度提高,殘膜率亦較高,未曝光部對顯影液之溶解性良 好,解像度提高的傾向。 The polystyrene-equivalent weight average molecular weight of the resin (B1) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is increased, the residual film ratio is also high, and the solubility of the unexposed portion to the developer is good. Ok, the tendency to improve resolution.

樹脂(B1)之分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.1~6,更佳為1.2~4。 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B1) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

樹脂(B1)之酸值較佳為50~170 mg-KOH/g,更佳為60~150 mg-KOH/g,進而較佳為70~135 mg-KOH/g。此處,酸值係作為中和樹脂1 g所需之氫氧化鉀之量(mg)而測定之值,例如可藉由使用氫氧化鉀水溶液進行滴定而求得。 The acid value of the resin (B1) 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. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

樹脂(B1)之含量相對於樹脂(B1)與樹脂(B2)之合計量較佳為10~90質量%,更佳為25~85質量%,進而較佳為50~80質量%。 The content of the resin (B1) is preferably from 10 to 90% by mass, more preferably from 25 to 85% by mass, even more preferably from 50 to 80% by mass, based on the total amount of the resin (B1) and the resin (B2).

<樹脂(B2)> <Resin (B2)>

樹脂(B2)係包含(a)、及源自具有脂環式烴結構之單體之結構單元(以下,有時稱作「(x)」)的樹脂。其中,樹脂(B2)不包含源自具有碳數2~4之環狀醚結構及乙烯性不飽和鍵之單體之結構單元(b)。樹脂(B2)亦可進而具有源自與(a)、(b)及(x)不同,且可與該等共聚合之單體(以下,有時稱作「(d)」)之結構單元。 The resin (B2) is a resin containing (a) and a structural unit derived from a monomer having an alicyclic hydrocarbon structure (hereinafter sometimes referred to as "(x)"). Here, the resin (B2) does not contain the structural unit (b) derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. The resin (B2) may further have a structural unit derived from a monomer which is different from (a), (b), and (x) and which is copolymerizable with the above (hereinafter, sometimes referred to as "(d)"). .

作為樹脂(B2),可列舉以下之樹脂[K3]及樹脂[K4]。 The resin (B2) is exemplified by the following resin [K3] and resin [K4].

樹脂[K3]:(a)及(x)之共聚物;樹脂[K4]:(a)、(x)及(d)之共聚物。 Resin [K3]: a copolymer of (a) and (x); a resin [K4]: a copolymer of (a), (x) and (d).

作為(a),可列舉與樹脂(B1)之(a)相同者。該等之中,就共聚合反應性之方面或對鹼水溶液之溶解性之方面而言,較佳為(甲基)丙烯酸及順丁烯二酸酐,更佳為(甲基) 丙烯酸。 (a) is the same as (a) of the resin (B1). Among these, (meth)acrylic acid and maleic anhydride are more preferable in terms of the aspect of copolymerization reactivity or the solubility in an aqueous alkali solution, more preferably (meth) acrylic acid.

作為(x),例如可列舉:(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸-2-甲基環己酯等具有單環之脂環式烴結構的(甲基)丙烯酸酯類;(甲基)丙烯酸三環[5.2.1.02,6]癸-8-基酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-基酯、(甲基)丙烯酸二環戊基氧基乙酯、(甲基)丙烯酸異酯、(甲基)丙烯酸金剛烷基酯等具有多環之脂環式烴結構的(甲基)丙烯酸酯類;雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物類;N-環己基順丁烯二醯亞胺等具有脂環式烴結構之N-取代順丁烯二醯亞胺類等。 Examples of (x) include a monocyclic alicyclic hydrocarbon structure such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, or 2-methylcyclohexyl (meth)acrylate. (meth) acrylates; trimethyl [meth) acrylate [5.2.1.0 2,6 ] 癸-8-yl ester, trimethyl [meth) acrylate [5.2.1.0 2,6 ] decene-8 -yl ester, dicyclopentyloxyethyl (meth)acrylate, (meth)acrylic acid a (meth) acrylate having a polycyclic alicyclic hydrocarbon structure such as an ester or an adamantyl (meth) acrylate; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo[2.2. 1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1] Hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxyl Bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2- Alkene, 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-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5 -cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo [2.2.1] Bicyclic unsaturated compounds such as hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene N- cyclohexyl-maleic N- acyl imine having the alicyclic hydrocarbon structure substituted maleic acyl imines.

其中,(x)較佳為選自由具有脂環式烴結構之(甲基)丙烯 酸酯類及雙環不飽和化合物類所組成之群中的至少1種,更佳為具有脂環式烴結構之(甲基)丙烯酸酯類,進而較佳為具有多環之脂環式烴結構的(甲基)丙烯酸酯類。若(x)為該等單體,則由包含樹脂(B2)的本發明之著色感光性樹脂組合物製造著色圖案時,於顯影後之顯影液中,來自著色感光性樹脂組合物之剝離片產生減少。又,亦可抑制因該等剝離片附著於著色圖案上所造成之異物。 Wherein (x) is preferably selected from (meth) propylene having an alicyclic hydrocarbon structure At least one of the group consisting of an acid ester and a bicyclic unsaturated compound is more preferably a (meth) acrylate having an alicyclic hydrocarbon structure, and further preferably a polycyclic alicyclic hydrocarbon structure. (meth) acrylates. When (x) is such a monomer, when a colored pattern is produced from the colored photosensitive resin composition of the present invention containing the resin (B2), the release sheet derived from the colored photosensitive resin composition in the developing solution after development Reduced production. Further, it is possible to suppress foreign matter caused by adhesion of the release sheets to the colored pattern.

作為(d),例如可列舉自樹脂(B1)之(c)中將與(x)相當之單體除外者。 Examples of (d) include those excluding monomers corresponding to (x) in (c) of the resin (B1).

作為(d),例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯類;(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯等含有羥基之(甲基)丙烯酸酯類;順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等二羧酸二酯;N-苯基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-丁二醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-丁二醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-丁二醯亞胺基-3-順丁烯二醯亞胺丙 酸酯及N-(9-吖啶基)順丁烯二醯亞胺等二羰基醯亞胺衍生物類;苯乙烯、α-甲基苯乙烯、鄰乙烯基甲苯、間乙烯基甲苯、對乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Examples of (d) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (methyl) (meth)acrylates such as allyl acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate; (methyl) a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, and y Dicarboxylic acid diester such as diethyl benzoate; N-phenyl maleimide, N-benzyl maleimide, N-butyl quinone imin-3-butene Diterpene imide benzoate, N-butanediamine-4-butyleneimine butyrate, N-butanediamine-6-m-butyleneimine Acid ester, N-butyl diimide imino-3-butane diimide Dicarbonyl quinone imine derivatives such as acid esters and N-(9-acridinyl) maleimide; styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, Vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene Diene, 2,3-dimethyl-1,3-butadiene, and the like.

其中,較佳為苯乙烯、乙烯基甲苯、N-苯基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、(甲基)丙烯酸苄酯等具有芳香族烴結構之單體,更佳為苯乙烯、乙烯基甲苯及(甲基)丙烯酸苄酯。若(d)為該等單體,則存在聚合過程中或聚合後之樹脂(B2)溶液之黏度不會過高,故而容易操作之傾向。又,若將包含源自該等單體之結構單元之樹脂(B2)使用於著色感光性樹脂組合物中,則可更進一步抑制顯影時之剝離片產生。 Among them, preferred are styrene, vinyl toluene, N-phenyl maleimide, N-benzyl maleimide, and benzyl (meth)acrylate having an aromatic hydrocarbon structure. The monomer is more preferably styrene, vinyl toluene or benzyl (meth)acrylate. When (d) is such a monomer, the viscosity of the resin (B2) solution during or after the polymerization is not excessively high, so that it tends to be easy to handle. In addition, when the resin (B2) containing the structural unit derived from the monomers is used in the colored photosensitive resin composition, the occurrence of the release sheet during development can be further suppressed.

於樹脂[K3]中,源自各單體之結構單元之比率相對於構成樹脂[K3]之全部結構單元較佳為:源自(a)之結構單元:2~60莫耳% In the resin [K3], the ratio of the structural unit derived from each monomer is preferably relative to the entire structural unit constituting the resin [K3]: the structural unit derived from (a): 2 to 60 mol%

源自(x)之結構單元:40~98莫耳%,更佳為:源自(a)之結構單元:10~50莫耳% Structural unit derived from (x): 40 to 98% by mole, more preferably: structural unit derived from (a): 10 to 50% by mole

源自(x)之結構單元:50~90莫耳%。 Structural unit derived from (x): 50 to 90 mol%.

若樹脂[K3]之結構單元之比率在上述範圍內,則存在可獲得形狀良好之著色圖案之傾向。 When the ratio of the structural unit of the resin [K3] is within the above range, there is a tendency that a colored pattern having a good shape can be obtained.

樹脂[K3]例如可以與作為樹脂[K1]之製造方法所揭示之方法相同之方式而製造。 The resin [K3] can be produced, for example, in the same manner as the method disclosed in the method for producing the resin [K1].

於樹脂[K4]中,源自各單體之結構單元之比率於構成樹脂[K4]之全部結構單元中較佳為:源自(a)之結構單元:2~45莫耳% In the resin [K4], the ratio of the structural unit derived from each monomer to all the structural units constituting the resin [K4] is preferably: structural unit derived from (a): 2 to 45 mol%

源自(x)之結構單元:2~95莫耳% Structural unit derived from (x): 2~95 mol%

源自(d)之結構單元:1~65莫耳%,更佳為:源自(a)之結構單元:5~40莫耳% The structural unit derived from (d): 1 to 65 mol%, more preferably: structural unit derived from (a): 5 to 40 mol%

源自(x)之結構單元:5~80莫耳% Structural unit derived from (x): 5~80 mol%

源自(d)之結構單元:5~60莫耳%。 The structural unit derived from (d): 5 to 60 mol%.

若樹脂[K4]之結構單元之比率在上述範圍內,則存在可獲得形狀良好之著色圖案之傾向。 When the ratio of the structural unit of the resin [K4] is within the above range, there is a tendency that a colored pattern having a good shape can be obtained.

於包含源自具有芳香族烴結構之單體之結構單元(以下稱為「(d')」)作為樹脂[K4]之(d)之情形時,較佳為:源自(a)之結構單元:5~45莫耳% In the case of a structural unit containing a monomer derived from an aromatic hydrocarbon structure (hereinafter referred to as "(d')") as the resin (K4) (d), it is preferred that the structure derived from (a) Unit: 5~45mol%

源自(x)之結構單元:5~80莫耳% Structural unit derived from (x): 5~80 mol%

源自(d')之結構單元:30~65莫耳%,更佳為:源自(a)之結構單元:10~40莫耳% Structural unit derived from (d'): 30 to 65 mol%, more preferably: structural unit derived from (a): 10 to 40 mol%

源自(x)之結構單元:5~40莫耳% Structural unit derived from (x): 5~40 mol%

源自(d')之結構單元:40~65莫耳%。 The structural unit derived from (d'): 40 to 65 mol%.

若樹脂[K4]為此種樹脂,則存在因顯影所致之剝離片之產生更進一步減少,可獲得形狀良好之著色圖案的傾向。 When the resin [K4] is such a resin, the occurrence of the release sheet due to development is further reduced, and a color pattern having a good shape tends to be obtained.

樹脂[K4]例如可以與作為樹脂[K1]之製造方法所揭示之方法相同之方式而製造。 The resin [K4] can be produced, for example, in the same manner as the method disclosed in the method for producing the resin [K1].

作為樹脂(B2),具體而言可列舉:樹脂[K3],(甲基)丙烯酸環己酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸三環癸酯/(甲基)丙烯酸共聚物、雙環[2.2.1]庚-2-烯/(甲基)丙烯酸共聚物等;樹脂[K4],(甲基)丙烯酸環己酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸三環癸酯/乙烯基甲苯/(甲基)丙烯酸共聚物、雙環[2.2.1]庚-2-烯/苯乙烯/(甲基)丙烯酸共聚物等。 Specific examples of the resin (B2) include a resin [K3], a cyclohexyl (meth)acrylate/(meth)acrylic acid copolymer, and a tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer. , bicyclo[2.2.1]hept-2-ene/(meth)acrylic acid copolymer, etc.; resin [K4], cyclohexyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid Copolymer, tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, Tricyclodecyl (meth)acrylate/vinyltoluene/(meth)acrylic acid copolymer, bicyclo[2.2.1]hept-2-ene/styrene/(meth)acrylic acid copolymer, and the like.

其中,作為樹脂(B2),較佳為樹脂[K4]。 Among them, as the resin (B2), a resin [K4] is preferred.

樹脂(B2)之聚苯乙烯換算之重量平均分子量較佳為3,000~100,000,更佳為3,000~30,000,進而較佳為4,000~15,000。若分子量在上述範圍內,則存在彩色濾光片之硬度提高,殘膜率亦較高,未曝光部對顯影液之溶解性良好,解像度提高之傾向。 The polystyrene-equivalent weight average molecular weight of the resin (B2) is preferably from 3,000 to 100,000, more preferably from 3,000 to 30,000, still more preferably from 4,000 to 15,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is also high, the solubility of the unexposed portion to the developer is good, and the resolution tends to be improved.

樹脂(B2)之分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.1~6,更佳為1.2~4。 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B2) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

樹脂(B2)之酸值較佳為50~170 mg-KOH/g,更佳為60~150 mg-KOH/g,進而較佳為70~135 mg-KOH/g。若酸值在上述範圍內,則存在可獲得形狀良好之著色圖案之傾向。於酸值超出上述範圍而較高之情形時,著色圖案容易產生底切(undercut),而成為圖案剝離之原因。又,於酸 值超出上述範圍而較低之情形時,有產生顯影殘渣之虞。此處,酸值係作為中和樹脂1 g所需之氫氧化鉀之量(mg)而測定之值,例如可藉由使用氫氧化鉀水溶液進行滴定而求得。 The acid value of the resin (B2) 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. When the acid value is within the above range, there is a tendency that a colored pattern having a good shape can be obtained. When the acid value is higher than the above range, the colored pattern is likely to be undercut, which causes the pattern to peel off. Again, in acid When the value is lower than the above range, there is a problem that development residue is generated. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

樹脂(B2)之含量相對於樹脂(B1)與樹脂(B2)之合計量較佳為10~90質量%,更佳為15~75質量%,進而較佳為50~80質量%。 The content of the resin (B2) is preferably from 10 to 90% by mass, more preferably from 15 to 75% by mass, even more preferably from 50 to 80% by mass, based on the total amount of the resin (B1) and the resin (B2).

樹脂(B1)與樹脂(B2)之合計量相對於固形物成分之總量較佳為7~65質量%,更佳為13~60質量%,進而較佳為17~55質量%。若上述合計量在上述範圍內,則存在著色圖案之解像度及殘膜率提高之傾向。 The total amount of the resin (B1) and the resin (B2) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, still more preferably 17 to 55 mass%, based on the total amount of the solid content component. When the total amount is within the above range, the resolution of the colored pattern and the residual film ratio tend to increase.

<聚合性化合物(C)> <Polymerizable compound (C)>

聚合性化合物(C)係可藉由熱、或者由聚合起始劑(D)產生之活性自由基及/或酸而進行聚合之化合物,例如可列舉具有聚合性之乙烯性不飽和鍵之化合物等,較佳為(甲基)丙烯酸酯化合物。 The polymerizable compound (C) is a compound which can be polymerized by heat or an active radical and/or an acid produced by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. And the like, preferably a (meth) acrylate compound.

其中,作為聚合性化合物(C),較佳為具有3個以上乙烯性不飽和鍵之聚合性化合物。作為此種聚合性化合物,例如可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、四季戊四醇十(甲基)丙烯酸酯、四季戊四醇九(甲基)丙烯酸酯、三(2-(甲基)丙烯醯氧基乙基)異氰尿酸酯、乙 二醇改性季戊四醇四(甲基)丙烯酸酯、乙二醇改性二季戊四醇六(甲基)丙烯酸酯、丙二醇改性季戊四醇四(甲基)丙烯酸酯、丙二醇改性二季戊四醇六(甲基)丙烯酸酯、己內酯改性季戊四醇四(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylic acid. Ester, dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nin (meth) acrylate Ester, tris(2-(meth)acryloxyethyl)isocyanurate, B Glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth) acrylate, propylene glycol modified pentaerythritol tetra(meth) acrylate, propylene glycol modified dipentaerythritol hexa(methyl) Acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

其中,較佳為二季戊四醇五(甲基)丙烯酸酯及二季戊四醇六(甲基)丙烯酸酯。 Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

聚合性化合物(C)之重量平均分子量較佳為150以上2,900以下,更佳為250~1,500以下。 The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 to 1,500 or less.

聚合性化合物(C)之含量相對於固形物成分之總量較佳為7~65質量%,更佳為13~60質量%,進而較佳為17~55質量%。若聚合性化合物(C)之含量在上述範圍內,則存在著色圖案之殘膜率及耐化學品性提高之傾向。 The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the total amount of the solid content component. When the content of the polymerizable compound (C) is within the above range, the residual film ratio and chemical resistance of the colored pattern tend to be improved.

<聚合起始劑(D)> <Polymerization initiator (D)>

聚合起始劑(D)只要為藉由光或熱之作用而產生活性自由基、酸等而可使聚合開始進行之化合物,則無特別限定,可使用眾所周知之聚合起始劑。 The polymerization initiator (D) is not particularly limited as long as it is a compound which can initiate polymerization by the action of light or heat to generate an active radical, an acid or the like, and a known polymerization initiator can be used.

作為聚合起始劑(D),可列舉:烷基苯酮化合物、三化合物、醯基氧化膦化合物、O-醯基肟化合物及聯咪唑化合物等。其中,較佳為包含O-醯基肟化合物之聚合起始劑,更佳為包含O-醯基肟化合物及烷基苯酮化合物之聚合起始劑。 As the polymerization initiator (D), an alkylphenone compound, three a compound, a mercaptophosphine oxide compound, an O-mercaptopurine compound, a biimidazole compound, and the like. Among them, a polymerization initiator containing an O-fluorenyl ruthenium compound is preferable, and a polymerization initiator containing an O-fluorenyl ruthenium compound and an alkyl phenone compound is more preferable.

O-醯基肟化合物係具有由式(d1)所表示之部分結構之化合物。 The O-indenyl compound is a compound having a partial structure represented by the formula (d1).

以下,*表示鍵結鍵。 Hereinafter, * indicates a keying key.

作為O-醯基肟化合物,例如可列舉:N-苯甲醯氧基-1-(4-苯基硫烷基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫烷基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二氧雜環戊基甲氧基)苯甲醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺、N-苯甲醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-酮-2-亞胺等。亦可使用Irgacure(註冊商標)OXE01、OXE02(以上,由BASF公司製造),N-1919(ADEKA公司製造)等市售品。 Examples of the O-indenyl hydrazine compound include N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzidine. Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)- 3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 -yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxearylmethoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-( 2-methylbenzimidyl)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6- (2-Methylbenzylidene)-9H-oxazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used.

烷基苯酮化合物係具有由式(d2)所表示之部分結構或由式(d3)所表示之部分結構之化合物。於該等部分結構中,苯環亦可具有取代基。 The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may also have a substituent.

作為具有由式(d2)所表示之部分結構之化合物,例如可列舉:2-甲基-2-啉基-1-(4-甲基硫烷基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-啉基苯基)-2-苄基丁烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]丁烷-1-酮等。亦可使用Irgacure(註冊商標)369、907及379(以上,由BASF公司製造)等市售品。 As the compound having a partial structure represented by the formula (d2), for example, 2-methyl-2- Lolinyl-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Morpholinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

作為具有由式(d3)所表示之部分結構之化合物,例如可列舉:2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮之低聚物、α,α-二乙氧基苯乙酮、苯偶醯二甲基縮酮等。 Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[ 4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane - 1-ketone oligomer, α,α-diethoxyacetophenone, benzoin dimethyl ketal, and the like.

就感光度之方面而言,烷基苯酮化合物較佳為具有由式(d2)所表示之部分結構之化合物。 The alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2) in terms of sensitivity.

作為三化合物,例如可列舉:2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三等。 As three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-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-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

作為醯基氧化膦化合物,可列舉2,4,6-三甲基苯甲醯基二苯基氧化膦等。亦可使用Irgacure(註冊商標)819(BASF 公司製造)等市售品。 The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. Irgacure (registered trademark) 819 (BASF) Commercial products such as the company's manufacturing).

作為聯咪唑化合物,例如可列舉:2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基聯咪唑(例如,參照JPH06-75372-A、JPH06-75373-A等)、2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(二烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)聯咪唑(例如,參照JPS48-38403-B、JPS62-174204-A等)、4,4',5,5'-位之苯基經烷氧羰基取代之咪唑化合物(例如,參照JPH07-10913-A等)等。 Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis(2-chlorobenzene) -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(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to JPS48-38403-B, JPS62-174204-A, etc.), 4, 4', 5, An imidazole compound in which a phenyl group at the 5'-position is substituted with an alkoxycarbonyl group (for example, refer to JPH07-10913-A, etc.) and the like.

進而,作為聚合起始劑(D),可列舉:安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚等安息香化合物;二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯硫醚、3,3',4,4'-四(第三丁基過氧羰基羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等二苯甲酮化合物;9,10-菲醌、2-乙基蒽醌、樟腦醌等醌化合物;10-丁基-2-氯吖啶酮、苯偶醯、苯基乙醛酸甲酯、二茂鈦化合物等。該等較佳為與下述之聚合起始助劑(D1)(尤其是胺類)組合使用。 Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and methyl benzoyl benzoate; , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonylcarbonyl)diphenyl a benzophenone compound such as ketone or 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine or camphorquinone; 10-butyl-2- Chloramphenicone, benzoin, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with the polymerization starting assistant (D1) (especially an amine) described below.

作為酸產生劑,例如可列舉:4-羥基苯基二甲基鋶對甲苯磺酸鹽、4-羥基苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶對甲苯磺酸鹽、4-乙醯氧基苯基-甲基-苄基鋶六氟銻酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻 酸鹽、二苯基錪對甲苯磺酸鹽、二苯基錪六氟銻酸鹽等鎓鹽類,或硝基苄基甲苯磺酸酯/鹽類、安息香甲苯磺酸酯/鹽類等。 Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenoxyphenyldimethylate.鋶p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzylphosphonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate An acid salt, a diphenylsulfonium p-toluenesulfonate, a phosphonium salt such as diphenylsulfonium hexafluoroantimonate, or a nitrobenzyl tosylate/salt, a benzoin tosylate/salt or the like.

聚合起始劑(D)之含量相對於樹脂(B1)、樹脂(B2)及聚合性化合物(C)之合計量100質量份,較佳為0.1~30質量份,更佳為1~20質量份。若聚合起始劑(D)之含量在上述範圍內,則存在感光度提高而曝光時間縮短之傾向,故而生產性提高。 The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total of the resin (B1), the resin (B2) and the polymerizable compound (C). Share. When the content of the polymerization initiator (D) is within the above range, the sensitivity is improved and the exposure time tends to be shortened, so that productivity is improved.

亦可與聚合起始劑(D)一起進而包含聚合起始助劑(D1)。聚合起始助劑(D1)係用以對藉由聚合起始劑而開始聚合之光聚合性化合物的聚合進行促進之化合物、或增感劑。 Further, together with the polymerization initiator (D), a polymerization initiation aid (D1) may be further contained. The polymerization initiation aid (D1) is a compound or a sensitizer for promoting polymerization of a photopolymerizable compound which starts polymerization by a polymerization initiator.

作為聚合起始助劑(D1),可列舉胺化合物、烷氧基蒽化合物、9-氧硫化合物及羧酸化合物等,較佳為9-氧硫化合物。 As the polymerization initiation aid (D1), an amine compound, an alkoxy oxime compound, and 9-oxosulfuric acid can be cited. a compound, a carboxylic acid compound or the like, preferably 9-oxosulfur Compound.

作為胺化合物,可列舉三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸-2-二甲基胺基乙酯、4-二甲基胺基苯甲酸-2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(俗稱米其勒酮)、4,4'-雙(二乙基胺基)二苯甲酮、4,4'-雙(乙基甲基胺基)二苯甲酮等,其中較佳為4,4'-雙(二乙基胺基)二苯甲酮。亦可使用EAB-F(保土谷化學工業(股)製造)等市售品。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as mickleone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylamino)benzophenone or the like, of which 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

作為烷氧基蒽化合物,可列舉:9,10-二甲氧基蒽、2-乙 基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、9,10-二丁氧基蒽、2-乙基-9,10-二丁氧基蒽等。 As the alkoxy ruthenium compound, 9,10-dimethoxy oxime, 2-B Base-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-B Base-9,10-dibutoxyanthracene, and the like.

作為9-氧硫化合物,可列舉2-異丙基-9-氧硫、4-異丙基-9-氧硫、2,4-二乙基-9-氧硫、2,4-二氯-9-氧硫、1-氯-4-丙氧基-9-氧硫等。 9-oxosulfur The compound may, for example, be 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

作為羧酸化合物,可列舉:苯基硫烷基乙酸、甲基苯基硫烷基乙酸、乙基苯基硫烷基乙酸、甲基乙基苯基硫烷基乙酸、二甲基苯基硫烷基乙酸、甲氧基苯基硫烷基乙酸、二甲氧基苯基硫烷基乙酸、氯苯基硫烷基乙酸、二氯苯基硫烷基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫代乙酸、N-萘基甘胺酸、萘氧基乙酸等。 Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethylphenylsulfide. Alkylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

於使用該等聚合起始助劑(D1)之情形時,其使用量相對於樹脂(B1)、樹脂(B2)及聚合性化合物(C)之合計量100質量份,較佳為0.1~30質量份,更佳為1~20質量份。若聚合起始助劑(D1)之量在該範圍內,則存在可以更高感光度形成著色圖案,彩色濾光片之生產性提高之傾向。 When the polymerization initiator (D1) is used, the amount thereof is 100 parts by mass, preferably 0.1 to 30, based on the total amount of the resin (B1), the resin (B2), and the polymerizable compound (C). The mass part is more preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<溶劑(E)> <Solvent (E)>

溶劑(E)並無特別限定,可使用該領域內通常使用之溶劑。例如,可自下述溶劑中選擇使用:酯溶劑(於分子內含有-COO-且不含-O-之溶劑)、醚溶劑(於分子內含有-O-且不含-COO-之溶劑)、醚酯溶劑(於分子內含有-COO-與-O-之溶劑)、酮溶劑(於分子內含有-CO-且不含-COO-之溶劑)、醇溶劑、芳香族烴溶劑、醯胺溶劑、二甲基亞碸等。 The solvent (E) is not particularly limited, and a solvent which is usually used in the field can be used. For example, it can be selected from the following solvents: an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- in the molecule and containing no -COO-) , an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule and containing no -COO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine Solvent, dimethyl hydrazine, and the like.

作為酯溶劑,可列舉:乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己醇乙酸酯、γ-丁內酯等。 Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ring Hexanol acetate, γ-butyrolactone, and the like.

作為醚溶劑,可列舉:乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙醚、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯乙醚、甲基苯甲醚等。 Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and two. Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, methyl Anisole and the like.

作為醚酯溶劑,可列舉:甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、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、乙二醇單乙醚乙酸酯、二乙二醇單乙醚乙酸 酯、二乙二醇單丁醚乙酸酯等。 Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Ethyl acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate Ester, diethylene glycol monobutyl ether acetate, and the like.

作為酮溶劑,可列舉:4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮、異佛爾酮等。 Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone and the like.

作為醇溶劑,可列舉:甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、丙三醇等。 Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

作為芳香族烴溶劑,可列舉:苯、甲苯、二甲苯、均三甲苯等。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

作為醯胺溶劑,可列舉:N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮等。 Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

該等溶劑可單獨使用,亦可組合2種以上而使用。 These solvents may be used singly or in combination of two or more.

於上述溶劑之中,就塗敷性、乾燥性之方面而言,較佳為1 atm下之沸點為120℃以上180℃以下之有機溶劑。作為溶劑(E),較佳為丙二醇單甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、二乙二醇單甲醚、二乙二醇單乙醚及4-羥基-4-甲基-2-戊酮,更佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、乳酸乙酯及3-乙氧基丙酸乙酯。 Among the above solvents, an organic solvent having a boiling point of from 120 ° C to 180 ° C at 1 atm is preferred in terms of coatability and drying property. As the solvent (E), preferred is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether and 4-hydroxy-4-methyl-2-pentanone, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 3-ethoxypropionic acid ester.

溶劑(E)之含量相對於著色感光性樹脂組合物之總量較佳為70~95質量%,更佳為75~92質量%。換言之,著色感光性樹脂組合物之固形物成分較佳為5~30質量%,更佳為8~25質量%。 The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the colored photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass.

若溶劑(E)之含量在上述範圍內,則存在塗敷時之平坦性變得良好,並且形成彩色濾光片時色濃度不會不充分, 故而顯示特性變得良好之傾向。 When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density is not insufficient when the color filter is formed. Therefore, the tendency to display characteristics is good.

<界面活性劑(F)> <Interacting Agent (F)>

作為界面活性劑(F),可列舉聚矽氧系界面活性劑、氟系界面活性劑及具有氟原子之聚矽氧系界面活性劑等。該等亦可於側鏈具有聚合性基。 Examples of the surfactant (F) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may also have a polymerizable group in the side chain.

作為聚矽氧系界面活性劑,可列舉於分子內具有矽氧烷鍵之界面活性劑等。具體而言,可列舉Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400(商品名:Dow Corning Toray(股)製造);KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(股)製造);TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452及TSF4460(Momentive Performance Materials Japan附屬公司製造)等。 Examples of the polyoxymethylene-based surfactant include a surfactant having a decane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Dow Corning Toray); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan) )Wait.

作為上述氟系界面活性劑,可列舉於分子內具有氟碳鏈之界面活性劑等。具體而言,可列舉Fluorad(註冊商標)FC430、Fluorad FC431(住友3M(股)製造),Megafac(註冊商標)F142D、Megafac F171、Megafac F172、Megafac F173、Megafac F177、Megafac F183、Megafac F554、Megafac R30、Megafac RS-718-K(DIC(股)製造),Eftop(註冊商標)EF301、Eftop EF303、Eftop EF351、Eftop EF352(三菱綜合材料電子化成(Mitsubishi Materials Electronic Chemicals)(股)製造),Surflon(註冊商標)S381、Surflon S382、Surflon SC101、Surflon SC105(旭硝子(股)製造),E5844(大金精密化學(股)(Daikin Fine Chemical)研究所製造)等。 The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (Mitsubishi Materials Electronic) (manufactured by Chemicals), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.) .

作為上述具有氟原子之聚矽氧系界面活性劑,可列舉於分子內具有矽氧烷鍵及氟碳鏈之界面活性劑等。具體而言,可列舉Megafac(註冊商標)R08、Megafac BL20、Megafac F475、Megafac F477、Megafac F443(DIC(股)製造)等。 Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC).

該等界面活性劑可單獨使用,亦可組合2種以上而使用。 These surfactants may be used singly or in combination of two or more.

界面活性劑(F)之含量相對於著色感光性樹脂組合物之總量較佳為0.001質量%以上0.2質量%以下,更佳為0.002質量%以上0.1質量%以下,進而較佳為0.01質量%以上0.05質量%以下。再者,該含量中不包括上述顏料分散劑之含量。若界面活性劑(F)之含量在上述範圍內,則可使彩色濾光片之平坦性變得良好。 The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and further preferably 0.01% by mass or less based on the total amount of the coloring photosensitive resin composition. The above 0.05% by mass or less. Further, the content of the above 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.

<其他成分> <Other ingredients>

本發明之著色感光性樹脂組合物亦可視需要包含填充劑、其他高分子化合物、密接促進劑、抗氧化劑、光穩定劑、鏈轉移劑等該技術領域內眾所周知之添加劑。 The colored photosensitive resin composition of the present invention may optionally contain additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, which are well known in the art.

<著色感光性樹脂組合物之製造方法> <Method for Producing Colored Photosensitive Resin Composition>

本發明之著色感光性樹脂組合物例如可藉由將著色劑(A)、樹脂(B1)、樹脂(B2)、聚合性化合物(C)及聚合起始 劑(D)、以及視需要而使用之聚合起始助劑(D1)、溶劑(E)、界面活性劑(F)及其他成分加以混合而製備。 The colored photosensitive resin composition of the present invention can be started, for example, by coloring agent (A), resin (B1), resin (B2), polymerizable compound (C), and polymerization. The agent (D) and, if necessary, a polymerization starting aid (D1), a solvent (E), a surfactant (F), and other components are mixed and prepared.

於包含顏料(A2)作為著色劑(A)之情形時,較佳為將顏料(A2)預先與溶劑(E)混合,並使用珠磨機等進行分散直至顏料之平均粒徑成為0.2 μm以下之程度為止。此時,亦可視需要調配上述顏料分散劑、樹脂(B1)之一部分或全部或者樹脂(B2)之一部分或全部。向所獲得之顏料分散液中,將樹脂(B1)之剩餘部分、樹脂(B2)之剩餘部分及聚合性化合物(C)、以及視需要所使用之染料(A1)、聚合起始劑(D)、溶劑(E)之剩餘部分、界面活性劑(F)及其他成分等以成為特定濃度之方式混合,藉此可製備目標之著色感光性樹脂組合物。 When the pigment (A2) is contained as the coloring agent (A), it is preferred to mix the pigment (A2) with the solvent (E) in advance, and to use a bead mill or the like to disperse until the average particle diameter of the pigment is 0.2 μm or less. The extent of it. At this time, a part or all of the above-mentioned pigment dispersant, one part or all of the resin (B1) or one part of the resin (B2) may be blended as needed. To the obtained pigment dispersion, the remainder of the resin (B1), the remainder of the resin (B2), and the polymerizable compound (C), and optionally the dye (A1), polymerization initiator (D) The remaining portion of the solvent (E), the surfactant (F), and other components are mixed so as to have a specific concentration, whereby the intended colored photosensitive resin composition can be prepared.

包含染料(A1)之情形時之染料(A1)亦可預先分別溶解於溶劑(E)中。該溶液較佳為利用孔徑0.01~1 μm左右之過濾器進行過濾。 The dye (A1) in the case where the dye (A1) is contained may also be separately dissolved in the solvent (E) in advance. The solution is preferably filtered using a filter having a pore size of about 0.01 to 1 μm.

混合後之著色感光性樹脂組合物較佳為利用孔徑0.1~10 μm左右之過濾器進行過濾。 The colored photosensitive resin composition after mixing is preferably filtered using a filter having a pore diameter of about 0.1 to 10 μm.

<彩色濾光片及液晶顯示裝置之製造方法> <Color filter and method of manufacturing liquid crystal display device>

作為由本發明之著色感光性樹脂組合物製造彩色濾光片之著色圖案化塗膜(有時將「著色圖案化塗膜」簡記為「著色圖案」)之方法,可列舉光微影法、噴墨法、印刷法等。其中,較佳為光微影法。光微影法係將本發明之著色感光性樹脂組合物塗敷於基板上,並藉由將溶劑等揮發成分去除等使其乾燥而形成組合物層,繼而,經由光罩將 該組合物層曝光且進行顯影之方法。顯影後,視需要進行加熱,藉此可形成著色圖案。藉由於上述著色圖案之形成方法中,在曝光時不使用光罩及/或不進行顯影,可形成作為上述組合物層之硬化物之著色塗膜。可將如此獲得之著色圖案化塗膜及著色塗膜作為彩色濾光片。 A method of producing a color-patterned coating film (hereinafter, a "coloring pattern coating film" is simply referred to as a "coloring pattern") for producing a color filter from the colored photosensitive resin composition of the present invention includes a photolithography method and a spray method. Ink method, printing method, etc. Among them, photolithography is preferred. In the photolithography method, the colored photosensitive resin composition of the present invention is applied onto a substrate, and dried by removing a volatile component such as a solvent to form a composition layer, and then, via a photomask The composition layer is exposed and developed. After development, heating is performed as needed, whereby a colored pattern can be formed. In the method of forming the colored pattern described above, a colored coating film which is a cured product of the composition layer can be formed without using a photomask and/or without developing at the time of exposure. The colored patterned coating film and the colored coating film thus obtained can be used as a color filter.

所製作之彩色濾光片之膜厚並無特別限定,可根據目的或用途等而適當調整,例如為0.1~30 μm,較佳為0.1~20 μm,進而較佳為0.5~6 μm。 The film thickness of the produced color filter is not particularly limited, and can 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, and more preferably 0.5 to 6 μm.

作為基板,可使用石英玻璃、硼矽酸玻璃、鋁矽酸鹽玻璃、表面經二氧化矽塗佈之鹼石灰玻璃等玻璃板,或聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等樹脂板,矽,於上述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。該等基板上亦可形成有另一彩色濾光層、樹脂層、電晶體、電路等。 As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda lime glass coated with cerium oxide, or polycarbonate, polymethyl methacrylate or polyparaphenyl may 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. Another color filter layer, a resin layer, a transistor, a circuit, or the like may be formed on the substrates.

以下,對在形成有薄膜電晶體(以下,稱作「TFT」)之玻璃基板上形成圖案之方法進行說明。 Hereinafter, a method of forming a pattern on a glass substrate on which a thin film transistor (hereinafter referred to as "TFT") is formed will be described.

具體而言,利用光微影技術等眾所周知之方法,在玻璃基板21上對每1個像素形成複數個TFT22(參照圖1)。TFT22包括:閘極電極22a,其係於玻璃基板21上利用例如鉬(Mo)而形成,並且構成閘極線之一部分;閘極絕緣膜22b,其係形成於該閘極電極22a上且包含例如氮化膜(SiNx)與氧化膜(SiO2)之積層膜;多晶矽膜22c,其形成於該閘極絕緣膜22b上;及保護膜22d,其係由例如氧化膜(SiO2)與氮化膜(SiNx)之積層膜所形成。多晶矽膜22c之與 閘極電極22a相對向之區域成為TFT22之通道區域,又,該通道區域之兩側之區域成為源極區域或汲極區域。多晶矽膜22c之源極區域係經由保護膜22d中設置之連接孔(接觸孔)而電性連接於例如由鋁(Al)所形成之信號線27。再者,多晶矽膜22c之汲極區域係如後文所述般經由連接孔(接觸孔)201而與像素電極24電性連接。 Specifically, a plurality of TFTs 22 are formed on the glass substrate 21 for each pixel by a well-known method such as photolithography (see FIG. 1). The TFT 22 includes a gate electrode 22a which is formed on the glass substrate 21 by, for example, molybdenum (Mo), and constitutes a part of the gate line, and a gate insulating film 22b which is formed on the gate electrode 22a and includes For example, a laminated film of a nitride film (SiN x ) and an oxide film (SiO 2 ); a polycrystalline germanium film 22c formed on the gate insulating film 22b; and a protective film 22d made of, for example, an oxide film (SiO 2 ) and A laminated film of a nitride film (SiN x ) is formed. A region of the polysilicon film 22c opposed to the gate electrode 22a serves as a channel region of the TFT 22, and a region on both sides of the channel region becomes a source region or a drain region. The source region of the polysilicon film 22c is electrically connected to a signal line 27 formed of, for example, aluminum (Al) via a connection hole (contact hole) provided in the protective film 22d. Further, the drain region of the polysilicon film 22c is electrically connected to the pixel electrode 24 via a connection hole (contact hole) 201 as will be described later.

於在玻璃基板21上對每1個像素形成複數個TFT22時,在玻璃基板21上與TFT22同時形成對準標記(未圖示)。該對準標記如後文所述般成為彩色濾光層23之形成步驟中的位置對準基準。再者,該等對準標記亦可兼用作成為驅動基板與對向基板之貼合基準之標記。對準標記可於在TFT22之製造製程中形成配線等金屬層或多晶矽層時,利用至少其一層且以相同步驟形成。 When a plurality of TFTs 22 are formed for each pixel on the glass substrate 21, alignment marks (not shown) are formed on the glass substrate 21 simultaneously with the TFTs 22. This alignment mark serves as a position alignment reference in the formation step of the color filter layer 23 as will be described later. Further, the alignment marks may also serve as a mark for bonding the drive substrate and the counter substrate. The alignment mark can be formed by using at least one layer and in the same step when a metal layer or a polysilicon layer such as a wiring is formed in the manufacturing process of the TFT 22.

其次,於形成有TFT22及對準標記之玻璃基板21上,塗敷本發明之著色感光性樹脂組合物,進行加熱乾燥(預烘烤)及/或減壓乾燥,藉此去除溶劑等揮發成分使其乾燥,形成膜厚0.5~5.0 μm,例如1.0 μm之組合物層。 Next, the colored photosensitive resin composition of the present invention is applied onto the glass substrate 21 on which the TFT 22 and the alignment mark are formed, and dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent. It is dried to form a composition layer having a film thickness of 0.5 to 5.0 μm, for example, 1.0 μm.

作為塗敷方法,可列舉:旋轉塗佈法、狹縫式塗佈法、狹縫-旋轉塗佈法等。 Examples of the coating method include a spin coating method, a slit coating method, and a slit-spin coating method.

進行加熱乾燥之情形時之溫度較佳為30~120℃,更佳為50~110℃。又,作為加熱時間,較佳為10秒~60分鐘,更佳為30秒~30分鐘。 The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

於進行減壓乾燥之情形時,較佳為在50~150 Pa之壓力下,於20~25℃之溫度範圍內進行。 In the case of drying under reduced pressure, it is preferably carried out at a temperature of from 20 to 25 ° C under a pressure of 50 to 150 Pa.

其次,經由光罩(未圖示)對組合物層照射紫外線,進而利用顯影液選擇性地去除不需要部(未曝光部),藉此獲得形成有到達至多晶矽膜22c之汲極區域的連接孔(接觸孔)201之成形於像素上之組合物層,然後進行水洗。 Then, the composition layer is irradiated with ultraviolet rays through a photomask (not shown), and the unnecessary portion (unexposed portion) is selectively removed by the developer, whereby the connection to the drain region reaching the polysilicon film 22c is obtained. The layer of the composition of the hole (contact hole) 201 formed on the pixel is then washed with water.

藉由顯影,組合物層之未曝光部溶解於顯影液中而得以去除。作為顯影液,例如較佳為氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物之水溶液。該等鹼性化合物於水溶液中之濃度較佳為0.01~10質量%,更佳為0.03~5質量%。進而,顯影液亦可含有界面活性劑。 By developing, the unexposed portion of the composition layer is dissolved in the developer to be removed. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration of the basic compound in the aqueous solution is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

顯影方法可為浸置法(puddle method)、浸漬法及噴霧法等之任一種。進而,顯影時可使基板傾斜為任意角度。 The developing method may be any one of a puddle method, a dipping method, and a spray method. Further, the substrate can be inclined at an arbitrary angle during development.

其後,為使形成有連接孔(接觸孔)201之組合物層再流動(回焊(reflow))及/或硬化,在例如150~250℃之範圍、較佳為160~235℃之範圍之溫度下加熱10~60分鐘,較佳為1~120分鐘。如此,形成著色感光性樹脂組合物層23A。該著色感光性樹脂組合物層23A對應本發明之彩色濾光片。 Thereafter, in order to reflow (reflow) and/or harden the composition layer in which the connection holes (contact holes) 201 are formed, it is, for example, in the range of 150 to 250 ° C, preferably 160 to 235 ° C. The temperature is heated for 10 to 60 minutes, preferably 1 to 120 minutes. Thus, the colored photosensitive resin composition layer 23A was formed. The colored photosensitive resin composition layer 23A corresponds to the color filter of the present invention.

反覆進行該操作,由紅色著色感光性樹脂組合物、綠色著色感光性樹脂組合物及藍色著色感光性樹脂組合物分別形成著色感光性樹脂組合物層23A,藉此對應各像素列而形成包含紅色濾光片23a、綠色濾光片23b及藍色濾光片23c之彩色濾光層23(參照圖2)。彩色濾光層23之各濾光片間之區域成為相鄰接之顏色之混合區域,但因該區域為與信號線27相對向之遮光區域,故而於品質上並無特別妨礙。再者,亦可使該各濾光片間之區域不著色。 By repeating this operation, the colored photosensitive resin composition layer 23A is formed of the red colored photosensitive resin composition, the green colored photosensitive resin composition, and the blue colored photosensitive resin composition, respectively, thereby forming inclusions corresponding to the respective pixel columns. The color filter layer 23 of the red color filter 23a, the green color filter 23b, and the blue color filter 23c (refer FIG. 2). The region between the filters of the color filter layer 23 is a mixed region of adjacent colors. However, since this region is a light-blocking region facing the signal line 27, there is no particular disadvantage in quality. Furthermore, the area between the filters may not be colored.

繼而,利用例如旋轉塗佈法,以覆蓋彩色濾光層23之方式,形成例如膜厚0.3~2.0 μm之作為保護膜之感光性樹脂膜29。繼而,經由光罩(未圖示)對感光性樹脂膜29照射紫外線,進而利用顯影液選擇性地去除與連接孔201對應之區域及不需要部,藉此形成到達至多晶矽膜22c之汲極區域的連接孔(接觸孔)202,然後進行水洗。其後,為使感光性樹脂膜29再流動(回焊),在100~300℃之範圍之溫度、例如200℃下進行加熱。繼而,為去除沈積於接觸孔202內之染料等殘渣及有機物而利用氧電漿進行蝕刻,進而,為去除由氧電漿所形成之氧化膜,利用例如稀氫氟酸進行蝕刻。 Then, for example, a photosensitive resin film 29 as a protective film having a film thickness of 0.3 to 2.0 μm is formed by, for example, a spin coating method so as to cover the color filter layer 23. Then, the photosensitive resin film 29 is irradiated with ultraviolet rays through a photomask (not shown), and the region corresponding to the connection hole 201 and the unnecessary portion are selectively removed by the developer, thereby forming a drain reaching the polysilicon film 22c. The connection hole (contact hole) 202 of the area is then washed with water. Thereafter, in order to reflow (reflow) the photosensitive resin film 29, it is heated at a temperature in the range of 100 to 300 ° C, for example, 200 ° C. Then, in order to remove residues and organic substances such as dyes deposited in the contact holes 202, etching is performed by oxygen plasma, and further, etching is performed by using, for example, dilute hydrofluoric acid to remove the oxide film formed of the oxygen plasma.

其次,於感光性樹脂膜29上,利用例如濺鍍法形成透明導電材料,例如ITO(Indium-Tin Oxide:銦與錫之氧化物混合膜),利用光微影技術及蝕刻而將該ITO膜圖案化,形成透明之像素電極24(參照圖3)。再者,該像素電極24亦可根據所製作之器件之不同而由鋁(Al)或銀(Ag)等金屬所形成。其後,利用已知方法形成配向膜後,將該驅動基板與對向基板貼合,藉此可製造液晶顯示裝置。 Next, a transparent conductive material such as ITO (Indium-Tin Oxide: mixed film of indium and tin oxide) is formed on the photosensitive resin film 29 by, for example, a sputtering method, and the ITO film is formed by photolithography and etching. The pattern is formed to form a transparent pixel electrode 24 (see Fig. 3). Furthermore, the pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag) depending on the device to be fabricated. Thereafter, the alignment film is formed by a known method, and then the driving substrate and the counter substrate are bonded together, whereby a liquid crystal display device can be manufactured.

根據本發明之著色感光性樹脂組合物,尤其可良率良好地製作表面異物較少的高性能之彩色濾光片,故而該彩色濾光片可用作顯示裝置(例如,液晶顯示裝置、有機EL(electroluminescence,電致發光)裝置等)、電子紙、固體攝像元件等中所使用之彩色濾光片。 According to the colored photosensitive resin composition of the present invention, a high-performance color filter having less surface foreign matter can be produced with good yield, and thus the color filter can be used as a display device (for example, a liquid crystal display device, organic A color filter used in an EL (electroluminescence) device, an electronic paper, a solid-state imaging device, or the like.

實施例 Example

其次,列舉實施例,對本發明進行更具體說明。例中之表示含量或使用量之%及份只要無特別說明則為質量基準。 Next, the present invention will be more specifically described by way of examples. The % and the parts indicating the content or the amount used in the examples are based on mass unless otherwise specified.

[合成例1] [Synthesis Example 1]

於包括冷卻管及攪拌裝置之燒瓶內,投入由式(A1-1a)所表示之化合物與由式(A1-1b)所表示之化合物的混合物(商品名Chugai Aminol Fast Pink R;中外化成製造)15份、氯仿150份及N,N-二甲基甲醯胺8.9份,於攪拌下一面維持為20℃以下,一面滴加添加亞硫醯氯10.9份。於滴加結束後,升溫至50℃,在該溫度下維持5小時進行反應,其後冷卻至20℃。將冷卻後之反應溶液於攪拌下一面維持為20℃以下,一面滴加添加2-乙基己胺12.5份與三乙胺22.1份之混合液。其後,在該溫度下攪拌5小時進行反應。繼而,將所獲得之反應混合物利用旋轉蒸發器將溶劑蒸餾去除後,添加少量甲醇且遽烈攪拌。將該混合物一面攪拌一面添加至離子交換水375份之混合液中,析出結晶。將所析出之結晶過濾分離,利用離子交換水充分洗淨,並在60℃下進行減壓乾燥,獲得染料(A1-1)(由式(A1-1-1)~式(A1-1-8)所表示之化合物之混合物)11.3份。 In a flask including 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 Sinotrans) 15 parts, 150 parts of chloroform, and 8.9 parts of N,N-dimethylformamide were maintained at 20 ° C or less while stirring, and 10.9 parts of sulfite chloride was added dropwise thereto. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was maintained at this temperature for 5 hours, and then cooled to 20 ° C. The reaction solution after cooling was maintained at 20 ° C or lower while stirring, and a mixed liquid 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 this temperature for 5 hours. Then, after the obtained reaction mixture was distilled off by a rotary evaporator, a small amount of methanol was added and stirred vigorously. 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, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a dye (A1-1) (from the formula (A1-1-1) to the formula (A1-1- 8) A mixture of the indicated compounds) 11.3 parts.

[合成例2] [Synthesis Example 2]

使氮氣以0.02 L/min流入於包括回流冷卻器、滴液漏斗及攪拌機之燒瓶內而調整為氮氣環境,加入乳酸乙酯305質量份,一面攪拌,一面加熱至70℃為止。 Nitrogen gas was introduced into a flask including a reflux condenser, a dropping funnel and a stirrer at 0.02 L/min to adjust to a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring.

繼而,將丙烯酸60質量份及丙烯酸-3,4-環氧三環[5.2.1.02.6]癸酯(將由式(I-1)所表示之化合物與由式(II-1)所表示之化合物以莫耳比50:50混合)240質量份溶解於乳酸 乙酯140質量份而製備溶液,將該溶解液使用滴液漏斗歷時4小時滴加至保溫為70℃之燒瓶內。 Then, 60 parts by mass of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2.6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) A solution was prepared by dissolving 240 parts by mass of ethyl lactate in an amount of 240 parts by mass in a molar ratio of 50:50, and the solution was added dropwise to a flask maintained at 70 ° C for 4 hours using a dropping funnel.

另一方面,將使聚合起始劑2,2'-偶氮雙(2,4-二甲基戊腈)30質量份溶解於乳酸乙酯225質量份中所得之溶液,使用另一滴液漏斗歷時4小時滴加至燒瓶內。於聚合起始劑之溶液滴加結束後,於70℃保持4小時,其後冷卻至室溫為止,獲得重量平均分子量Mw為9.1×103、分子量分佈為2.1、固形物成分26質量%、固形物成分酸值120 mg-KOH/g之樹脂(B1-1)溶液。 On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate, using another dropping funnel It was added dropwise to the flask over 4 hours. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 9.1 × 10 3 , a molecular weight distribution of 2.1, and a solid content of 26% by mass. A solution of a resin (B1-1) having a solid content of 120 mg-KOH/g.

樹脂(B1-1)具有下述結構單元。 The resin (B1-1) has the following structural unit.

[合成例3] [Synthesis Example 3]

使氮氣以0.02 L/min流入於包括攪拌機、溫度計、回流冷卻器及滴液漏斗之燒瓶內而調整為氮氣環境,加入丙二醇單甲醚乙酸酯257質量份,一面攪拌,一面加熱至70℃為止。繼而,將丙烯酸57質量份、乙烯基甲苯83份、丙烯酸-3,4-環氧三環[5.2.1.02.6]癸酯(將由式(I-1)所表示之化合 物與由式(II-1)所表示之化合物以莫耳比50:50混合)238質量份溶解於丙二醇單甲醚乙酸酯140質量份而製備溶液,將該溶液使用滴液漏斗歷時4小時滴加至保溫為70℃之燒瓶內。另一方面,將使聚合起始劑2,2'-偶氮雙(2,4-二甲基戊腈)30質量份溶解於丙二醇單甲醚乙酸酯225質量份中所得之溶液,使用另一滴液漏斗歷時4小時滴加至燒瓶內。於聚合起始劑之溶液滴加結束後,於70℃保持4小時,其後冷卻至室溫為止,獲得重量平均分子量Mw為9.9×103、固形物成分37.5%、固形物成分酸值112 mg-KOH/g之樹脂(B1-2)溶液。樹脂(B1-2)具有下述結構單元。 Nitrogen gas was introduced into a flask including a stirrer, a thermometer, a reflux condenser, and a dropping funnel at 0.02 L/min to adjust to a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 70 ° C while stirring. until. Then, 57 parts by mass of acrylic acid, 83 parts of vinyltoluene, and 3,4-epoxytricyclo[5.2.1.0 2.6 ]decyl acrylate (the compound represented by the formula (I-1) and the formula (II-) 1) The compound represented by dissolving 140 parts by mass of propylene glycol monomethyl ether acetate in 238 parts by mass of a molar ratio of 50:50 was prepared, and the solution was added dropwise to a heat retention rate of 70 using a dropping funnel over 4 hours. In a °C flask. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 225 parts by mass of propylene glycol monomethyl ether acetate is used. Another dropping funnel was added dropwise to the flask over 4 hours. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 9.9 × 10 3 , a solid content of 37.5%, and a solid component acid value of 112. A solution of mg-KOH/g of resin (B1-2). The resin (B1-2) has the following structural unit.

[合成例4] [Synthesis Example 4]

將包括攪拌機、溫度計、回流冷卻管、滴液漏斗及氮氣導入管之燒瓶內調整為氮氣環境,加入丙二醇單甲醚乙酸酯210份,一面攪拌,一面升溫至100℃為止。繼而,將使甲基丙烯酸苄酯106份、丙烯酸22份及甲基丙烯酸二環戊酯(日立化成(股)製造FA-513M)22份溶解於丙二醇單甲醚乙酸酯215份,進而溶解2,2'-偶氮雙異丁腈3.6份而製備之溶液滴加至燒瓶內,在100℃下持續攪拌5小時,藉此獲得重量平均分子量Mw為1.00×104、固形物成分34.1%、固形 物成分酸值為109 mgKOH/g之樹脂(B2-1)溶液。樹脂(B2-1)具有下述結構單元。 The flask including a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube was adjusted to a nitrogen atmosphere, and 210 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 100 ° C while stirring. Then, 22 parts of benzyl methacrylate, 22 parts of acrylic acid, and dicyclopentyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) were dissolved in 215 parts of propylene glycol monomethyl ether acetate, and dissolved. A solution prepared by dissolving 3.6 parts of 2,2'-azobisisobutyronitrile was added dropwise to the flask, and stirring was continued at 100 ° C for 5 hours, whereby a weight average molecular weight Mw of 1.00 × 10 4 and a solid content of 34.1% were obtained. A resin (B2-1) solution having a solid content of 109 mgKOH/g. The resin (B2-1) has the following structural unit.

[合成例5] [Synthesis Example 5]

使氮氣以0.02 L/min流入於包括回流冷卻器、滴液漏斗及攪拌機之燒瓶內而調整為氮氣環境,加入乳酸乙酯220份,一面攪拌,一面加熱至70℃為止。繼而,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(將由式(I-1)所表示之化合物與由式(II-1)所表示之化合物以莫耳比50:50混合)336份溶解於乳酸乙酯140份而製備溶液,將該溶液使用滴液漏斗歷時4小時滴加至保溫為70℃之燒瓶內。另一方面,將使聚合起始劑2,2'-偶氮雙(2,4-二甲基戊腈)30份溶解於乳酸乙酯95份中所得之溶液,使用另一滴液漏斗歷時4小時滴加至燒瓶內。於聚合起始劑之溶液滴加結束後,於70℃保持4小時,其後冷卻至室溫為止,獲得重量平均分子量Mw為8.0×103、分子量分佈為2.5、固形物成分為48%、溶液酸值為50 mg-KOH/g(固形物成分換算之酸值為104 mgKOH/g)之樹脂(B1-3)溶液。樹脂(B1-3)具有下述結構單元。 Nitrogen gas was introduced into a flask including a reflux condenser, a dropping funnel and a stirrer at 0.02 L/min to adjust to a nitrogen atmosphere, and 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Then, 84 parts of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 2.6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) A solution was prepared by dissolving 336 parts of the compound in a molar ratio of 50:50, 140 parts of ethyl lactate, and the solution was added dropwise to a flask maintained at 70 ° C for 4 hours using a dropping funnel. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate, and using another dropping funnel for 4 Add dropwise to the flask in an hour. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture 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, and a solid content of 48%. A solution of a resin (B1-3) having a solution acid value of 50 mg-KOH/g (acid value of solid content of 104 mgKOH/g). The resin (B1-3) has the following structural unit.

合成例中所獲得之樹脂之重量平均分子量(Mw)及數量平均分子量(Mn)之測定係使用GPC法(Gel Permeation Chromatography,凝膠滲透層析法),在以下條件下進行。 The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured by GPC method (Gel Permeation Chromatography) under the following conditions.

裝置:K2479(島津製作所(股)製造) Device: K2479 (made by Shimadzu Corporation)

管柱:SHIMADZU Shim-pack GPC-80M Column: 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:1.0 mL/min Flow rate: 1.0 mL/min

檢測器:RI Detector: RI

校正用標準物質:TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(東曹(Tosoh)(股)製造)將上述中所獲得之聚苯乙烯換算之重量平均分子量及數量平均分子量之比(Mw/Mn)作為分子量分佈。 Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh) to convert the weight of polystyrene obtained in the above The ratio of the average molecular weight to the number average molecular weight (Mw/Mn) is taken as the molecular weight distribution.

實施例1~6及比較例1 Examples 1 to 6 and Comparative Example 1 [著色感光性樹脂組合物之製備] [Preparation of Colored Photosensitive Resin Composition]

將表1所示之量之各成分混合而獲得著色感光性樹脂組合物。 The components of the amounts shown in Table 1 were mixed to obtain a colored photosensitive resin composition.

再者,表1中,各成分表示以下者。 In addition, in Table 1, each component shows the following.

著色劑(A)之(A1-1):染料(A1-1) Coloring Agent (A) (A1-1): Dye (A1-1)

著色劑(A)之(A1-2):C.I.直接藍264與十二烷基苯磺酸之鹽(Orient化學工業(股)製造)(染料) (A1-2) of coloring agent (A): C.I. salt of direct blue 264 and dodecylbenzenesulfonic acid (manufactured by Orient Chemical Industry Co., Ltd.) (dye)

著色劑(A)之(A2-1):C.I.顏料藍15:6(顏料) Coloring Agent (A) (A2-1): C.I. Pigment Blue 15:6 (Pigment)

樹脂(B1)之(B1-1):樹脂(B1-1) Resin (B1) (B1-1): Resin (B1-1)

樹脂(B1)之(B1-2):樹脂(B1-2) Resin (B1) (B1-2): Resin (B1-2)

樹脂(B1)之(B1-3):樹脂(B1-3) Resin (B1) (B1-3): Resin (B1-3)

樹脂(B2)之(B2-1):樹脂(B2-1) Resin (B2) (B2-1): Resin (B2-1)

聚合性化合物(C):二季戊四醇六丙烯酸酯(KAYARAD註冊商標)DPHA;日本化藥(股)製造) Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

聚合起始劑(D)之(D-1):N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE 01;BASF公司製造;O-醯基肟化合物) (D-1) of polymerization initiator (D): N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered) Trademark) OXE 01; manufactured by BASF; O-mercaptopurine compound)

聚合起始劑(D)之(D-2):2-甲基-2-啉基-1-(4-甲基硫烷基苯基)丙烷-1-酮(Irgacure(註冊商標)907;BASF公司製造;烷基苯酮化合物) (D-2) of polymerization initiator (D): 2-methyl-2- Orolinyl-1-(4-methylsulfanylphenyl)propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF Corporation; alkylphenone compound)

聚合起始助劑(D1):2,4-二乙基-9-氧硫KAYACURE(註冊商標)DETX-S;日本化藥(股)製造;9-氧硫化合物) Polymerization start aid (D1): 2,4-diethyl-9-oxosulfur KAYACURE (registered trademark) DETX-S; manufactured by Nippon Chemical Co., Ltd.; 9-oxygen sulfur Compound)

溶劑(E)之(E-1):丙二醇單甲醚乙酸酯 Solvent (E) (E-1): propylene glycol monomethyl ether acetate

溶劑(E)之(E-2):丙二醇單甲醚 Solvent (E) (E-2): propylene glycol monomethyl ether

溶劑(E)之(E-3):乳酸乙酯 Solvent (E) (E-3): ethyl lactate

界面活性劑(F)之(F-1):聚醚改性聚矽氧油(Toray Silicone SH8400;Dow Corning Toray(股)製造) Surfactant (F) (F-1): Polyether modified polyoxyxide oil (Toray Silicone SH8400; manufactured by Dow Corning Toray)

[顯影性評價] [Developability evaluation]

於2英吋見方之玻璃基板(Eagle XG;Corning公司製造)上,利用旋轉塗佈法塗敷著色感光性樹脂組合物後,在 100℃下預烘烤3分鐘而形成組合物層。於裝有包含非離子系界面活性劑0.12%與碳酸鈉2%之水系顯影液10 ml之培養皿中,將形成有上述組合物層之基板在25℃下浸漬120秒,目視觀察浸漬後之顯影液。於顯影液中未確認到來自著色感光性樹脂組合物之剝離片之情形時,判斷顯影性良好且評價為○,於確認到剝離片之情形時,評價為×。若顯影液中確認到來自著色感光性樹脂組合物之剝離片,則剝離片作為異物而附著於彩色濾光片上成為產生不良之原因,故不佳。將結果示於表2。 After coating the colored photosensitive resin composition by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) of 2 inches square, The composition layer was formed by prebaking at 100 ° C for 3 minutes. The substrate on which the above composition layer was formed was immersed at 25 ° C for 120 seconds in a petri dish containing 10 ml of a water-based developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate, and visually observed after immersion. Developer solution. When the peeling sheet from the coloring photosensitive resin composition was not confirmed in the developing solution, the developability was judged to be good and evaluated as ○, and when the peeling sheet was confirmed, it was evaluated as ×. When the release sheet from the colored photosensitive resin composition is confirmed in the developer, the release sheet adheres to the color filter as a foreign matter, which causes a defect, which is not preferable. The results are shown in Table 2.

[彩色濾光片之製作] [Production of color filter]

於2英吋見方之玻璃基板(Eagle XG;Corning公司製造)上,利用旋轉塗佈法塗敷著色感光性樹脂組合物後,在100℃下預烘烤3分鐘而形成組合物層。冷卻後,將形成有該組合物層之基板與具有圖案之石英玻璃製光罩之間隔設為200 μm,並使用曝光機(TME-150RSK;TOPCON(股)製造),在大氣環境下,以40 mJ/cm2之曝光量(365 nm基準)進行光照射。再者,此時之光照射係使來自超高壓水銀燈之發射光穿透濾光器(UV-35;朝日分光(股)製造)而進行。又,光照射係經由將圖案(具有1邊為30 μm之正方形之遮光部,且該正方形之間隔為100 μm)形成於同一平面上之光罩而進行(以下,將光罩之與透光部對應地受到光照射之部分稱作「曝光部」,將光罩之與遮光部對應地未受到光照射之部分稱作「未曝光部」)。於光照射後,將上述塗膜在25℃下於包含非離子系界面活性劑0.12%與碳酸鈉 2%之水系顯影液中進行60秒浸漬顯影,水洗後,於烘箱中、230℃下後烘烤20分鐘,藉此獲得於未曝光部形成有30 μm見方之孔的彩色濾光片。 The colored photosensitive resin composition was applied by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning) of 2 inches square, and then prebaked at 100 ° C for 3 minutes to form a composition layer. After cooling, the interval between the substrate on which the composition layer was formed and the patterned quartz glass mask was set to 200 μm, and an exposure machine (TME-150RSK; TOPCON) was used in an atmosphere to Light exposure was performed at an exposure of 40 mJ/cm 2 (365 nm reference). Further, the light irradiation at this time is performed by passing the emitted light from the ultrahigh pressure mercury lamp through a filter (UV-35; manufactured by Asahi Separation Co., Ltd.). Further, the light irradiation is performed by forming a mask (a light-shielding portion having a square of 30 μm on one side and a square interval of 100 μm) on the same plane (hereinafter, the light shield is transparent to light). A portion that is irradiated with light correspondingly is referred to as an "exposure portion", and a portion of the photomask that is not irradiated with light corresponding to the light shielding portion is referred to as an "unexposed portion". After the light irradiation, the coating film was immersed and developed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 25 ° C for 60 seconds, washed with water, and then placed in an oven at 230 ° C. Baking was carried out for 20 minutes, whereby a color filter having a hole of 30 μm square formed in the unexposed portion was obtained.

[膜厚測定] [Measurement of film thickness]

於所獲得之彩色濾光片之曝光部,使用膜厚測定裝置(DEKTAK3;日本真空技術(股)製造))測定膜厚。將結果示於表2。 The film thickness of the obtained color filter was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.

[色度評價] [Color Evaluation]

於所獲得之彩色濾光片之曝光部,使用色度計(OSP-SP-200;奧林巴斯(Olympus)(股)製造)測定分光,並使用C光源之色匹配函數測定CIE之XYZ表色系統中之xy色度座標(x,y)及三刺激值Y。Y值越大,表示亮度越高。將結果示於表2。 The spectrophotometer (OSP-SP-200; manufactured by Olympus Co., Ltd.) was used to measure the spectroscopic portion of the obtained color filter, and the color matching function of the C light source was used to measure the XYZ of the CIE. The xy chromaticity coordinates (x, y) and the tristimulus value Y in the color system. The larger the Y value, the higher the brightness. The results are shown in Table 2.

已確認實施例之著色感光性樹脂組合物在形成彩色濾光 片時,未確認到顯影所造成之剝離片之產生。由此,可利用由本發明之著色感光性樹脂組合物所製作之彩色濾光片,以較高之良率製造顯示裝置。 It has been confirmed that the colored photosensitive resin composition of the embodiment forms color filter At the time of filming, the occurrence of the peeling sheet by the development was not confirmed. Thus, the color filter produced by the colored photosensitive resin composition of the present invention can be used to manufacture a display device at a high yield.

根據本發明之著色感光性樹脂組合物,於顯影後之顯影液中,較少產生來自著色感光性樹脂組合物之剝離片。 According to the colored photosensitive resin composition of the present invention, a release sheet derived from the colored photosensitive resin composition is less likely to be produced in the developer after development.

21‧‧‧玻璃基板 21‧‧‧ glass substrate

22‧‧‧TFT(開關元件) 22‧‧‧TFT (switching element)

22a‧‧‧閘極電極 22a‧‧‧Gate electrode

22b‧‧‧閘極絕緣膜 22b‧‧‧gate insulating film

22c‧‧‧多晶矽膜 22c‧‧‧ Polysilicon film

22d‧‧‧保護膜 22d‧‧‧Protective film

23‧‧‧彩色濾光層 23‧‧‧Color filter layer

23A‧‧‧著色感光性樹脂組合物層(彩色濾光片) 23A‧‧‧Colored photosensitive resin composition layer (color filter)

23a‧‧‧紅色濾光片 23a‧‧‧Red Filter

23b‧‧‧綠色濾光片 23b‧‧‧Green Filter

23c‧‧‧藍色濾光片 23c‧‧‧Blue filter

24‧‧‧像素電極 24‧‧‧pixel electrode

27‧‧‧信號線 27‧‧‧ signal line

29‧‧‧感光性樹脂膜(保護膜) 29‧‧‧Photosensitive resin film (protective film)

201、202‧‧‧連接孔 201, 202‧‧‧ connection holes

圖1係說明本發明之彩色濾光片之製造方法之概略圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a method of producing a color filter of the present invention.

圖2係說明本發明之彩色濾光片之製造方法之概略圖。 Fig. 2 is a schematic view showing a method of manufacturing the color filter of the present invention.

圖3係說明本發明之彩色濾光片之製造方法之概略圖。 Fig. 3 is a schematic view showing a method of manufacturing the color filter of the present invention.

Claims (5)

一種著色感光性樹脂組合物,其包含(A)、(B1)、(B2)、(C)及(D):(A)著色劑;(B1)包含源自選自由不飽和羧酸及不飽和羧酸酐所組成之群中的至少1種之結構單元、及源自具有碳數2~4之環狀醚結構及乙烯性不飽和鍵之單體之結構單元的樹脂;(B2)包含源自選自由不飽和羧酸及不飽和羧酸酐所組成之群中的至少1種之結構單元、及源自具有脂環式烴結構之單體之結構單元的樹脂(其中,不包含源自具有碳數2~4之環狀醚結構及乙烯性不飽和鍵之單體之結構單元);(C)聚合性化合物;及(D)聚合起始劑。 A colored photosensitive resin composition comprising (A), (B1), (B2), (C) and (D): (A) a colorant; (B1) comprising a source selected from the group consisting of unsaturated carboxylic acids and not a structural unit of at least one of a group consisting of a saturated carboxylic anhydride; and a resin derived from a structural unit having a cyclic ether structure having a carbon number of 2 to 4 and a monomer having an ethylenically unsaturated bond; (B2) comprising a source a resin derived from at least one structural unit selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer having an alicyclic hydrocarbon structure (wherein a structural unit of a cyclic ether structure having 2 to 4 carbon atoms and a monomer having an ethylenically unsaturated bond; (C) a polymerizable compound; and (D) a polymerization initiator. 如請求項1之著色感光性樹脂組合物,其中(B2)進而包含源自具有芳香族烴基之單體之結構單元。 The colored photosensitive resin composition of claim 1, wherein (B2) further comprises a structural unit derived from a monomer having an aromatic hydrocarbon group. 如請求項1或2之著色感光性樹脂組合物,其中(B2)之含量相對於(B1)與(B2)之合計量為10~90質量%。 The colored photosensitive resin composition of claim 1 or 2, wherein the content of (B2) is from 10 to 90% by mass based on the total of (B1) and (B2). 一種彩色濾光片,其係由如請求項1至3中任一項之著色感光性樹脂組合物所形成。 A color filter formed of the colored photosensitive resin composition according to any one of claims 1 to 3. 一種顯示裝置,其包含如請求項4之彩色濾光片。 A display device comprising a color filter as in claim 4.
TW101137000A 2011-10-07 2012-10-05 Colored photosensitive resin composition TWI610134B (en)

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