TWI566045B - Coloring the photosensitive resin composition - Google Patents
Coloring the photosensitive resin composition Download PDFInfo
- Publication number
- TWI566045B TWI566045B TW101103847A TW101103847A TWI566045B TW I566045 B TWI566045 B TW I566045B TW 101103847 A TW101103847 A TW 101103847A TW 101103847 A TW101103847 A TW 101103847A TW I566045 B TWI566045 B TW I566045B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- acid
- compound
- resin composition
- copolymer
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Liquid Crystal (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本發明係有關於一種著色感光性樹脂組合物。 The present invention relates to a colored photosensitive resin composition.
著色感光性樹脂組合物,係被廣泛應用於:液晶顯示裝置、有機電致發光顯示裝置、電漿顯示器等之顯示裝置所使用的彩色濾光片的製造上。以此種著色感光性樹脂組合物而言,已知有:含有甲基丙烯酸及丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯的共聚物作為樹脂之著色感光性樹脂組合物(專利文獻1)。 The colored photosensitive resin composition is widely used in the production of color filters used in display devices such as liquid crystal display devices, organic electroluminescence display devices, and plasma displays. In such a colored photosensitive resin composition, a copolymer containing methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate as a coloring property of a resin is known. Resin composition (Patent Document 1).
[專利文獻1]特開2010-211198號公報 [Patent Document 1] JP-A-2010-211198
習知以來皆知,當將上述的著色感光性樹脂組合物利用微影法來形成著色圖形之際,其未曝光部對於顯影液的 溶解性仍有無法充分地滿足需求之情形發生。 It is known that when the color-developing photosensitive resin composition described above is formed into a colored pattern by a lithography method, the unexposed portion is applied to the developer. Solubility still occurs when the demand is not adequately met.
本發明係為提供以下[1]~[6]所述物者。 The present invention provides the following items [1] to [6].
[1]著色感光性樹脂組合物,包括:著色劑、黏合劑樹脂、聚合性化合物及聚合引發劑;該黏合劑樹脂係為包括具有以下結構單元的共聚物之黏合劑樹脂:來自甲基丙烯酸之結構單元、來自丙烯酸之結構單元、以及來自可跟甲基丙烯酸和丙烯酸共聚合的單體之結構單元。 [1] A colored photosensitive resin composition comprising: a colorant, a binder resin, a polymerizable compound, and a polymerization initiator; the binder resin is a binder resin comprising a copolymer having the following structural unit: from methacrylic acid The structural unit, the structural unit derived from acrylic acid, and the structural unit derived from a monomer copolymerizable with methacrylic acid and acrylic acid.
[2]如[1]所述之著色感光性樹脂組合物,其中上述共聚物係為包括來自具有碳數2~4的環狀醚結構的不飽和化合物之結構單元的共聚物。 [2] The colored photosensitive resin composition according to [1], wherein the copolymer is a copolymer comprising a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms.
[3]如[1]或[2]所述之著色感光性樹脂組合物,其中上述共聚物的含有量,係相對於黏合劑樹脂的含有量而言,為10質量%以上、100質量%以下。 [3] The colored photosensitive resin composition according to the above [1], wherein the content of the copolymer is 10% by mass or more and 100% by mass based on the content of the binder resin. the following.
[4]如[1]、[2]或[3]所述之著色感光性樹脂組合物,其中該著色劑係為包括染料之著色劑。 [4] The colored photosensitive resin composition according to [1], [2] or [3], wherein the coloring agent is a coloring agent including a dye.
[5]彩色濾光片,係由如[1]、[2]、[3]或[4]所述之著色感光性樹脂組合物所形成。 [5] A color filter formed of the colored photosensitive resin composition according to [1], [2], [3] or [4].
[6]顯示裝置,包括如[5]所述之彩色濾光片。 [6] A display device comprising the color filter according to [5].
本發明的著色感光性樹脂組合物,可在形成著色圖形時,令未曝光部對於顯影液具有高溶解性。 In the colored photosensitive resin composition of the present invention, when the colored pattern is formed, the unexposed portion can have high solubility to the developer.
本發明的著色感光性樹脂組合物,包括:著色劑(A)、黏合劑樹脂(B)、聚合性化合物(C)及聚合引發劑(D);黏合劑樹脂(B)係為包括具有以下結構單元的共聚物之黏合劑樹脂:來自甲基丙烯酸之結構單元、來自丙烯酸之結構單元、以及來自可跟甲基丙烯酸和丙烯酸共聚合的單體之結構單元。 The colored photosensitive resin composition of the present invention comprises a coloring agent (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D); and the binder resin (B) includes the following The binder resin of the copolymer of the structural unit: a structural unit derived from methacrylic acid, a structural unit derived from acrylic acid, and a structural unit derived from a monomer copolymerizable with methacrylic acid and acrylic acid.
本發明的著色感光性樹脂組合物,係含有著色劑(A)。以著色劑(A)而言,可舉例如:染料(A1)及顏料(A2),並以為含有染料(A1)的著色劑較佳。以染料(A1)而言,可舉例如:油溶性染料、酸性染料、酸性染料之胺(amine)鹽及酸性染料之磺胺(sulfonamide)衍生物等之染料,例如,色彩索引(Color Index,The Society of Dyers and Colourists出版)中所記載的染料,亦即分類在顏料(pigment)以外之具有色相的化合物,以及染色NOTE(色染社)所記載的公知染料。此外,若依據化學結構區分,可舉例如:偶氮(azo)染料、蒽醌(anthraquinone)染料、三苯甲烷染料、呫噸(xanthene)染料及酞菁(phthalocyanine)染料等。上述等之染料可以單獨使用,也可以將2種以上合併使用之。上述等物質之中,係以有機溶劑可溶性染料為較佳。 The colored photosensitive resin composition of the present invention contains a coloring agent (A). The coloring agent (A) may, for example, be a dye (A1) or a pigment (A2), and is preferably a coloring agent containing the dye (A1). The dye (A1) may, for example, be a dye such as an oil-soluble dye, an acid dye, an amine salt of an acid dye, or a sulfonamide derivative of an acid dye, for example, a color index (The Color Index, The The dyes described in the Society of Dyers and Colourists, that is, the compounds having a hue other than the pigment, and the known dyes described in the dyed NOTE. Further, depending on the chemical structure, for example, an azo dye, an anthraquinone dye, a triphenylmethane dye, a xanthene dye, a phthalocyanine dye, or the like can be given. The dyes of the above may be used singly or in combination of two or more. Among the above substances, an organic solvent-soluble dye is preferred.
具體而言,可舉例如下:C.I.溶劑黃(solvent yellow)4(以下省略C.I.溶劑黃的敘述,僅列出號碼)、 14、15、23、24、38、62、63、68、82、94、98、99、117、162、163、167、189;C.I.溶劑紅(solvent red)45、49、111、125、130、143、145、146、150、151、155、168、169、172、175、181、207、218、222、227、230;245、247;C.I.溶劑橙(solvent orange)2、7、11、15、26、56、77、86;C.I.溶劑紫(solvent violet)11、13、14、26、31、36、37、38、45、47、48、51、59、60;C.I.溶劑藍(solvent blue)4、5、14、18、35、36、37、45、58、59、59:1、63、67、68、69、70、78、79、83、90、94、97、98、100、101、102、104、105、111、112、122、128、132、136、139;C.I.溶劑綠(solvent green)1、3、4、5、7、28、29、32、33、34、35等之C.I.溶劑染料。 Specifically, it can be exemplified as follows: C.I. solvent yellow 4 (hereinafter, C.I. description of solvent yellow is omitted, only numbers are listed), 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; solvent violet violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue (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 so on CI solvent dye.
C.I.酸性黃(acid yellow)1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251;C.I.酸性紅(acid red)1、4、8、14、17、18、26、27、 29、31、34、35、37、42、44、50、51、52、57、66、73、76、80、87、88、91、92、94、95、97、98、103、111、114、129、133、134、138、143、145、150、151、158、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(acid orange)6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169、173;C.I.酸性紫(acid violet)6B、7、9、17、19、30、34、102;C.I.酸性藍(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;C.I.酸性綠(acid green)1、3、5、9、16、25、27、28、41、50、58、63、65、80、104、105、106、109等之 C.I.酸性染料。 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, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 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, 3, 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, 63, 65, 80, 104, 105, 106 , 109, etc. C.I. Acid dyes.
C.I.直接黃(direct yellow)2、33、34、35、38、39、43、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、136、138、141;C.I.直接紅(direct red)79、82、83、84、91、92、96、97、98、99、105、106、107、172、173、176、177、179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250;C.I.直接橙(direct orange)34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107;C.I.直接紫(direct violet)47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104;C.I.直接藍(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;C.I.直接綠(direct green)25、27、31、32、34、 37、63、65、66、67、68、69、72、77、79、82等之C.I.直接染料。 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 (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 34, 39 , 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct violet (direct 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 direct green 25, 27 , 31, 32, 34, C.I. Direct dyes of 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.
C.I.分散黃(disperse yellow)51、54、76;C.I.分散紫(disperse violet)26、27;C.I.分散藍(disperse blue)1、14、56、60;C.I.基本紅(basic red)1、10;C.I.基本藍(basic blue)1、3、5、7、9、19、21、22、24、25、26、28、29、40、41、45、47、54、58、59、60、64、65、66、67、68;C.I.基本綠(basic green)1;等之C.I.基本染料、C.I.活性黃(reactive yellow)2、76、116;C.I.活性橙(reactive orange)16;C.I.活性紅(reactive red)36;等之C.I.活性染料、C.I.酸性媒介黃(mordant yellow)5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65;C.I.酸性媒介紅(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;C.I.酸性媒介橙(mordant orange)3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48;C.I.酸性媒介紫(mordant violet)1、2、4、5、7、14、 22、24、30、31、32、37、40、41、44、45、47、48、53、58;C.I.酸性媒介藍(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;C.I.酸性媒介綠(mordant green)1、3、4、5、10、15、19、26、29、33、34、35、41、43、53等之C.I.酸性媒介染料、C.I.還原綠(vat green)1等之C.I.還原染料等等。 CI disperse yellow 51, 54, 76; CI disperse violet 26, 27; CI disperse blue 1, 14, 56, 60; CI basic red 1, 10; CI basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64 , 65, 66, 67, 68; CI basic green 1; etc. CI basic dye, CI reactive yellow 2, 76, 116; CI active orange 16; CI active red ( Reactive red) 36; etc. CI reactive dye, CI acid medium yellow (mordant yellow) 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 ; CI acid medium red (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 acid orange (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 acidity Medium purple (mordant violet) 1,2,4,5,7,14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI acid blue (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 acid medium green (mord green) 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. CI acid medium dye, CI reduction green ( Vat green) 1 etc. CI vat dyes and the like.
以染料(Al)而言,係以呫噸染料(Aa)為較佳。 In the case of the dye (Al), a xanthene dye (Aa) is preferred.
呫噸染料(Aa)係為含有具有呫噸骨幹之化合物的染料。 Xanthene dye (Aa) is a dye containing a compound having a xanthene backbone.
以呫噸染料(Aa)而言,可舉例如:C.I.酸性紅51、52、87、92、94、289、388;C.I.酸性紫9、30、102;C.I.基本紅1(若丹明6G,Rhodamin 6G)、2、3、4、8;C.I.基本紅10(若丹明B,Rhodamin B)、11;C.I.基本紫10、11、25;C.I.溶劑紅218;C.I.酸性媒介紅27;C.I.活性紅36(Rose Bengal B);磺醯若丹明G(Sulforhodamine);特開2010-32999號公報所揭露之呫噸染料及特許第4492760號所揭露之呫噸染料等。 The xanthene dye (Aa) may, for example, be CI Acid Red 51, 52, 87, 92, 94, 289, 388; CI Acid Violet 9, 30, 102; CI Basic Red 1 (Rhodamine 6G, Rhodamin 6G), 2, 3, 4, 8; CI basic red 10 (Rhodamin B), 11; CI basic purple 10, 11, 25; CI solvent red 218; CI acid medium red 27; CI activity Red Bengal B; Sulforhodamine; the xanthene dye disclosed in Japanese Laid-Open Patent Publication No. 2010-32999, and the xanthene dye disclosed in Japanese Patent No. 4492760.
以呫噸染料(Aa)而言,係以使用含有下式(1)中所表示的化合物(以下也稱為「化合物(1)」)的染料為較佳。化合物(1)也可為其互變異構體(tautomer)。使用化合物(1)時,相對於呫噸染料(Aa)的總量之化合物(1)的含有量係以 50質量%以上較佳、70質量%以上更佳、90質量%以上特佳。尤其是,以實質上僅使用化合物(1)來作為呫噸染料(Aa)較佳。 In the case of the xanthene dye (Aa), a dye containing a compound represented by the following formula (1) (hereinafter also referred to as "compound (1)") is preferred. Compound (1) can also be a tautomer thereof. When the compound (1) is used, the content of the compound (1) relative to the total amount of the xanthene dye (Aa) is 50% by mass or more is preferable, 70% by mass or more is more preferable, and 90% by mass or more is particularly preferable. In particular, it is preferred to use only the compound (1) as the xanthene dye (Aa).
R5係表示-OH、-SO3 -、-SO3H、-SO3 -M+、-CO2H、-CO2 -M+、-CO2R8、-SO3R8或-SO2NR9R10。 R 5 represents -OH, -SO 3 - , -SO 3 H, -SO 3 - M + , -CO 2 H, -CO 2 - M + , -CO 2 R 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 .
m係表示0~5的整數。當m為2以上時,複數的R5為相同或相異。 The m system represents an integer of 0 to 5. When m is 2 or more, the plural R 5 is the same or different.
R6及R7係分別獨立地表示氫原子或碳數1~6的烷基。 R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
M+係表示+N(R11)4、Na+或K+。 The M + system represents + N(R 11 ) 4 , Na + or K + .
X係表示鹵素原子。 X is a halogen atom.
a係表示0或1的整數。 a represents an integer of 0 or 1.
R8係表示碳數1~20的1價飽和烴基,該飽和烴基所含有的氫原子,也可以用鹵素原子來予以取代。 R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R11係分別獨立地表示氫原子、碳數1~20的1價飽和烴基或碳數7~10的芳烷基。 R 11 each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
R9及R10係分別獨立地表示氫原子、或碳數1~20的1價飽和烴基;該飽和烴基所含有的氫原子,也可以用羥基或鹵素原子來予以取代;該飽和脂肪族烴基所含有的-CH2-,也可以用-O-、-CO-、-NH-或-NR8-來予以取代;R9及R10亦可互相地結合而形成為含有氮原子的3~10圓環之複數環。] R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms; and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a hydroxyl group or a halogen atom; the saturated aliphatic hydrocarbon group The contained -CH 2 - may also be substituted with -O-, -CO-, -NH- or -NR 8 -; R 9 and R 10 may be bonded to each other to form a nitrogen atom-containing 3~ 10 rings of plural rings. ]
以R1~R4中碳數6~10的1價芳香族烴基而言,可舉例如:苯基、甲苯醯基(toluyl)、二甲苯基(xylyl)、三甲苯基(mesityl)、丙基苯基及丁基苯基等。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1 to R 4 include a phenyl group, a toluyl group, a xylyl group, a mesityl group, and a C group. Base phenyl and butyl phenyl and the like.
R1~R4中碳數6~10的1價芳香族烴基,以其取代基而言,係以具有擇自由-SO3 -、-SO3H、-SO3 -M+及-SO2NR9R10所構成的族群中至少1種者為較佳,並以具有擇自由-SO3 -M+及-SO2NR9R10所構成的族群中至少1種者為更佳。以此情形的-SO3 -M+而言,係以為-SO3 -+N(R11)4較佳。R1~R4若為上述等之官能基,則從含有化合物(1)的本發明之著色感光性樹脂組合物來看,可形成極少產生異物、且耐熱性優異的彩色濾光片。 The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1 to R 4 is selected from the group consisting of -SO 3 - , -SO 3 H, -SO 3 - M + and -SO 2 At least one of the groups consisting of NR 9 R 10 is preferable, and at least one of the groups consisting of -SO 3 - M + and -SO 2 NR 9 R 10 is more preferable. In the case of -SO 3 - M + in this case, it is preferred that -SO 3 -+ N(R 11 ) 4 is preferable. When R 1 to R 4 are the above-mentioned functional groups, it is possible to form a color filter which is less likely to generate foreign matter and is excellent in heat resistance from the colored photosensitive resin composition of the present invention containing the compound (1).
針對R1及R2同時形成之環、以及R3及R4同時形成之 環而言,可舉例如以下所列示者。 The ring formed simultaneously with R 1 and R 2 and the ring formed by R 3 and R 4 at the same time may, for example, be listed below.
以R1~R4、R8~R11中碳數1~20的1價飽和烴基而言,可舉例如:甲基、乙基、丙基、異丙基、丁基、異丁基、戊基、異戊基、新戊基、己基、庚基、辛基、2-乙基己基、壬基、癸基、十二烷基、十六烷基、二十烷基等之碳數1~20的烷基;環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等之碳數3~20的脂環式飽和烴基。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1 to R 4 and R 8 to R 11 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Carbon number of pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, decyl, dodecyl, hexadecyl, eicosyl, etc. An alkyl group of ~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.
以-OR8而言,可舉例如:甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、2-乙基己氧基及二十烷氧基等。 The -OR 8 may, for example, be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group or a 2-ethylhexyloxy group. And eicosyloxy and the like.
以-CO2R8而言,可舉例如:甲氧羰基、乙氧羰基、丙氧羰基、第3-丁氧羰基、己氧羰基及二十烷氧羰基等。 The -CO 2 R 8 may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a 3-butoxycarbonyl group, a hexyloxycarbonyl group or an eicosyloxycarbonyl group.
以-SR8而言,可舉例如:甲硫基(methylsulfanyl)、乙硫基、丁硫基、己硫基、癸硫基及二十烷硫基。 The -SR 8 may, for example, be a methylsulfanyl group, an ethylthio group, a butylthio group, a hexylthio group, a thiol group or an eicosylthio group.
以-SO2R8而言,可舉例如:甲磺醯基(methylsulfonyl)、乙磺醯基、丁磺醯基、己磺醯基、癸磺醯基及二十烷磺醯基。 Examples of the -SO 2 R 8 include a methylsulfonyl group, an ethylsulfonyl group, a butasulfonyl group, a hexylsulfonyl group, a sulfonyl group, and an eicosylsulfonyl group.
以-SO3R8而言,可舉例如:甲氧磺醯基(methoxysulfonyl)、乙氧磺醯基、丙氧磺醯基、第3-丁氧磺醯基、己氧磺醯基及二十烷氧磺醯基。 The -SO 3 R 8 may, for example, be methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, 3-butoxysulfonyl, hexyloxysulfonyl and Decaloxysulfonyl.
以-SO2NR9R10而言,可舉例如:氨磺醯基(sulfamoyl);N-甲基氨磺醯基、N-乙基氨磺醯基、N-丙基氨磺醯基、N- 異丙基氨磺醯基、N-丁基氨磺醯基、N-異丁基氨磺醯基、N-第2-丁基氨磺醯基、N-第3-丁基氨磺醯基、N-戊基氨磺醯基、N-(1-乙基丙基)氨磺醯基、N-(1,1-二甲基丙基)氨磺醯基、N-(1,2-二甲基丙基)氨磺醯基、N-(2,2-二甲基丙基)氨磺醯基、N-(1-甲基丁基)氨磺醯基、N-(2-甲基丁基)氨磺醯基、N-(3-甲基丁基)氨磺醯基、N-環戊基氨磺醯基、N-己基氨磺醯基、N-(1,3-二甲基丁基)氨磺醯基、N-(3,3-二甲基丁基)氨磺醯基、N-庚基氨磺醯基、N-(1-甲基己基)氨磺醯基、N-(1,4-二甲基戊基)氨磺醯基、N-辛基氨磺醯基、N-(2-乙基己基)氨磺醯基、N-(1,5-二甲基)己基氨磺醯基、N-(1,1,2,2-四甲基丁基)氨磺醯基等之N-1取代氨磺醯基;N,N-二甲基氨磺醯基、N,N-乙基甲基氨磺醯基、N,N-二乙基氨磺醯基、N,N-丙基甲基氨磺醯基、N,N-異丙基甲基氨磺醯基、N,N-第3-丁基甲基氨磺醯基、N,N-丁基乙基氨磺醯基、N,N-雙(1-甲基丙基)氨磺醯基、N,N-庚基甲基氨磺醯基等之N,N-2取代氨磺醯基等等。 The -SO 2 NR 9 R 10 may, for example, be sulfamoyl; N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-butyl-2-butylsulfonyl, N-tert 3-butylsulfonate Sulfhydryl, N-pentylsulfamoyl, N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-(1, 2-dimethylpropyl)sulfasulfonyl, N-(2,2-dimethylpropyl)sulfamoyl, N-(1-methylbutyl)sulfamoyl, N-(2 -Methylbutyl)Aminosulfonyl, N-(3-methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(1,3 - dimethyl butyl) amsulfoxonyl, N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfonyl, N-(1-methylhexyl)sulfonate Sulfhydryl, N-(1,4-dimethylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5 N-substituted sulfonamide of N-methyl)hexylsulfonyl, N-(1,1,2,2-tetramethylbutyl)sulfamoyl; N,N-dimethyl Amisulphol, N,N-ethylmethylsulfamoyl, N,N-diethylsulfonate N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N-3-butylmethylsulfamoyl, N,N-butyl N,N-2 substituted amisulphtyl, etc. of N,N-bis(1-methylpropyl)sulfamoyl, N,N-heptylmethylsulfamoyl, etc. .
又,關於R9及R10所表示的碳數1~20的1價飽和烴基,該飽和烴基所含有的氫原子,也可以用-OH或鹵素原子來予以取代;該飽和烴基所含有的-CH2-,也可以用-O-、-CO-、-NH-或-NR8-來予以取代。 In addition, as for the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 9 and R 10 , the hydrogen atom contained in the saturated hydrocarbon group may be substituted with -OH or a halogen atom; and the saturated hydrocarbon group may contain - CH 2 - may also be substituted with -O-, -CO-, -NH- or -NR 8 -.
R9及R10,也可以互相地結合而形成為含有氮原子的3~10圓環之複數環。以該複數環而言,可舉例如以下所列示者。 R 9 and R 10 may be bonded to each other to form a complex ring of 3 to 10 rings containing a nitrogen atom. The plural ring may be, for example, the following list.
R5係以為-CO2H、-CO2R8、-SO3 -、-SO3 -M+、-SO3H或SO2NHR9較佳,並以為-SO3 -、-SO3 -M+、-SO3H或SO2NHR9更佳。 R 5 is preferably -CO 2 H, -CO 2 R 8 , -SO 3 - , -SO 3 - M + , -SO 3 H or SO 2 NHR 9 and is considered to be -SO 3 - , -SO 3 - M + , -SO 3 H or SO 2 NHR 9 is more preferred.
m係以為1~4較佳,為1或2則更佳。 The m system is preferably 1 to 4, more preferably 1 or 2.
以R6及R7中碳數1~6的烷基而言,可舉例如:前述所列舉的烷基之中,碳數為1~6者。 The alkyl group having 1 to 6 carbon atoms in R 6 and R 7 may, for example, be a group having 1 to 6 carbon atoms among the alkyl groups listed above.
以R11中碳數7~10的芳烷基而言,可舉例如:苄基、苯乙基、苯丁基等。 The aralkyl group having 7 to 10 carbon atoms in R 11 may, for example, be a benzyl group, a phenethyl group or a phenylbutyl group.
M+係為+N(R11)4、Na+或K+,並以為+N(R11)4較佳。 The M + system is + N(R 11 ) 4 , Na + or K + , and is preferably + N(R 11 ) 4 .
以+N(R11)4而言,係以4個R11之中至少2個為碳數5~20的1價飽和烴基為較佳。又,4個R11的合計碳數係以為20~80較佳、20~60更佳。當化合物(1)中存在有+N(R11)4時,R11若為上述等之基,則從含有化合物(1)的本發明之著色感光性樹脂組合物來看,即可形成異物極少的彩色濾光片。 In the case of + N(R 11 ) 4 , it is preferred that at least two of the four R 11 be 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 + N(R 11 ) 4 is present in the compound (1), and R 11 is the above-mentioned group, the foreign color can be formed from the colored photosensitive resin composition of the present invention containing the compound (1). Very few color filters.
化合物(1)係以為下式(2)中所表示的化合物(以下也稱為「化合物(2)」)較佳,而以呫噸染料(Aa)而言,係以為含有化合物(2)的染料更佳。化合物(2)也可為其互變異構體。使用化合物(2)時,呫噸染料(Aa)中之化合物(2)的含有量係以50質量%以上較佳、70質量%以上更佳、90質量%以上特佳。尤其是,以單獨使用化合物(2)來作為呫噸染料(Aa)特佳。 The compound (1) is preferably a compound represented by the following formula (2) (hereinafter also referred to as "compound (2)"), and a xanthene dye (Aa) is a compound (2). The dye is better. Compound (2) can also be a tautomer thereof. When the compound (2) is used, the content of the compound (2) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more. In particular, it is particularly preferable to use the compound (2) alone as the xanthene dye (Aa).
Xa係表示鹵素原子。 X a represents a halogen atom.
a1係表示0或1的整數。 a 1 represents an integer of 0 or 1.
m1係表示0~5的整數。當m1為2以上的整數時,複數的R25為相同或相異。 M1 represents an integer from 0 to 5. When m1 is an integer of 2 or more, the plural R 25 is the same or different.
Ma+係表示+N(R27)4、Na+或K+。 M a+ represents + N(R 27 ) 4 , Na + or K + .
R25係表示-SO3 -、-SO3 -Ma+、-SO3H或SO2NHR26。 R 25 represents -SO 3 - , -SO 3 - M a+ , -SO 3 H or SO 2 NHR 26 .
R26係表示碳數1~20的1價飽和烴基。 R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R27係分別獨立地表示碳數1~20的1價飽和烴基或苄基。] R 27 each independently represents a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms. ]
以R21~R24中碳數6~10的1價芳香族烴基而言,可舉例如:跟R1~R4中芳香族烴基所列舉出之官能基相同者。 The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 21 to R 24 may be, for example, the same as those exemplified as the aromatic hydrocarbon group in R 1 to R 4 .
其中,以R21~R24的組合而言,較佳者為:R21及R23為氫原子,且R22及R24為碳數6~10的1價芳香族烴基;該芳香族烴基所含有的氫原子,也可以用-SO3 -、-SO3 -M+、-SO3H、-SO3R26或-SO2NHR26來予以取代。更佳者則為:R21及R23為氫原子,且R22及R24為碳數6~10的1價芳香族 烴基;該芳香族烴基所含有的氫原子,也可以用-SO3 -M+或-SO2NHR26來予以取代。R21~R24若為上述等之官能基,則從含有化合物(2)的本發明之著色感光性樹脂組合物來看,即可形成耐熱性優異的彩色濾光片。 In particular, in the combination of R 21 to R 24 , R 21 and R 23 are a hydrogen atom, and R 22 and R 24 are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; The hydrogen atom contained may be substituted with -SO 3 - , -SO 3 - M + , -SO 3 H, -SO 3 R 26 or -SO 2 NHR 26 . More preferably, R 21 and R 23 are 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 may also be -SO 3 - M + or -SO 2 NHR 26 to replace. When R 21 to R 24 are the above-mentioned functional groups, a color filter excellent in heat resistance can be formed from the colored photosensitive resin composition of the present invention containing the compound (2).
以R26及R27中碳數1~20的1價飽和烴基而言,可舉例如:跟R8~R11中飽和烴基所列舉出之官能基相同者。 The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 26 and R 27 may, for example, be the same as those exemplified as the saturated hydrocarbon group in R 8 to R 11 .
當R21~R24為-R26時,-R26係以分別獨立地為氫原子、甲基或乙基較佳。 When R 21 to R 24 are -R 26 , -R 26 is preferably independently a hydrogen atom, a methyl group or an ethyl group.
以-SO3R26及-SO2NHR26中之R26而言,係以為碳數3~20的分支鏈狀烷基較佳、碳數6~12的分支鏈狀烷基更佳、2-乙基己基則特佳。R26若為上述等之官能基,則從含有化合物(2)的著色感光性樹脂組合物來看,即可形成極少產生異物的彩色濾光片。 In -SO 3 R 26, and in the -SO 2 NHR 26 R 26, the line that branched chain alkyl group having 3 to 20 carbon atoms, preferably carbon atoms branched alkyl group having 6 to 12 more preferably, 2 - Ethylhexyl is particularly preferred. When R 26 is a functional group such as the above, a color filter in which foreign matter is rarely generated can be formed from the coloring photosensitive resin composition containing the compound (2).
Ma+係為+N(R27)4、Na+或K+,並以+N(R27)4為較佳。 M a+ is + N(R 27 ) 4 , Na + or K + , and preferably + N(R 27 ) 4 .
以+N(R27)4而言,係以4個R27之中至少2個為碳數5~20的1價飽和烴基為較佳。又,4個R27的合計碳數係以為20~80較佳、20~60更佳。當化合物(2)中存在有+N(R27)4時,R27若為上述等之官能基,則從含有化合物(2)的本發明之著色感光性樹脂組合物來看,即可形成極少產生異物的彩色濾光片。 In the case of + N(R 27 ) 4 , it is preferred that at least two of the four R 27 be 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 + N(R 27 ) 4 is present in the compound (2), if R 27 is a functional group such as the above, it can be formed from the colored photosensitive resin composition of the present invention containing the compound (2). A color filter that produces little foreign matter.
以化合物(1)而言,可舉例如:下述式(1-1)~式(1-30)所表示的化合物。另外,在下述式中,Ra係表示碳數1~20的1價飽和烴基,並以為碳數6~12的分支鏈狀烷基更佳、2-乙基己基則特佳。在上述等物質之中,又以C.I. 酸性紅289的磺胺化合物、C.I.酸性紅289的4級氨鹽、C.I.酸性紫102的磺胺化合物或C.I.酸性紫102的4級氨鹽為較佳。以上述種類的化合物而言,可舉例如:如式(1-1)~式(1-8)、式(1-11)或式(1-12)所表示的化合物等。 The compound (1) is, for example, a compound represented by the following formula (1-1) to formula (1-30). In the following formula, the Ra system represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and more preferably a branched chain alkyl group having 6 to 12 carbon atoms and a 2-ethylhexyl group. Among the above substances, C.I. A sulfonamide compound of acid red 289, a grade 4 ammonia salt of C.I. Acid Red 289, a sulfonamide compound of C.I. Acid Violet 102 or a grade 4 ammonia salt of C.I. Acid Violet 102 is preferred. The compound of the above-mentioned type may, for example, be a compound represented by the formula (1-1) to the formula (1-8), the formula (1-11) or the formula (1-12).
又,以呫噸染料(Aa)而言,係以為含有下式(3)中所表示的化合物(以下也稱為「化合物(3)」)的染料更佳。化合物(3)也可為其互變異構體。使用化合物(3)時,呫噸染料(Aa)中之化合物(3)的含有量係以50質量%以上較佳、70質量%以上更佳、90質量%以上特佳。 In addition, it is more preferable that the dye containing the compound represented by the following formula (3) (hereinafter also referred to as "compound (3)") is more preferable. Compound (3) can also be a tautomer thereof. When the compound (3) is used, the content of the compound (3) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more.
p及q係分別獨立地表示0~5的整數。當p為2以上時,複數的R33可互為相同者或不同者;當q為2以上時,複數的R34可互為相同者或不同者。 The p and q are each independently representing an integer from 0 to 5. When p is 2 or more, the plural R 33 may be the same or different from each other; when q is 2 or more, the plural R 34 may be the same or different from each other.
以R31及R32所表示的碳數1~10的烷基而言,可舉例如:甲基、乙基、丙基、丁基、異丙基、異丁基、第2-丁基、第3-丁基、己基、2-乙基己基、壬基、癸基等。以R33及R34所表示的碳數1~4的烷基而言,可舉例如:上述所列舉的烷基之中,碳數到4之官能基。 Examples of the alkyl group having 1 to 10 carbon atoms represented by R 31 and R 32 include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a 2-butyl group. Tertiary 3-butyl, hexyl, 2-ethylhexyl, decyl, decyl and the like. The alkyl group having 1 to 4 carbon atoms represented by R 33 and R 34 may, for example, be a functional group having a carbon number of 4 among the above-exemplified alkyl groups.
以R33及R34所表示的碳數1~4的烷硫基(alkyl sulfanyl)而言,可舉例如:甲硫基、乙硫基、丙硫基、丁硫基及異丙硫基。 Examples of the alkyl sulfanyl group having 1 to 4 carbon atoms represented by R 33 and R 34 include a methylthio group, an ethylthio group, a propylthio group, a butylthio group and an isopropylthio group.
以R33及R34所表示的碳數1~4的烷磺醯基(alkyl sulfonyl)而言,可舉例如:甲磺醯基、乙磺醯基、丙磺醯基、丁磺醯基及異丙磺醯基。 The alkyl sulfonyl having 1 to 4 carbon atoms represented by R 33 and R 34 may, for example, be a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group or a sulfonyl group. Isopropyl sulfonyl.
R31及R32係以分別獨立地為甲基、乙基、丙基或異丙基較佳。R33及R34則以為碳數1~4的烷基較佳,並以為甲基則更佳。 R 31 and R 32 are each independently a methyl group, an ethyl group, a propyl group or an isopropyl group. R 33 and R 34 are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
p及q係以分別獨立地為0~2的整數較佳,並以為1或2更佳。 Preferably, p and q are each independently an integer of 0 to 2, and more preferably 1 or 2.
以化合物(3)而言,可舉例如:如式(1-31)~式(1-43)所分別表示的化合物。其中,若以對有機溶劑的溶解性優良之觀點來看,係以式(1-31)~式(1-40)所表示的化合物為較佳。 The compound (3) may, for example, be a compound represented by the formula (1-31) to the formula (1-43), respectively. In particular, a compound represented by formula (1-31) to formula (1-40) is preferred from the viewpoint of excellent solubility in an organic solvent.
以呫噸染料(Aa)來說,也可以使用市售的呫噸染料(例如,中外化成(股份有限)製之「Chugai Aminol Fast Pink R-H/C」、田岡化學工業(股份有限)製之「Rhodamin 6G」等)。又,亦可利用市售的呫噸染料作為起始原料,而參考特開2010-32999號公報來進行合成。 For the xanthene dye (Aa), it is also possible to use a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Sino-foreign Chemical Co., Ltd., and "Tokyo Chemical Industry Co., Ltd." Rhodamin 6G", etc.). Further, a commercially available xanthene dye can be used as a starting material, and the synthesis can be carried out in accordance with JP-A-2010-32999.
著色劑(A)也可以含有顏料(A2)。 The colorant (A) may also contain a pigment (A2).
以顏料而言,並未特別予以限制,可使用公知的原料,如色彩索引(Color Index,The Society of Dyers and Colourists出版)中分類於顏料的化合物,可舉例如:C.I.顏料黃(pigment yellow)1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、194、214等之黃色顏料;C.I.顏料橙(pigment orange)13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等之橙色顏料; C.I.顏料紅(pigment red)9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265等之紅色顏料;C.I.顏料藍(pigment blue)15、15:3、15:4、15:6、60等之藍色顏料;C.I.顏料紫(pigment violet)1、19、23、29、32、36、38等之紫色顏料;C.I.顏料綠(pigment green)7、36、58等之綠色顏料;C.I.顏料棕(pigment yellow)23、25等之棕色顏料;C.I.顏料黑(pigment black)1、7等之黑色顏料等等。 The pigment is not particularly limited, and a known raw material such as a color index (Color Index, published by The Society of Dyers and Colourists) classified as a pigment may be used, and for example, CI pigment yellow (pigment yellow) 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, Yellow pigments of 148, 150, 153, 154, 166, 173, 194, 214, etc.; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64 , 65, 71, 73, etc. orange pigment; CI pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 Red pigment; CI pigment blue 15, 15:3, 15:4, 15:6, 60, etc. blue pigment; CI pigment violet 1, Pigeon violet 1, 19, 23, 29, 32, Purple pigment of 36, 38, etc.; green pigment of CI pigment green 7, 36, 58; CI pigment brown 23, 25, etc. brown pigment; CI pigment black 1, 7 Wait for black pigments and so on.
其中,係以使用以下顏料為較佳:C.I.顏料黃138、139、150;C.I.顏料紅177、209、242、254;C.I.顏料紫23;C.I.顏料藍15:3、15:6以及C.I.顏料綠7、36、58。以本發明的著色感光性樹脂組合物所使用的顏料而言,係以使用含有擇自由以下顏料所構成的族群中至少1種者的顏料為更佳:C.I.顏料藍15:6、C.I.顏料紅254、C.I.顏料紅242、C.I.顏料紅177、C.I.顏料綠58、C.I.顏料黃150以及C.I.顏料黃138。藉由含有上述的顏料,就可使得穿透光譜的最適化變得容易,耐藥品性也變得良好。 Among them, the following pigments are preferred: CI Pigment Yellow 138, 139, 150; CI Pigment Red 177, 209, 242, 254; CI Pigment Violet 23; CI Pigment Blue 15:3, 15:6 and CI Pigment Green 7, 36, 58. The pigment used in the colored photosensitive resin composition of the present invention is preferably a pigment containing at least one of the group consisting of the following pigments: CI Pigment Blue 15:6, CI Pigment Red 254, CI Pigment Red 242, CI Pigment Red 177, CI Pigment Green 58, CI Pigment Yellow 150, and CI Pigment Yellow 138. By containing the above-described pigment, the optimization of the breakthrough spectrum can be facilitated, and the chemical resistance can be improved.
上述等之顏料可以單獨使用,也可以將2種以上合併使用之。 The above-mentioned pigments may be used singly or in combination of two or more.
顏料在必要時也可以對應施予以下處理:松脂(rosin)處理、使用導入有酸性基或鹼性基的顏料衍生物等之表面 處理、利用高分子化合物等對顏料表面進行之接枝(graft)處理、利用硫酸微粒化法等之微粒化處理;或者是,用以去除雜質之使用有機溶劑及水等的洗淨處理、藉由離子交換法等去除離子性雜質之去除處理等等。 The pigment may be subjected to a corresponding treatment if necessary: rosin treatment, use of a pigment derivative into which an acidic group or a basic group is introduced, or the like The treatment, the graft treatment of the surface of the pigment by a polymer compound or the like, the micronization treatment by a sulfuric acid micronization method, or the like, or the washing treatment or the use of an organic solvent or water for removing impurities. The removal treatment of ionic impurities and the like are removed by an ion exchange method or the like.
顏料係以粒徑均勻者為較佳。藉由令其含有顏料分散劑來進行分散處理,就可得到顏料在溶液中呈現均勻地分散狀態之顏料分散液。 It is preferred that the pigment has a uniform particle size. By performing a dispersion treatment by containing a pigment dispersant, a pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained.
以上述的顏料分散劑而言,可舉例如:陽離子系、陰離子系、非離子系、雙性、聚酯系、聚胺系、丙烯系等之界面活性劑等等。上述等之顏料分散劑可以單獨使用,也可以將2種以上組合使用之。以顏料分散劑而言,可舉例如以下商品名:KP(信越化學工業(股份有限)製)、Floren(共榮社化學(股份有限)製)、Solspers(Zeneca(股份有限)製)、EFKA(CIBA公司製)、Ajisper(味之素Fine-Techno(股份有限)製)、Disperbyk(BYK化學公司製)等。 Examples of the pigment dispersant described above include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and propylene. The above-mentioned pigment dispersing agents may be used singly or in combination of two or more kinds. In the case of the pigment dispersant, for example, the following trade names: KP (Shin-Etsu Chemical Co., Ltd.), Floren (Kyoei Chemical Co., Ltd.), Solspers (Zeneca (limited stock)), EFKA (manufactured by CIBA Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), and the like.
當使用顏料分散劑時,其使用量係以相對於顏料(A2)100質量份而言,為100質量份以下較佳,並以為5質量份以上、50質量份以下更佳。顏料分散劑的使用量若在上述範圍內,就可得到均勻的分散狀態之顏料分散液。 When the pigment dispersant is used, the amount thereof is preferably 100 parts by mass or less based on 100 parts by mass of the pigment (A2), and more preferably 5 parts by mass or more and 50 parts by mass or less. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state can be obtained.
以著色劑(A)而言,係以同時含有染料(A1)及顏料(A2)兩者為較佳。此時,染料(A1)及顏料(A2)的含有量比率((A1):(A2))若以質量基準而言,係以1:99~99:1為較佳、3:97~90:10則更佳。藉由維持上述的比例,就可使 得穿透光譜的最適化變得容易,所得到的彩色濾光片也會在對比、明亮度、耐熱性、耐藥品性等方面具有優異的傾向。 In the case of the colorant (A), it is preferred to contain both the dye (A1) and the pigment (A2). In this case, the content ratio ((A1): (A2)) of the dye (A1) and the pigment (A2) is preferably 1:99 to 99:1 and 3:97 to 90 on a mass basis. :10 is even better. By maintaining the above ratio, The optimization of the breakthrough spectrum becomes easy, and the obtained color filter also has an excellent tendency in terms of contrast, brightness, heat resistance, chemical resistance, and the like.
特別是,當以本發明的著色感光性樹脂組合物作為藍色著色感光性樹脂組合物來進行調製時,以著色劑(A)而言,係以含有呫噸染料及藍色顏料的著色劑為較佳,並以含有呫噸染料及C.I.顏料藍15:6的著色劑為更佳。呫噸染料及藍色顏料的含有量比率若以質量基準而言,係以3:97~90:10為較佳、3:97~70:30更佳、3:97~50:50特佳、5:95~30:70則最佳。藉由令上述等之著色劑含有前述的含有量,就可得到高明亮度的藍色彩色濾光片。 In particular, when the colored photosensitive resin composition of the present invention is prepared as a blue colored photosensitive resin composition, the coloring agent (A) is a coloring agent containing a xanthene dye and a blue pigment. Preferably, a coloring agent containing xanthene dye and CI Pigment Blue 15:6 is more preferred. The ratio of the content of xanthene dye and blue pigment is preferably 3:97 to 90:10, more preferably 3:97 to 70:30, and 3:97 to 50:50. 5:95~30:70 is the best. By making the above-mentioned coloring agent contain the above-described content, a blue color filter of high brightness can be obtained.
著色劑(A)的含有量係相對於著色感光性樹脂組合物中的固形成份而言,以5~60質量%較佳、8~55質量%更佳、10~50質量%特佳、12~30質量%則最佳。著色劑(A)的含有量若落在前述範圍內,就可以得到作為彩色濾光片時所期望之分光及色濃度,並且可藉由在組合物中加入必要量的黏合劑樹脂及聚合性化合物,就可形成機械性強度非常充份的彩色濾光片。在此處所述及的固形成份,係指本發明的著色感光性樹脂組合物中除去溶劑以外之成份的合計量。針對固形成份及該固形成份中之各成份的含有量,可使用例如:液體層析法或氣體層析法等之公知的分析手段來進行測定。 The content of the coloring agent (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, even more preferably from 10 to 50% by mass, based on the solid content of the colored photosensitive resin composition. ~30% by mass is the best. When the content of the colorant (A) falls within the above range, the desired spectral and color concentration can be obtained as a color filter, and a necessary amount of binder resin and polymerizability can be added to the composition. The compound can form a color filter having a very strong mechanical strength. The solid content described herein means the total amount of components other than the solvent in the colored photosensitive resin composition of the present invention. The content of each component in the solid component and the solid component can be measured using a known analytical means such as liquid chromatography or gas chromatography.
本發明的著色感光性樹脂組合物係包括黏合劑樹脂(B),黏合劑樹脂(B)係為包括具有以下結構單元的共聚物 (B1)(以下也稱為共聚物(B1))之黏合劑樹脂:來自甲基丙烯酸之結構單元、來自丙烯酸之結構單元、以及來自可跟甲基丙烯酸和丙烯酸共聚合的單體(x)(以下稱為「單體(x)」)之結構單元。 The colored photosensitive resin composition of the present invention comprises a binder resin (B), and the binder resin (B) is a copolymer comprising the following structural unit. (B1) (hereinafter also referred to as copolymer (B1)) binder resin: structural unit derived from methacrylic acid, structural unit derived from acrylic acid, and monomer (3) derived from copolymerizable with methacrylic acid and acrylic acid (hereinafter referred to as "monomer (x)") structural unit.
以單體(x)而言,除了可跟甲基丙烯酸及丙烯酸進行共聚合,且為跟甲基丙烯酸及丙烯酸不相同的單體外,並未特別予以限制,可舉例如:(a)具有碳數2~4的環狀醚結構之不飽和化合物(以下也稱為「(a)」);(b)擇自由不飽和羧酸及不飽和羧酸酐所構成的族群中至少1種者(但是跟丙烯酸及甲基丙烯酸不相同)(以下也稱為「(b)」);(c)其他可共聚合的單體(但是跟丙烯酸、甲基丙烯酸、(a)及(b)不同)(以下也稱為「(c)」)。 The monomer (x) is not particularly limited as long as it can be copolymerized with methacrylic acid and acrylic acid, and is not the same as methacrylic acid and acrylic acid, and for example, (a) has An unsaturated compound having a cyclic ether structure of 2 to 4 carbon atoms (hereinafter also referred to as "(a)"); (b) at least one selected from the group consisting of a free unsaturated carboxylic acid and an unsaturated carboxylic anhydride ( However, it is different from acrylic acid and methacrylic acid) (hereinafter also referred to as "(b)"); (c) other copolymerizable monomers (but different from acrylic acid, methacrylic acid, (a) and (b)) (hereinafter also referred to as "(c)").
以(a)所具有的碳數2~4的環狀醚結構而言,可舉例如:環氧乙烷(oxirane)環、氧雜環丁烷(oxetane)環及四氫呋喃(tetrahydrofuran)環。就(a)來說,係以為具有碳數2~4的環狀醚結構及(甲基)丙烯醯氧基之單體較佳。 The cyclic ether structure having 2 to 4 carbon atoms which is contained in (a) may, for example, be an oxirane ring, an oxetane ring or a tetrahydrofuran ring. In the case of (a), a monomer having a cyclic ether structure of 2 to 4 carbon atoms and a (meth)acryloxy group is preferred.
另外,在本說明書中,「(甲基)丙烯酸」係表示擇自由丙烯酸及甲基丙烯酸所構成的族群中至少1種者。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等之表述方式,也代表同樣的意義。 In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions of "(meth)acrylonitrile" and "(meth)acrylate" also mean the same meaning.
以(a)而言,可舉例如:具有環氧乙烷基及乙烯性不飽和鍵結之單體(a1)(以下也稱為「(a1)」)、具有氧雜環丁 烷基及乙烯性不飽和鍵結之單體(a2)(以下也稱為「(a2)」)、具有四氫糠基(Tetrahydrofurfuryl)及乙烯性不飽和鍵結之單體(a3)(以下也稱為「(a3)」)等。 (a), for example, a monomer (a1) having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter also referred to as "(a1)"), having an oxetane Alkyl group and ethylenically unsaturated bonded monomer (a2) (hereinafter also referred to as "(a2)"), tetrahydroindenyl (Tetrahydrofurfuryl) and ethylenically unsaturated bonded monomer (a3) (below) Also known as "(a3)").
(a1)可舉例如:具有環氧化結構的直鏈狀或分支鏈狀脂肪族不飽和烴及乙烯性不飽和鍵結結構之單體(a1-1)(以下也稱為「(a1-1)」),以及具有環氧化結構的脂環式不飽和烴及乙烯性不飽和鍵結之單體(a1-2)(以下也稱為「(a1-2)」)。 (a1), for example, a linear or branched aliphatic hydrocarbon having an epoxidized structure and a monomer (a1-1) having an ethylenically unsaturated bonding structure (hereinafter also referred to as "(a1-1) ))), and an alicyclic unsaturated hydrocarbon having an epoxidized structure and an ethylenically unsaturated bonded monomer (a1-2) (hereinafter also referred to as "(a1-2)").
以(a1-1)而言,可舉例如:(甲基)丙烯酸環氧丙酯、β-甲基(甲基)丙烯酸環氧丙酯、β-乙基(甲基)丙烯酸環氧丙酯、環氧丙基乙烯醚、鄰-乙烯基苄基環氧丙醚、間-乙烯基苄基環氧丙醚、對-乙烯基苄基環氧丙醚、α-甲基-鄰-乙烯基苄基環氧丙醚、α-甲基-間-乙烯基苄基環氧丙醚、α-甲基-對-乙烯基苄基環氧丙醚、2,3-雙(環氧丙基氧甲基)苯乙烯、2,4-雙(環氧丙基氧甲基)苯乙烯、2,5-雙(環氧丙基氧甲基)苯乙烯、2,6-雙(環氧丙基氧甲基)苯乙烯、2,3,4-三(環氧丙基氧甲基)苯乙烯、2,3,5-三(環氧丙基氧甲基)苯乙烯、2,3,6-三(環氧丙基氧甲基)苯乙烯、3,4,5-三(環氧丙基氧甲基)苯乙烯、2,4,6-三(環氧丙基氧甲基)苯乙烯等。 In terms of (a1-1), for example, glycidyl (meth)acrylate, glycidyl β-methyl(meth)acrylate, and glycidyl β-ethyl(meth)acrylate , epoxidized propyl vinyl ether, o-vinylbenzyl epoxidized propyl ether, m-vinylbenzyl epoxidized propyl ether, p-vinylbenzyl epoxidized propyl ether, α-methyl-o-vinyl Benzyl epoxidized ether, α-methyl-m-vinylbenzyl epoxidized propyl ether, α-methyl-p-vinylbenzyl epoxidized propyl ether, 2,3-bis(epoxypropyloxy) Methyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(epoxypropyl) Oxymethyl)styrene, 2,3,4-tris(epoxypropyloxymethyl)styrene, 2,3,5-tris(epoxypropyloxymethyl)styrene, 2,3,6 -Tris(epoxypropyloxymethyl)styrene, 3,4,5-tris(epoxypropyloxymethyl)styrene, 2,4,6-tris(epoxypropyloxymethyl)benzene Ethylene and the like.
以(a1-2)而言,可舉例如:乙烯基環己烯單氧化物、1,2-環氧基-4-乙烯基環己烷(例如:CEL oxide 2000,Daicel化學工業(股份有限)製)、3,4-環氧基環己基(甲基)丙烯酸甲酯(例如:Cyclomer A400,Daicel化學工業(股 份有限)製)、3,4-環氧基環己基(甲基)丙烯酸甲酯(例如:Cyclomer M100,Daicel化學工業(股份有限)製)、下列式(I)所表示的化合物及式(II)所表示的化合物等。 In the case of (a1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example: CEL oxide 2000, Daicel Chemical Industry (limited shares) )), 3,4-epoxycyclohexyl (meth) acrylate methyl ester (for example: Cyclomer A400, Daicel Chemical Industry Co., Ltd. a limited amount), 3,4-epoxycyclohexyl (meth) acrylate (for example: Cyclomer M100, manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the following formula (I) and a formula ( II) Compounds and the like represented.
X1及X2係分別獨立地表示單鍵結、-RC-、*-RC-O-、*-RC-S-、*-RC-NH-。 X 1 and X 2 each independently represent a single bond, -R C -, *-R C -O-, *-R C -S-, *-R C -NH-.
RC係表示碳數1~6的亞烷基(alkanediyl)。 R C represents an alkanediyl group having 1 to 6 carbon atoms.
*係表示跟氧原子之結合鍵。] * indicates a bond with an oxygen atom. ]
以碳數1~4的烷基而言,可舉例如:甲基、乙基、正丙基、異丙基、正丁基、第2-丁基、第3-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, an n-butyl group, a 2-butyl group, and a 3-butyl group.
以將氫原子用羥基取代的烷基而言,可舉例如:羥甲基、1-羥乙基、2-羥乙基、1-羥丙基、2-羥丙基、3-羥丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥丁基、2-羥丁基、3-羥丁基、4-羥丁基等。 The alkyl group substituted with a hydroxyl group in a hydrogen atom may, for example, be a methylol group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group or a 3-hydroxypropyl group. , 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.
以Ra及Rb而言,較佳者為:氫原子、甲基、羥甲基、1-羥乙基、2-羥乙基等;更佳者為:氫原子、甲基。 R a and R b are preferably a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group or a 2-hydroxyethyl group; more preferably a hydrogen atom or a methyl group.
以亞烷基而言,可舉例如:亞甲基、亞乙基、亞丙-1,2-基、亞丙-1,3-基、亞丁-1,4-基、亞戊-1,5-基、亞己-1,6-基等。 Examples of the alkylene group include a methylene group, an ethylene group, a propylene-1,2-yl group, a propylene-1,3- group, a butylene-1,4-yl group, and a penta-1. 5-based, hexylene-1,6-yl and the like.
以X1及X2而言,較佳者為:單鍵結、亞甲基、亞乙基、*-CH2-O-(*係表示跟氧原子之結合鍵)基、*-CH2CH2-O-基;更佳者為:單鍵結、*-CH2CH2-O-基。 In the case of X 1 and X 2 , preferred are: single bond, methylene, ethylene, *-CH 2 -O- (* is a bond to an oxygen atom), *-CH 2 More preferably, CH 2 -O- group; single bond, *-CH 2 CH 2 -O- group.
以式(I)所表示的化合物而言,可舉例如:以下式(I-1)~式(I-15)所表示的化合物等。其中較佳者為:式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)或式(I-11)~式(I-15)所表示的化合物。更佳者為:式(I-1)、式(I-7)、式(I-9)或式(I-15)所表示的化合物。 The compound represented by the formula (I) may, for example, be a compound represented by the following formula (I-1) to formula (I-15). Preferred among them are: formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11)~ I-15) The compound represented. More preferably, it is a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).
以式(II)所表示的化合物而言,可舉例如:以下式 (II-1)~式(II-15)所表示的化合物等。其中較佳者為:式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)或式(II-11)~式(II-15)所表示的化合物。更佳者為:式(II-1)、式(II-7)、式(II-9)或式(II-15)所表示的化合物。 The compound represented by the formula (II) may, for example, be: (II-1)~ A compound represented by the formula (II-15). Preferred among them are: formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)~ Compounds represented by II-15). More preferably, it is a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).
上述式(I)所表示的化合物及式(II)所表示的化合物,可分別單獨使用之。此外,上述等化合物也可以任意的比率混合使用之。當混合使用時,其混合比例若以莫耳比而言,係以式(I):式(II)為5:95~95:5較佳、10:90~90:10更佳、20:80~80:20則特佳。 The compound represented by the above formula (I) and the compound represented by the formula (II) can be used singly. Further, the above compounds may be used in combination at any ratio. When mixed, the mixing ratio is in the formula (I): formula (II) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, 20: 80~80:20 is especially good.
以具有氧雜環丁烷基及乙烯性不飽和鍵結之單體(a2)而言,係以為具有氧雜環丁烷基及(甲基)丙烯醯氧基之單體較佳。以(a2)而言,可舉例如:3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-丙烯醯氧基乙基氧雜環丁烷等。 The monomer (a2) having an oxetane group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloxy group. In the case of (a2), for example, 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane , 3-ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methyl Propylene oxiranyloxyoxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane Alkane, 3-ethyl-3-propenyloxyethyloxetane, and the like.
以具有四氫糠基及乙烯性不飽和鍵結之單體(a3)而言,係以為具有四氫糠基及(甲基)丙烯醯氧基之單體較佳。 The monomer (a3) having a tetrahydroindenyl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydroindenyl group and a (meth)acryloxy group.
以(a3)而言,具體來說可舉例如:丙烯酸四氫糠酯(例如:Viscoat V # 150,大阪有機化學工業(股份有限)製)、甲基丙烯酸四氫糠酯等。 Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
就(a)來說,若從可更進一步地提高所得到的彩色濾光片之耐熱性、耐藥品性等信賴度的觀點來看,係以(a1)為較佳。更進一步,若從讓著色感光性樹脂組合物之保存穩定性變優異的觀點來看,則以(a1-2)為更佳。 In (a), (a1) is preferable from the viewpoint of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, from the viewpoint of improving the storage stability of the colored photosensitive resin composition, (a1-2) is more preferable.
以(b)而言,具體來說可舉例如:丁烯酸、鄰-、間-、對-乙烯基苯甲酸等之不飽和一元羧酸類;馬來酸(maleic acid)、富馬酸(fumaric acid)、檸康酸(citraconic acid)、中康酸(mesaconic acid)、衣康酸(itaconic acid)、3-乙烯酞酸(3-vinyl phthalic acid)、4-乙烯酞酸(4-vinyl phthalic acid)、3,4,5,6-四氫酞 酸、1,2,3,6-四氫酞酸、二甲基四氫酞酸、1,4-環己烷二羧酸等之不飽和二羧酸類;甲基-5-原菠烷-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-烯等之含有羧基的雙環不飽和化合物類;馬來酸酐、檸康酸酐、衣康酸酐、3-乙烯酞酸酐、4-乙烯酞酸酐、3,4,5,6-四氫酞酸酐、1,2,3,6-四氫酞酸酐、二甲基四氫酞酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯酸酐等之不飽和二羧酸酐類;琥珀酸單[2-[(2-(甲基)丙烯醯基)氧]乙基]酯(mono-2-((meth)acryloyloxy)ethyl succinate)、1,2-環己烷二甲酸單[2[(2-(甲基)-1-氧代-2-丙烯醯)氧基]乙基]酯(2-((meth)acryloyloxy)ethyl hexahydrophthalate)等之2價以上的多價羧酸之不飽和單[[(2-甲基丙烯醯基)氧]烷基]酯類;如同α-(羥甲基)丙烯酸般,於同一分子中含有羥基及羧基的不飽和丙烯酸酯類等等。 Specific examples of (b) include unsaturated monocarboxylic acids such as crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid; fumaric acid (maleic acid); Fumaric acid), citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid (4-vinyl) Phthalic acid), 3,4,5,6-tetrahydroanthracene An unsaturated dicarboxylic acid such as acid, 1,2,3,6-tetrahydrofurfuric acid, dimethyltetrahydrofurfuric acid or 1,4-cyclohexanedicarboxylic acid; methyl-5-protopane- 2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene a carboxyl group-containing bicyclic unsaturated compound such as 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4 -vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1 An unsaturated dicarboxylic anhydride such as hept-2-ene anhydride; succinic acid mono [2-[(2-(methyl)propenyl)oxy]ethyl]ester (mono-2-((meth)acryloyloxy) )ethyl succinate), 1,2-cyclohexanedicarboxylic acid mono[2[(2-(methyl)-1-oxo-2-propenyl)oxy]ethyl]ester (2-((meth)) Acrylyloxyethyl)ethyl hexahydrophthalate) an unsaturated mono[[(2-methylpropenyl)oxy]alkyl] ester of a polyvalent carboxylic acid having a valence of 2 or more; like α-(hydroxymethyl) Acrylic, unsaturated acrylates having a hydroxyl group and a carboxyl group in the same molecule, and the like.
就(c)來說,可舉例如:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第2丁酯、(甲基)丙烯酸第3丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸月桂酯、(甲基)丙 烯酸十八醯酯、(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-酯(在該技術領域中被稱呼的慣用名為:(甲基)丙烯酸二環戊酯)、(甲基)丙烯酸二環戊氧乙酯、(甲基)丙烯酸三環[5.2.1.02,6]癸-8-酯(在該技術領域中被稱呼的慣用名為:(甲基)丙烯酸二環戊酯)、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等之(甲基)丙烯酸酯類;(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯等之含有羥基的(甲基)丙烯酸酯類;馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等之二羧酸二酯;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(羥甲基)雙環[2.2.1]庚-2-烯、5,6-二(2’-羥乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[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-羥甲基-5-甲基雙環[2. 2.1]庚-2-烯、5-第3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3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-烯等之雙環不飽和化合物類;N-苯基馬來酸酐縮亞胺(N-phenyl maleimide)、N-環己基馬來酸酐縮亞胺、N-苄基馬來酸酐縮亞胺、N-琥珀醯亞胺基-3-馬來酸酐縮亞胺苯甲酸酯(N-succinimidyl-3-maleimidebenzoate)、N-琥珀醯亞胺基-4-馬來酸酐縮亞胺丁酯、N-琥珀醯亞胺基-6-馬來酸酐縮亞胺己酸酯、N-琥珀醯亞胺基-3-馬來酸酐縮亞胺丙酯、N-(9-吖啶基)馬來酸酐縮亞胺(N-(9-acridinyl)maleimide)等之二羰基醯亞胺衍生物類;苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、乙烯基甲苯、對-甲氧基苯乙烯、丙烯腈(acrylonitrile)、甲基丙烯腈、氯乙烯、偏氯乙烯(vinylidene chloride)、丙烯醯胺(acrylamide)、甲基丙烯醯胺、乙酸乙烯(vinyl acetate)、1,3-丁二烯、異戊二烯(isoprene)、2,3-二甲基-1,3-丁二烯等。 (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, dibutyl (meth)acrylate, (methyl) 3rd butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, (methyl) Cyclopentyl acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] 癸-8-ester (in this The conventional name referred to in the technical field is: dicyclopentyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate, tricyclo(methyl)acrylate [5.2.1.0 2,6 ]癸- 8-ester (common name referred to in the art: dicyclopentanyl (meth)acrylate), isobornyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid (meth) acrylates such as allyl ester, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate; (methyl) Hydroxy-containing (2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, etc. Acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate; 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]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5 -ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1] Hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene , 5,6-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-tert-butoxycarbonylbicyclo[2.2.1]hept-2 - alkene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis (3rd butoxy Bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-benzene N-phenyl maleimide, N-cyclohexyl maleic anhydride imide, N-benzyl maleic anhydride imide, N-ammonium imino-3- maleic anhydride N-succinimidyl-3-maleimidebenzoate, N-succinimide-4-maleic acid butylimide, N-succinimide-6-maleic anhydride Aminohexanoate, N-succinimide-3-maleic anhydride propylimide, N-(9-acridinyl)maleimide, N-(9-acridinyl)maleimide, etc. Dicarbonyl quinone imine derivatives; styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile ), methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene (isoprene), 2,3-dimethyl-1,3-butadiene, and the like.
上述等物質之中,若從共聚合反應性及耐熱性觀點來看,係以下列者為較佳:苯乙烯、乙烯基甲苯、N-苯基馬來酸酐縮亞胺、N-環己基馬來酸酐縮亞胺、N-苄基馬來酸酐縮亞胺、雙環[2.2.1]庚-2-烯等。 Among the above-mentioned substances, from the viewpoints of copolymerization reactivity and heat resistance, the following are preferred: styrene, vinyl toluene, N-phenylmaleic anhydride, imine, N-cyclohexyl Anhydrous imide, N-benzyl maleic anhydride, bicyclo[2.2.1]hept-2-ene, and the like.
以共聚物(B1)而言,若從所得到的彩色濾光片之明亮 度的觀點來看,係以含有:來自甲基丙烯酸之結構單元、來自丙烯酸之結構單元、以及(a)的共聚物為較佳。 In the case of the copolymer (B1), if the color filter obtained is bright From the viewpoint of the degree, it is preferred to contain a structural unit derived from methacrylic acid, a structural unit derived from acrylic acid, and a copolymer (a).
在共聚物(B1)中,來自甲基丙烯酸之結構單元、來自丙烯酸之結構單元、以及來單體(x)之結構單元的比率,其於構成共聚物(B1)的全結構單元中之佔有比率,係以分別在以下的範圍內較佳:來自甲基丙烯酸之結構單元:1~54莫耳%(更佳為1~45莫耳%);來自丙烯酸之結構單元:1~54莫耳%(更佳為1~45莫耳%);來自單體(x)之結構單元:55~98莫耳%(更佳為60~90莫耳%)。 In the copolymer (B1), the ratio of the structural unit derived from methacrylic acid, the structural unit derived from acrylic acid, and the structural unit derived from the monomer (x), which is possessed in the entire structural unit constituting the copolymer (B1) The ratio is preferably in the following ranges: structural unit derived from methacrylic acid: 1 to 54 mol% (more preferably 1 to 45 mol%); structural unit derived from acrylic acid: 1 to 54 mol % (more preferably 1 to 45 mol%); structural unit derived from monomer (x): 55 to 98 mol% (more preferably 60 to 90 mol%).
更進一步,來自甲基丙烯酸之結構單元及來自丙烯酸之結構單元的合計量,係以在構成共聚物(B1)的全結構單元中,為2~55莫耳%較佳、15~50莫耳%更佳。 Further, the total amount of the structural unit derived from methacrylic acid and the structural unit derived from acrylic acid is 2 to 55 mol%, preferably 15 to 50 mol, in the entire structural unit constituting the copolymer (B1). % is better.
共聚物(B1)之結構單元的比率,若位於上述的範圍內,則著色感光性樹脂組合物的保存穩定性、顯影性及彩色濾光片的耐溶劑性就會有變良好的傾向。 When the ratio of the structural unit of the copolymer (B1) is within the above range, the storage stability and developability of the colored photosensitive resin composition and the solvent resistance of the color filter tend to be improved.
共聚物(B1)可參考例如:文獻「高分子合成的實驗法」(大津隆行著,發行所(股份有限)化學同人,第1版第1刷,1972年3月1日發行)所記載的方法及該文獻所揭露的引用文獻等來施行製造。 For the copolymer (B1), for example, the document "Experimental method for polymer synthesis" (produced by Otsuka, the Institute of Chemicals, Ltd., the first edition of the first brush, issued on March 1, 1972) The method and the cited documents disclosed in the literature are used for manufacturing.
具體而言,係將甲基丙烯酸或丙烯酸及單體(x)之既定量、聚合引發劑及溶劑等放入反應容器中,再以例如:藉 由通入氮氣來取代氧氣,以形成脫氧氛圍,再一邊攪拌、一邊加熱及保溫之方法。另外,在此處所使用的聚合引發劑及溶劑等,並未特別予以限定,也可使用於該領域中的任何通用物質。例如,以聚合引發劑而言,可舉例如: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)及有機過氧化物(過氧化苯醯等);以溶劑而言,凡可溶解各單體的溶劑皆可使用,也可使用後述之作為本發明的著色感光性樹脂組合物的溶劑(E)之溶劑等。 Specifically, a predetermined amount of methacrylic acid or acrylic acid and a monomer (x), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and for example, The method of replacing oxygen with nitrogen gas to form a deoxidizing atmosphere, and heating and holding while stirring. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and can be used in any general-purpose substance in the field. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.). And an organic peroxide (benzoquinone benzoate or the like); in the solvent, any solvent which can dissolve each monomer can be used, and a solvent (E) which is a coloring photosensitive resin composition of the present invention described later can also be used. Solvents, etc.
另外,所得到的共聚物,可將反應後的溶液直接拿來使用,也可使用濃縮或稀釋後的溶液,或利用再沈澱等方法將其作成固體(粉體)再取出使用之。尤其是,藉由使用本發明的著色感光性樹脂組合物所包含的溶劑來作為進行聚合之際的溶劑,就可將反應後的溶液直接拿來用於調製本發明的著色感光性樹脂組合物,故可將本發明的著色感光性樹脂組合物之製造步驟予以簡略化。 Further, the obtained copolymer may be used as it is, or may be used as a solid (powder) by a concentrated or diluted solution or by reprecipitation or the like. In particular, by using the solvent contained in the colored photosensitive resin composition of the present invention as a solvent for polymerization, the solution after the reaction can be directly used for preparing the colored photosensitive resin composition of the present invention. Therefore, the manufacturing steps of the colored photosensitive resin composition of the present invention can be simplified.
共聚物(B1),也可以含有下式(III)所表示的結構單元及/或式(IV)所表示的結構單元來作為來自單體(x)之結構單元。 The copolymer (B1) may contain a structural unit represented by the following formula (III) and/or a structural unit represented by the formula (IV) as a structural unit derived from the monomer (x).
以Re及Rg中之碳數1~6的烷基而言,可舉例如:甲基、乙基、丙基、丁基、戊基、己基等。以Re及Rg而言,係以為氫原子或甲基較佳。 The alkyl group having 1 to 6 carbon atoms in R e and R g may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. In terms of R e and R g , a hydrogen atom or a methyl group is preferred.
例如,當共聚物(B1)為含有式(III)所表示的結構單元時,利用跟上述相同的方法來得到甲基丙烯酸均聚物或甲基丙烯酸跟單體(x)之共聚物,就可以藉由把式(IIIa)所表示的化合物加成於來自甲基丙烯酸之羧基上,而得到含有式(III)所表示的結構單元之共聚物(B1)。 For example, when the copolymer (B1) is a structural unit represented by the formula (III), a homopolymer of methacrylic acid or a copolymer of methacrylic acid and a monomer (x) is obtained by the same method as described above. The copolymer (B1) containing the structural unit represented by the formula (III) can be obtained by adding a compound represented by the formula (IIIa) to a carboxyl group derived from methacrylic acid.
又,當共聚物(B1)為含有式(IV)所表示的結構單元時,利用跟上述相同的方法來得到甲基丙烯酸均聚物或甲基丙烯酸跟單體(x)之共聚物,就可以藉由把式(IVa)所表示的化合物加成於來自甲基丙烯酸之羧基上,而得到含有式(III)所表示的結構單元的共聚物(B1)。 Further, when the copolymer (B1) is a structural unit represented by the formula (IV), a homopolymer of methacrylic acid or a copolymer of methacrylic acid and monomer (x) is obtained by the same method as above. The copolymer (B1) containing the structural unit represented by the formula (III) can be obtained by adding a compound represented by the formula (IVa) to a carboxyl group derived from methacrylic acid.
即使當共聚物(B1)係含有以式(III)所表示的結構單元及/或式(IV)所表示的結構單元來作為來自單體(x)之結構單元時,來自各個結構單元的比率係以在上述的範圍內較佳。 Even when the copolymer (B1) contains a structural unit represented by the formula (III) and/or a structural unit represented by the formula (IV) as a structural unit derived from the monomer (x), the ratio from each structural unit It is preferred to be within the above range.
當共聚物(B1)為含有式(III)所表示的結構單元及/或式(IV)所表示的結構單元時,上述等之結構單元的比率, 係在構成共聚物(B1)的全結構單元中,以5~80莫耳%較佳、15~70莫耳更佳。 When the copolymer (B1) is a structural unit represented by the formula (III) and/or a structural unit represented by the formula (IV), the ratio of the above structural unit, It is preferably from 5 to 80 mol%, more preferably from 15 to 70 mols, in the total structural unit constituting the copolymer (B1).
式(III)所表示的結構單元及/或式(IV)所表示的結構單元之含有比率若在上述的範圍內,則著色感光性樹脂組合物的保存穩定性、顯影性及靈敏度,以及彩色濾光片的耐溶劑性、耐熱性及機械性強度的平衡就會有變良好的傾向。 When the content ratio of the structural unit represented by the formula (III) and/or the structural unit represented by the formula (IV) is within the above range, storage stability, developability, sensitivity, and color of the colored photosensitive resin composition The balance of the solvent resistance, heat resistance, and mechanical strength of the filter tends to be good.
以共聚物(B1)而言,具體來說,可舉例如:(甲基)丙烯酸3,4-環氧基環己基甲酯/甲基丙烯酸/丙烯酸共聚物、丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/甲基丙烯酸/丙烯酸共聚物、(甲基)丙烯酸環氧丙酯/(甲基)丙烯酸苄酯/甲基丙烯酸/丙烯酸共聚物、(甲基)丙烯酸環氧丙酯/苯乙烯/甲基丙烯酸/丙烯酸共聚物、丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/N-環己基馬來酸酐縮亞胺/甲基丙烯酸/丙烯酸共聚物、3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷/苯乙烯/甲基丙烯酸/丙烯酸共聚物、(甲基)丙烯酸苄酯/甲基丙烯酸/丙烯酸共聚物、苯乙烯/甲基丙烯酸/丙烯酸共聚物、令(甲基)丙烯酸環氧丙酯跟(甲基)丙烯酸苄酯/甲基丙烯酸/丙烯酸共聚物進行加成反應而成之樹脂、令(甲基)丙烯酸環氧丙酯跟(甲基)丙烯酸三環癸酯/苯乙烯/甲基丙烯酸/丙烯酸共聚物進行加成反應而成之樹脂、令(甲基)丙烯酸環氧丙酯跟(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苄酯/甲基丙烯酸/丙烯酸共聚物進行加成反應而成之樹脂等。其中,又以(甲基)丙烯酸苄酯/甲基丙烯酸/丙烯酸共 聚物、苯乙烯/甲基丙烯酸/丙烯酸共聚物、以及丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/甲基丙烯酸/丙烯酸共聚物較佳。 Specific examples of the copolymer (B1) include 3,4-epoxycyclohexylmethyl (meth)acrylate/methacrylic acid/acrylic acid copolymer, and 3,4-epoxy acrylate. Tricyclo[5.2.1.0 2,6 ]decyl ester/methacrylic acid/acrylic acid copolymer, glycidyl (meth)acrylate/benzyl (meth)acrylate/methacrylic acid/acrylic acid copolymer, (methyl ) Glycidyl acrylate / styrene / methacrylic acid / acrylic acid copolymer, 3,4-epoxytricycloacrylic acid [5.2.1.0 2,6 ] decyl ester / N-cyclohexyl maleic anhydride imide / Methacrylic acid/acrylic acid copolymer, 3-methyl-3-(methyl)propenyloxymethyloxetane/styrene/methacrylic acid/acrylic acid copolymer, benzyl (meth)acrylate/ A methacrylic acid/acrylic acid copolymer, a styrene/methacrylic acid/acrylic acid copolymer, a glycidyl (meth)acrylate, and an benzyl (meth)acrylate/methacrylic acid/acrylic acid copolymer are subjected to an addition reaction. A resin, a resin obtained by adding a reaction of a glycidyl (meth) acrylate with a tricyclodecyl (meth) acrylate/styrene/methacrylic acid/acrylic acid copolymer. A resin obtained by addition reaction of glycidyl methacrylate with tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / methacrylic acid / acrylic acid copolymer. Among them, benzyl (meth)acrylate/methacrylic acid/acrylic acid copolymer, styrene/methacrylic acid/acrylic acid copolymer, and 3,4-epoxytricycloacrylic acid [5.2.1.0 2,6 ] An oxime ester/methacrylic acid/acrylic acid copolymer is preferred.
共聚物(B1)的聚苯乙烯換算之重量平均分子量係以3,000~100,000較佳、5,000~50,000更佳、5,000~30,000特佳,尤其以5,000~18,000特佳、5,000~12,000最佳。分子量若位於上述範圍,則未曝光部對於顯影液的溶解性就會很高,所得到的著色圖形之殘膜率及硬度也會有提高的傾向。 The polystyrene-equivalent weight average molecular weight of the copolymer (B1) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, more preferably 5,000 to 30,000, particularly preferably 5,000 to 18,000, and most preferably 5,000 to 12,000. When the molecular weight is in the above range, the solubility of the unexposed portion in the developer is high, and the residual film ratio and hardness of the obtained colored pattern tend to be improved.
共聚物(B1)的分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)],係以為1.1~6較佳、1.2~4更佳。 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the copolymer (B1) is preferably from 1.1 to 6, more preferably from 1.2 to 4.
共聚物(B1)的酸值,係以為50~180mg-KOH/g較佳、60~170mg-KOH/g更佳、100~150mg-KOH/g特佳。在此處,酸值係為用以中和樹脂1g所必要的氫氧化鉀的量(mg)之測定值,例如可藉由使用氫氧化鉀水溶液來進行滴定而求出。 The acid value of the copolymer (B1) is preferably from 50 to 180 mg-KOH/g, more preferably from 60 to 170 mg-KOH/g, and particularly preferably from 100 to 150 mg-KOH/g. Here, the acid value is a measured value of the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.
黏合劑樹脂(B)也可以含有共聚物(B1)以外的樹脂(以下也稱為「樹脂(B2)」)。以樹脂(B2)而言,除了需為鹼可溶性樹脂以外,並未特別予以限定,可舉例如:甲基丙烯酸及單體(x)之共聚物;丙烯酸及單體(x)之共聚物;甲基丙烯酸或丙烯酸及(a)之共聚物;(a)及(b)之共聚物;甲基丙烯酸或丙烯酸及(b)之共聚物;(b)及(c)之共聚物;(a)及(b)及(c)之共聚物;令(甲基)丙烯酸及/或(b)跟(a)及(c)之共聚物進行加成反應而成之樹脂;令(a)跟甲基丙烯酸及 /或(b)及(c)之共聚物進行加成反應,再進而使其反應變成酸酐的樹脂等。具體來說,可舉例如:特開2010-224204號公報中所揭示的作為鹼可溶性樹脂之樹脂等。 The binder resin (B) may contain a resin other than the copolymer (B1) (hereinafter also referred to as "resin (B2)"). The resin (B2) is not particularly limited as long as it needs to be an alkali-soluble resin, and examples thereof include a copolymer of methacrylic acid and a monomer (x); a copolymer of acrylic acid and a monomer (x); a copolymer of methacrylic acid or acrylic acid and (a); a copolymer of (a) and (b); a copolymer of methacrylic acid or acrylic acid and (b); a copolymer of (b) and (c); And copolymers of (b) and (c); resins obtained by addition reaction of (meth)acrylic acid and/or (b) copolymers of (a) and (c); Methacrylic acid and And the copolymer of (b) and (c) is subjected to an addition reaction, and further, a resin which is reacted to form an acid anhydride or the like. Specifically, for example, a resin which is an alkali-soluble resin disclosed in JP-A-2010-224204, and the like can be mentioned.
其中,較佳者為:甲基丙烯酸或丙烯酸及(a)之共聚物、(a)及(b)之共聚物、(a)及(b)及(c)之共聚物、甲基丙烯酸或丙烯酸及(c)之共聚物、以及(b)及(c)之共聚物;更佳者為:甲基丙烯酸或丙烯酸及(a)之共聚物、甲基丙烯酸或丙烯酸及(c)之共聚物。黏合劑樹脂(B)藉由令共聚物(B1)同時含有上述等之樹脂,可使其未曝光部對於顯影液具有高度的溶解性,且使所得到的著色圖形的形狀變得良好,故較佳。 Among them, preferred are: methacrylic acid or acrylic acid and (a) copolymer, (a) and (b) copolymer, (a) and (b) and (c) copolymer, methacrylic acid or Acrylic acid and copolymer of (c), and copolymer of (b) and (c); more preferably: copolymer of methacrylic acid or acrylic acid and (a), methacrylic acid or acrylic acid and (c) Things. The binder resin (B) can have the resin (B1) containing the above-mentioned resin at the same time, so that the unexposed portion has high solubility to the developer, and the shape of the obtained colored pattern is improved. Preferably.
樹脂(B2)的聚苯乙烯換算之重量平均分子量係以3,000~50,000較佳、5,000~30,000更佳、5,000~15,000特佳。 The polystyrene-equivalent weight average molecular weight of the resin (B2) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 5,000 to 15,000.
樹脂(B2)的分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)],係以為1.1~6較佳、1.2~4更佳。 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)的酸值,係以為50~180mg-KOH/g較佳、60~170mg-KOH/g更佳、90~160mg-KOH/g特佳。 The acid value of the resin (B2) is preferably from 50 to 180 mg-KOH/g, more preferably from 60 to 170 mg-KOH/g, and particularly preferably from 90 to 160 mg-KOH/g.
樹脂(B2)若為前述的樹脂,特別是當跟共聚物(B1)組合使用時,未曝光部對於顯影液的溶解性就會很高,所得到的著色圖形之殘膜率及硬度也會有提高的傾向。 When the resin (B2) is the above-mentioned resin, particularly when used in combination with the copolymer (B1), the solubility of the unexposed portion to the developer is high, and the residual film ratio and hardness of the obtained colored pattern are also There is a tendency to improve.
共聚物(B1)的含有量,係相對於黏合劑樹脂(B)的總量而言,以10~100質量%較佳、30~100質量%更佳、30~70質量%特佳、30~50質量%最佳。 The content of the copolymer (B1) is preferably from 10 to 100% by mass, more preferably from 30 to 100% by mass, particularly preferably from 30 to 70% by mass, based on the total amount of the binder resin (B). ~50% by mass is the best.
共聚物(B1)的含有量若位於上述範圍內,則未曝光部對於顯影液的溶解性就會提高,故著色圖形的產率會變優良。共聚物(B1)的含有量若少於上述範圍,本發明效果之顯影性就無法充分地被得到。 When the content of the copolymer (B1) is within the above range, the solubility of the unexposed portion in the developer is improved, so that the yield of the colored pattern is excellent. When the content of the copolymer (B1) is less than the above range, the developability of the effect of the present invention cannot be sufficiently obtained.
特別是,黏合劑樹脂(B)係以由共聚物(B1)、甲基丙烯酸或丙烯酸及(a)之共聚物、以及甲基丙烯酸或丙烯酸及(c)之共聚物所構成者為較佳。此情形下的含有量係以分別如下為較佳:共聚物(B1):15~70質量%、甲基丙烯酸或丙烯酸及(a)之共聚物:15~70質量%、甲基丙烯酸或丙烯酸及(c)之共聚物:15~70質量%;以下更佳:共聚物(B1):25~50質量%、甲基丙烯酸或丙烯酸及(a)之共聚物:25~50質量%、甲基丙烯酸或丙烯酸及(c)之共聚物:25~50質量%。 In particular, the binder resin (B) is preferably composed of a copolymer (B1), a copolymer of methacrylic acid or acrylic acid and (a), and a copolymer of methacrylic acid or acrylic acid and (c). . The content in this case is preferably as follows: copolymer (B1): 15 to 70% by mass, methacrylic acid or acrylic acid, and copolymer of (a): 15 to 70% by mass, methacrylic acid or acrylic acid. And (c) copolymer: 15 to 70% by mass; more preferably: copolymer (B1): 25 to 50% by mass, methacrylic acid or acrylic acid and (a) copolymer: 25 to 50% by mass, A A copolymer of acrylic acid or acrylic acid and (c): 25 to 50% by mass.
黏合劑樹脂(B)若為上述的組合,則未曝光部對於顯影液的溶解性就會提高,並且可形成優良形狀的著色圖形。 When the binder resin (B) is in the above combination, the solubility of the unexposed portion in the developer is improved, and a colored pattern having an excellent shape can be formed.
本發明的著色感光性樹脂組合物係包括聚合性化合物(C)。聚合性化合物(C)係藉由從聚合引發劑(D)所產生的活性自由基及酸等而聚合成的化合物,可舉例如:具有聚合性的乙烯性不飽和鍵結之化合物等,並以例如:(甲基)丙烯酸酯化合物為較佳。 The colored photosensitive resin composition of the present invention includes a polymerizable compound (C). The polymerizable compound (C) is a compound obtained by polymerizing an active radical derived from a polymerization initiator (D), an acid, or the like, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. For example, a (meth) acrylate compound is preferred.
其中,以聚合性化合物(C)而言,又以具有3個以上的乙烯性不飽和鍵結之聚合性化合物為較佳。以此種類的聚 合性化合物而言,可舉例如:三羥甲基丙烷三(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)丙烯醯基氧乙基)三聚異氰酸酯、乙二醇改質季戊四醇四(甲基)丙烯酸酯、乙二醇改質二季戊四醇六(甲基)丙烯酸酯、丙二醇改質季戊四醇四(甲基)丙烯酸酯、丙二醇改質二季戊四醇六(甲基)丙烯酸酯、己內酯改質季戊四醇四(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯等。其中,又以二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯為較佳。上述等之聚合性化合物可以單獨使用,也可以將2種以上合併使用之。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. This type of gathering The conjugated compound may, for example, be trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate. Ester, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol 九 (meth) acrylate, tris(2-(methyl) Propylene decyl oxyethyl) trimeric isocyanate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate Ester, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred. The above-mentioned polymerizable compounds may be used singly or in combination of two or more kinds.
聚合性化合物(C)的重量平均分子量,係以在150以上、2,900以下較佳、250~1,500以下更佳。 The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 to 1,500 or less.
聚合性化合物(C)的含有量,係相對於著色感光性樹脂組合物中的固形成份而言,以7~65質量%較佳、13~60質量%更佳、17~55質量%則特佳。聚合性化合物(C)之含有量若位於前述的範圍內,硬化就會完成的很充份,顯影時的殘膜率會向上提升,著色圖形上產生蝕刻不足(undercut)的情況也不易發生,而使得密著性有變良好的傾向,故而較佳。 The content of the polymerizable compound (C) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, and more preferably 17 to 55 mass%, based on the solid content of the coloring photosensitive resin composition. good. When the content of the polymerizable compound (C) is within the above range, the hardening is completed sufficiently, the residual film ratio during development is increased upward, and the undercut of the colored pattern is less likely to occur. Further, the adhesion tends to be good, so that it is preferable.
本發明的著色感光性樹脂組合物係包括聚合引發劑(D)。 The colored photosensitive resin composition of the present invention includes a polymerization initiator (D).
以前述的聚合引發劑(D)而言,凡是可利用光的作用來產生活性自由基及/或酸等而使聚合性化合物(C)開始進行聚合的化合物皆可使用,並未特別予以限制,可使用公知的聚合引發劑。 In the above-mentioned polymerization initiator (D), any compound which can be polymerized by the action of light to generate an active radical and/or an acid to start polymerization of the polymerizable compound (C) can be used without particular limitation. A known polymerization initiator can be used.
以聚合引發劑(D)而言,係以可藉由光的作用而產生活性自由基的化合物為較佳,並以含有擇自由烷基苯酮(alkyl phenone)化合物、三嗪化合物(triazine)、醯基氧化膦(acyl phosphine oxide)化合物、肟(oxime)化合物以及雙咪唑(biimidazole)化合物所構成的族群中至少1種者的聚合引發劑為更佳,而含有肟化合物及烷基苯酮化合物的聚合引發劑則特佳。 In the case of the polymerization initiator (D), a compound which can generate an active radical by the action of light is preferred, and a compound containing an alkyl phenone or a triazine is preferably contained. More preferably, a polymerization initiator of at least one of the group consisting of an acyl phosphine oxide compound, an oxime compound, and a biimidazole compound contains a ruthenium compound and an alkyl benzophenone. The polymerization initiator of the compound is particularly preferred.
前述烷基苯酮化合物,係為具有下式(d2)所表示的部份結構或式(d3)所表示的部份結構之化合物。上述等之部份結構中,苯環也可以具有取代基。 The alkylphenone compound is a compound having a partial structure represented by the following formula (d2) or a partial structure represented by the formula (d3). In some of the above structures, the benzene ring may have a substituent.
以具有式(d2)所表示的部份結構之化合物而言,可舉例如:2-甲基-2-嗎啉代-1-(4-甲基硫基苯基)丙-1-酮、2-二甲基氨基-1-(4-嗎啉代苯基)-2-苄基丁-1-酮、2-(二甲基氨基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉代基)苯基]丁-1-酮等。也可以使用IRGACURE(註冊商標)369、907及379(以上為BASF公司製)等之市售產品。 The compound having a partial structure represented by the formula (d2) may, for example, be 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one. 2-Dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)- ]]-1-[4-(4-morpholino)phenyl]butan-1-one. Commercial products such as IRGACURE (registered trademark) 369, 907, and 379 (above, BASF Corporation) can also be used.
以具有式(d3)所表示的部份結構之化合物而言,可舉 例如:2-羥基-2-甲基-1-苯基丙-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙-1-酮、1-羥基環己基苯酮、2-羥基-2-甲基-1-(4-異丙基苯基)丙-1-酮等之寡聚物,α,α-二乙氧基苯乙酮、苄基二甲基縮酮等。 In the case of a compound having a partial structure represented by the formula (d3), For example: 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1- Oligomers such as ketone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)propan-1-one, α,α-diethoxybenzene Ethyl ketone, benzyl dimethyl ketal, and the like.
從靈敏度的觀點來看,以上述烷基苯酮化合物而言,係以為具有式(d2)所表示的部份結構之化合物較佳,並以為2-甲基-2-嗎啉代-1-(4-甲基硫基苯基)丙-1-酮及2-二甲基氨基-1-(4-嗎啉代苯基)-2-苄基丁-1-酮更佳。 From the viewpoint of sensitivity, in the case of the above alkylphenone compound, a compound having a partial structure represented by the formula (d2) is preferred, and is considered to be 2-methyl-2-morpholino-1- (4-Methylthiophenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one are more preferred.
以上述三嗪化合物而言,可舉例如:2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)醚]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)醚]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基氨基-2-甲基苯基)醚]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)醚]-1,3,5-三嗪等。 The above triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-double. (trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5 -triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-[2-(5-methylfuran-2-yl)ether]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2- Ether]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ether]-1 , 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ether]-1,3,5-triazine, and the like.
以上述醯基氧化膦化合物而言,可舉例如:2,4,6-三甲基苯醯二苯基氧化膦等。也可使用IRGACURE(註冊商標)819(BASF公司製)等之市售產品。 The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylphenylphosphonium diphenylphosphine oxide or the like. A commercially available product such as IRGACURE (registered trademark) 819 (manufactured by BASF Corporation) can also be used.
上述肟化合物係為具有下式(d1)所表示的部份結構之化合物。以下,*係用以表示鍵結處。 The above hydrazine compound is a compound having a partial structure represented by the following formula (d1). Hereinafter, * is used to indicate the bond.
以上述肟化合物而言,可舉例如:N-苯甲酸基-1-(4-苯基硫基苯基)丁-1-酮-2-亞胺、N-苯甲酸基-1-(4-苯基硫基苯基)辛-1-酮-2-亞胺、N-苯甲酸基-1-(4-苯基硫基苯基)-3-環戊基丙-1-酮-2-亞胺、N-乙酸基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙-1-亞胺、N-乙酸基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二噁環戊基甲基氧)苯甲醯基}-9H-咔唑-3-基]乙-1-亞胺、N-乙酸基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙-1-亞胺、N-苯甲酸基-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。也可以使用IRGACURE(註冊商標)OXE 01、OXE 02(以上為BASF公司製)、N-1919(ADEKA公司製)等之市售產品。其中,又係以下述者為較佳:N-苯甲酸基-1-(4-苯基硫基苯基)丁-1-酮-2-亞胺、N-苯甲酸基-1-(4-苯基硫基苯基)辛-1-酮-2-亞胺以及N-苯甲酸基-1-(4-苯基硫基苯基)-3-環戊基丙-1-酮-2-亞胺。若使用上述等之肟化合物,特別是在將本發明的著色感光性樹脂組合物調製成藍色著色感光性樹脂組合物時,就可得到高明亮度的彩色濾光片。 The above hydrazine compound may, for example, be N-benzoic acid-1-(4-phenylthiophenyl)butan-1-one-2-imine or N-benzoic acid-1-(4) -phenylthiophenyl)oct-1-one-2-imine, N-benzoic acid-1-(4-phenylthiophenyl)-3-cyclopentylpropan-1-one-2 -imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]e-i-imine, N-acetoxy -1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethyloxy)benzimidyl}-9H-oxime Zyrid-3-yl]e-i-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-3 -cyclopentylpropan-1-imine, N-benzoic acid-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-3- Cyclopentylpropan-1-one-2-imine and the like. Commercial products such as IRGACURE (registered trademark) OXE 01, OXE 02 (above, BASF), and N-1919 (made by Adeka) can also be used. Among them, the following are preferred: N-benzoic acid-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzoic acid-1-(4) -phenylthiophenyl)oct-1-one-2-imine and N-benzoic acid-1-(4-phenylthiophenyl)-3-cyclopentylpropan-1-one-2 - Imine. When the above-mentioned ruthenium compound is used, in particular, when the colored photosensitive resin composition of the present invention is prepared into a blue colored photosensitive resin composition, a high-brightness color filter can be obtained.
以雙咪唑化合物而言,可舉例如:2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基雙咪唑(例如,請參照特開平6-75372號公報、特開平6-75373號公報等)、2,2’-雙(2- 氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(二烷氧基苯基)雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧基苯基)雙咪唑(例如,請參照特公昭48-38403號公報、特開昭62-174204號公報)、將4,4’,5,5’-位的苯基以烷氧基羰基來取代的咪唑化合物(例如,請參照特開平7-10913號公報)等。較佳者為:2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基雙咪唑等。 The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis (2, 3-Dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.), 2, 2' - double (2- Chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)bisimidazole, 2,2'-bis (2 -Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (for example, see Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204) An imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, see JP-A-7-10913). Preferred are: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl) -4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole Wait.
更進一步,以聚合引發劑(D)而言,可舉例如:苯偶因(benzoin)、苯偶因甲醚、苯偶因***、苯偶因異丙醚、苯偶因異丁醚等之苯偶因化合物;二苯甲酮(benzophenone)、鄰-苯醯苯甲酸甲酯、4-苯基二苯甲酮、4-苯醯-4’-甲基二苯基硫化物、3,3’,4,4’-四(第3丁基過氧化羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等之二苯甲酮化合物;9,10-菲醌(9,10-phenanthrenequinone)、2-乙基蒽醌(2-ethyl anthraquinone)、莰醌(camphorquinone)等之醌化合物;10-丁基-2-氯吖啶酮(10-butyl-2-chloro acridone)、苯偶醯(benzil)、苯基乙醛酸甲酯、環戊二烯鈦(titanocene)化合物等。上述等物質,係以跟後述的聚合引發助劑(D1)(特別是胺類)組合使用為較佳。 Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Benzoin compound; benzophenone, methyl o-benzoquinone, 4-phenylbenzophenone, 4-phenylhydrazine-4'-methyldiphenyl sulfide, 3,3 a benzophenone compound such as ',4,4'-tetra (t-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone ( 9,10-phenanthrenequinone), 2-ethyl anthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone (10-butyl-2-chloro acridone) ), benzil, methyl phenylglyoxylate, titanium tetradecene compound, and the like. The above-mentioned materials are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.
以藉由光來產生酸的酸產生劑而言,可舉例如:4-羥 基苯基二甲基鋶化物對-甲苯磺酸鹽、4-羥基苯基二甲基鋶化物氫六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶化物對-甲苯磺酸鹽、4-乙醯氧基苯基甲基苄基鋶化物氫六氟銻酸鹽、三苯基鋶化物對-甲苯磺酸鹽、三苯基鋶化物氫六氟銻酸鹽、二苯基碘鎓對-甲苯磺酸鹽、二苯基碘鎓氫六氟銻酸鹽等之鎓鹽(onium salt)類,對甲苯磺酸硝基苄酯(nitrobenzyl tosylate)類,對甲苯磺酸苯偶因酯(benzoin tosylate)類等。 In the case of an acid generator which generates an acid by light, for example, 4-hydroxyl Phenyl dimethyl phthalate p-toluene sulfonate, 4-hydroxyphenyl dimethyl hydrazine hydrohexafluoro decanoate, 4-ethyl methoxy phenyl dimethyl phthalate p-toluene sulfonic acid Salt, 4-acetoxyphenylmethylbenzyl halide hydrogen hexafluoroantimonate, triphenyl telluride p-toluenesulfonate, triphenyl phosphonium hydrogen hexafluoroantimonate, diphenyl Onium salt of iodonium p-toluenesulfonate, diphenyliodonium hydrogen hexafluoroantimonate, nitrobenzyl tosylate, p-toluenesulfonate Benzoate (benzoin tosylate) and the like.
聚合引發劑(D)的含有量,係以相對於黏合劑樹脂(B)及聚合性化合物(C)的合計量100質量份而言,為0.1~30質量份較佳、1~20質量份則更佳。聚合引發劑(D)的含有量若位於前述的範圍內,就能夠以高靈敏度來形成著色圖形,故能縮短曝光時間而提高產率。 The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the total of the binder resin (B) and the polymerizable compound (C). It is better. When the content of the polymerization initiator (D) is within the above range, the colored pattern can be formed with high sensitivity, so that the exposure time can be shortened and the yield can be improved.
本發明的著色感光性樹脂組合物可更包括聚合引發助劑(D1)。在含有聚合引發助劑(D1)的情況下,通常會跟聚合引發劑(D)組合使用之。聚合引發助劑(D1)係一種化合物,用以促進藉由聚合引發劑而引發聚合之聚合性化合物的聚合反應,或稱為增敏劑。 The colored photosensitive resin composition of the present invention may further include a polymerization initiation aid (D1). In the case where the polymerization initiating aid (D1) is contained, it is usually used in combination with the polymerization initiator (D). The polymerization initiating aid (D1) is a compound for promoting polymerization of a polymerizable compound which initiates polymerization by a polymerization initiator, or a sensitizer.
以聚合引發助劑(D1)而言,可舉例如:胺化合物、烷氧基蒽(alkoxy anthracene)化合物、噻噸酮(thioxanthone)化合物、羧酸化合物等,其中並以噻噸酮化合物為較佳。 The polymerization initiation aid (D1) may, for example, be an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound or the like, wherein a thioxanthone compound is used. good.
以上述胺化合物而言,可舉例如:三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基氨基苯甲酸甲酯、4-二甲基氨基苯甲酸乙酯、4-二甲基氨基苯甲酸異戊酯、苯甲酸 2-二甲基氨基乙酯、4-二甲基氨基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲基氨基)二苯甲酮(通稱為米希勒酮(Michler’s ketone))、4,4’-雙(二乙基氨基)二苯甲酮、4,4’-雙(乙基甲基氨基)二苯甲酮等,其中又以4,4’-雙(二乙基氨基)二苯甲酮為較佳。也可以使用EAB-F(保土谷化學工業(股份有限)製)等之市售產品。 The above amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Isoamyl methylaminobenzoate, benzoic acid 2-Dimethylaminoethyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)diphenyl Ketone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. A commercially available product such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.
以上述烷氧基蒽化合物而言,可舉例如: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。 The above alkoxy fluorene compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2 -ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.
以上述噻噸酮化合物而言,可舉例如:2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、1-氯-4-丙氧基噻噸酮等。 Examples of the above thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthene. Ketone, 1-chloro-4-propoxythioxanthone, and the like.
以上述羧酸化合物而言,可舉例如:苯硫基乙酸、甲基苯硫基乙酸、乙基苯硫基乙酸、甲基乙基苯硫基乙酸、二甲基苯硫基乙酸、甲氧基苯硫基乙酸、二甲氧基苯硫基乙酸、氯苯硫基乙酸、二氯苯硫基乙酸、N-苯基氨基乙酸、苯氧基乙酸、萘基硫代乙酸、N-萘基氨基乙酸、萘氧基乙酸等。 Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxy. Phenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthyl Glycine, naphthyloxyacetic acid, and the like.
聚合引發助劑(D1),可單獨使用,也可將2種以上合併使用之。 The polymerization initiation aid (D1) may be used singly or in combination of two or more.
當使用上述等之聚合引發助劑(D1)時,其使用量係以相對於黏合劑樹脂(B)及聚合性化合物(C)的合計量100質量份而言,為0.1~30質量份較佳、1~20質量份則更佳。 聚合引發助劑(D1)的量若位於前述的範圍內,就更能夠以高靈敏度來形成著色圖形,故可提高著色圖形的產率。 When the above-mentioned polymerization initiation aid (D1) is used, the amount thereof is 0.1 to 30 parts by mass based on 100 parts by mass of the total of the binder resin (B) and the polymerizable compound (C). Good, 1~20 parts by mass is better. When the amount of the polymerization initiation aid (D1) is within the above range, the colored pattern can be formed with high sensitivity, so that the yield of the colored pattern can be improved.
本發明的著色感光性樹脂組合物係以含有溶劑(E)為較佳。 The colored photosensitive resin composition of the present invention preferably contains a solvent (E).
關於溶劑(E),並未特別予以限定,可使用該領域所通常使用的溶劑。例如,可從以下所列的溶劑之中予以選用之:酯溶劑(於分子內含有-COO-、但不含-O-的溶劑)、醚溶劑(於分子內含有-O-、但不含-COO-的溶劑)、醚酯溶劑(於分子內含有-COO-及-O-的溶劑)、酮溶劑(於分子內含有-CO-、但不含-COO-的溶劑)、醇溶劑(於分子內含有OH、但不含-O-、-CO-及-COO-的溶劑)、芳香族烴溶劑、醯胺溶劑、二甲亞碸(dimethyl sulfoxide)等。 The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, it can be selected from the solvents listed below: an ester solvent (a solvent containing -COO- in the molecule but not containing -O-), an ether solvent (containing -O- in the molecule, but not containing a solvent of -COO-), an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule but not containing -COO-), an alcohol solvent ( A solvent containing OH in the molecule but not containing -O-, -CO-, and -COO-, an aromatic hydrocarbon solvent, a guanamine solvent, or a dimethyl sulfoxide.
以酯溶劑而言,可舉例如: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、乙酸戊酯、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-丁內醯胺(γ-butyrolactum)等。 Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and acetic acid. Isoamyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate Ester, cyclohexanol acetate, γ-butyrolactum, and the like.
以醚溶劑而言,可舉例如:乙二醇一甲醚、乙二醇一***、乙二醇一丙醚、乙二醇一丁醚、二乙二醇一甲醚、二乙二醇一***、二乙二醇一丁醚、丙二醇一甲醚、丙二醇一***、丙二醇一丙醚、丙二醇一丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃 (tetrahydropyran)、1,4-二噁烷(1,4-dioxane)、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲***、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚(anisole)、苯***(phenetole)、甲基苯甲醚等。 The ether solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether or diethylene glycol. Ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl Butanol, tetrahydrofuran, tetrahydropyran (tetrahydropyran), 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, two Ethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.
以醚酯溶劑而言,可舉例如: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、丙二醇一甲醚乙酸酯、丙二醇一***乙酸酯、丙二醇一丙醚乙酸酯、乙二醇一甲醚乙酸酯、乙二醇一***乙酸酯、二乙二醇一***乙酸酯、二乙二醇一丁醚乙酸酯等。 Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxyl. Methyl propyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate , 2-ethoxy-2-methylpropionic acid ethyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Butyl ether acetate and the like.
以酮溶劑而言,可舉例如: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(isophorone)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 group. -2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.
以醇溶劑而言,可舉例如:甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、丙三醇等。 The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol or glycerin.
以芳香族烴溶劑而言,可舉例如:苯、甲苯、二甲苯、均三甲苯(mesitylene)等。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like.
以醯胺溶劑而言,可舉例如:N,N-二甲基甲醯胺(N,N-dimethylformamide)、N,N-二甲替乙醯胺(N,N- dimethylacetamide)、N-甲基吡咯烷酮(N-methylpyrrolidone)等。 In the case of a decylamine solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide (N,N- Dimethylacetamide), N-methylpyrrolidone, and the like.
上述等之溶劑,可單獨使用,也可將2種以上合併使用之。 The solvent of the above may be used singly or in combination of two or more.
上述的溶劑之中,若從塗佈性、乾燥性等觀點來看,係以在1atm下之沸點為120℃以上、180℃以下的有機溶劑較佳。其中,較佳者為:丙二醇一甲醚乙酸酯、乳酸乙酯、丙二醇一甲醚、3-乙氧基丙酸乙酯、乙二醇一甲醚、二乙二醇一甲醚、二乙二醇一***、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮、N,N-二甲基甲醯胺等;更佳者為:丙二醇一甲醚乙酸酯、丙二醇一甲醚、二丙二醇甲醚乙酸酯、乳酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、3-乙氧基丙酸乙酯等。 Among the above-mentioned solvents, an organic solvent having a boiling point of 120 ° C or more and 180 ° C or less at 1 atm is preferred from the viewpoints of coatability and drying properties. Among them, preferred are: propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethyl group More preferred are: propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy 1-butanol, ethyl 3-ethoxypropionate, and the like.
著色感光性樹脂組合物中溶劑(E)的含有量,係相對於本發明的著色感光性樹脂組合物的總量而言,以70~95質量%為較佳、75~92質量%為更佳。換言之,著色感光性樹脂組合物的固形成份係以為5~30質量%較佳、8~25質量%更佳。溶劑(E)的含有量若在前述的範圍內,於塗佈時的平坦性就會變得良好,此外,在形成彩色濾光片之際,由於不會有色濃度不足的情況發生,故顯示特性就會變得良好。 The content of the solvent (E) in the coloring photosensitive resin composition is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored photosensitive resin composition of the present invention. good. 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. When the content of the solvent (E) is within the above range, the flatness at the time of coating is improved, and when the color filter is formed, since the color density is not insufficient, the display is performed. The features will get better.
在本發明的著色感光性樹脂組合物中,也可以更包括有界面活性劑(F)。以界面活性劑(F)而言,可舉例如:矽系界面活性劑、氟系界面活性劑及具有氟原子之矽系界面活性劑等。上述等物質,也可為於側鏈上具有聚合性基者。 In the colored photosensitive resin composition of the present invention, a surfactant (F) may be further included. Examples of the surfactant (F) include a ruthenium-based surfactant, a fluorine-based surfactant, and a ruthenium-based surfactant having a fluorine atom. The above substances may also be those having a polymerizable group in the side chain.
以矽系界面活性劑而言,可舉例如:具有矽氧烷鍵結之界面活性劑等。具體而言,可舉例如:TORAY SILICON(商品名)DC3PA、同系列SH7PA、同系列DC11PA、同系列SH21PA、同系列SH28PA、同系列SH29PA、同系列SH30PA、同系列8400(Toray Dow Corning(股份有限)製);KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(股份有限)製);TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452、TSF4460(Momentive Performance Materials Japan聯合公司製)等。 The lanthanoid surfactant may, for example, be a surfactant having a siloxane coupling. Specifically, for example, TORAY SILICON (trade name) DC3PA, the same series SH7PA, the same series DC11PA, the same series SH21PA, the same series SH28PA, the same series SH29PA, the same series SH30PA, the same series 8400 (Toray Dow Corning (limited shares) )); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance) Materials Japan Co., Ltd.).
以上述的氟系界面活性劑而言,可舉例如:具有氟碳鏈之界面活性劑等。具體而言,可舉例如:FLUORAD(註冊商標)FC430、同系列FC431(住友3M(股份有限)製);MEGAFAC(註冊商標)F142D、同系列F171、同系列F172、同系列F173、同系列F177、同系列F183、同系列F554、同系列R30、同系列RS-718-K(DIC(股份有限)製);FTOP(註冊商標)EF301、同系列EF303、同系列EF351、同系列EF352(三菱Materials電子化成(股份有限)製);SURFLON(註冊商標)S381、同系列S382、同系列SC101、同系列SC105(旭硝子(股份有限)製);E5844((股份有限)Daikin Fine Chemical研究所製)等。 The fluorine-based surfactant described above may, for example, be a surfactant having a fluorocarbon chain. Specifically, for example, FLUORAD (registered trademark) FC430, the same series FC431 (Sumitomo 3M (share limited) system); MEGAFAC (registered trademark) F142D, the same series F171, the same series F172, the same series F173, the same series F177 , the same series F183, the same series F554, the same series R30, the same series RS-718-K (DIC (share limited) system); FTOP (registered trademark) EF301, the same series EF303, the same series EF351, the same series EF352 (Mitsubishi Materials) E-Chemical (trademark) system; SURFLON (registered trademark) S381, the same series S382, the same series SC101, the same series SC105 (Asahi Glass (share limited) system); E5844 ((share limited) Daikin Fine Chemical Research Institute), etc. .
以上述的具有氟原子之矽系界面活性劑而言,可舉例如:具有矽氧烷鍵結及氟碳鏈之界面活性劑等。具體而言,可舉例如:MEGAFAC(註冊商標)R08、同系列BL20、同系列F475、同系列F477、同系列F433(DIC(股份有限)製)等。 The above-mentioned fluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a siloxane coupling or a fluorocarbon chain. Specifically, for example, MEGAFAC (registered trademark) R08, the same series BL20, the same series F475, the same series F477, and the same series F433 (DIC (stock limited) system) can be mentioned.
上述等之界面活性劑,可以單獨使用,也可以將2種以上合併使用之。 The above-mentioned surfactants may be used singly or in combination of two or more.
界面活性劑(F)的含有量,係相對於本發明的著色感光性樹脂組合物之總量而言,以0.001質量%以上、0.2質量%以下為較佳,0.002質量%以上、0.1質量%以下更佳,0.01質量%以上、0.05質量%以下則特佳。另外,在上述的含有量之內,並不包含前述顏料分散劑的含有量。界面活性劑(F)的含有量若位於上述的範圍內,彩色濾光片的平坦性就會變得良好。 The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and 0.002% by mass or more and 0.1% by mass based on the total amount of the coloring photosensitive resin composition of the present invention. More preferably, it is particularly preferably 0.01% by mass or more and 0.05% by mass or less. Further, the content of the pigment dispersant is not included in the above content. When the content of the surfactant (F) is within the above range, the flatness of the color filter becomes good.
本發明的著色感光性樹脂組合物中,必要時亦可對應添加以下所例示之在該技術領域所公知的各種添加劑(以下也稱為「其他成份」):填充劑、其他的高分子化合物、密著促進劑、抗氧化劑、紫外線吸收劑、光安定劑、鏈轉移劑等。 In the colored photosensitive resin composition of the present invention, various additives (hereinafter also referred to as "other components") known in the art, which are exemplified below, may be added as needed: a filler, other polymer compound, Adhesion promoter, antioxidant, ultraviolet absorber, light stabilizer, chain transfer agent, and the like.
本發明的著色感光性樹脂組合物係包括了例如:著色劑(A)、黏合劑樹脂(B)、聚合性化合物(C)及聚合引發劑(D),並且於必要時可再對應混合使用聚合引發助劑(D1)、溶劑(E)、界面活性劑(F)及其他成份來進行調製。 The colored photosensitive resin composition of the present invention includes, for example, a coloring agent (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D), and may be used in combination if necessary. The polymerization initiation aid (D1), the solvent (E), the surfactant (F), and other components are used for preparation.
當含有顏料(A2)時,係以將顏料(A2)預先跟溶劑(E)的一部份或全部進行混合,直到令顏料的平均粒徑達到為0.2μm以下的程度,再使用珠磨機(beads-mill)來予以分散會較佳。此時,必要時也可對應配合加入前述顏料分散劑、黏合劑樹脂(B)的一部份或全部。在所得到的顏料分散液中,將殘存的成份等依據要變成的既定濃度來予以混 合,就可調製出本發明目的的著色感光性樹脂組合物。 When the pigment (A2) is contained, the pigment (A2) is previously mixed with a part or all of the solvent (E) until the average particle diameter of the pigment is 0.2 μm or less, and then the bead mill is used. It is better to disperse (beads-mill). At this time, a part or all of the above-mentioned pigment dispersant and binder resin (B) may be added in combination as necessary. In the obtained pigment dispersion liquid, the remaining components and the like are mixed according to a predetermined concentration to be converted. The colored photosensitive resin composition for the purpose of the present invention can be prepared.
當含有染料(A1)時,染料(A1)係以預先溶解於溶劑(E)的一部份或全部來調製成溶液較佳。該溶液係以利用孔徑0.01~1μm左右的過濾器來進行過濾較佳。 When the dye (A1) is contained, the dye (A1) is preferably prepared by dissolving a part or all of the solvent (E) in advance. This solution is preferably filtered by using a filter having a pore diameter of about 0.01 to 1 μm.
如上所述而混合調製出的著色感光性樹脂組合物,係以利用孔徑0.01~10μm左右的過濾器來進行過濾較佳。 The colored photosensitive resin composition prepared and mixed as described above is preferably filtered by a filter having a pore diameter of about 0.01 to 10 μm.
以使用本發明的著色感光性樹脂組合物來形成彩色濾光片的著色圖形之方法而言,可舉例如:微影法、噴墨法等。利用微影法來形成著色圖形之方式,係將本發明的著色感光性樹脂組合物先塗佈於基板或別的樹脂層(例如,在基板上已先形成有別的著色感光性樹脂組合物層等)之上,去除(乾燥)溶劑等揮發成份而形成乾燥後塗膜,再藉由光罩而讓該著色層曝光、顯影。在上述的微影法中,若於曝光之際未使用光罩,及/或不進行顯影,就可形成作為著色塗膜之乾燥後塗膜的硬化物。上述等之著色圖形及著色塗膜可用來製作成彩色濾光片。 The method of forming the colored pattern of the color filter using the colored photosensitive resin composition of the present invention may, for example, be a lithography method or an inkjet method. The method of forming a colored pattern by a lithography method is to apply the colored photosensitive resin composition of the present invention to a substrate or another resin layer (for example, a different colored photosensitive resin composition is formed on the substrate). On the layer or the like, the volatile component such as a solvent is removed (dried) to form a dried coating film, and the colored layer is exposed and developed by a photomask. In the above lithography method, if a mask is not used at the time of exposure, and/or development is not performed, a cured product which is a dried coating film of the colored coating film can be formed. The above-mentioned colored pattern and colored coating film can be used to form a color filter.
所製作出的彩色濾光片之膜厚,並未特別予以限制,可依據所使用的材料、用途等而適當地予以調整,例如為0.1~30μm,並以為0.5~20μm較佳、0.5~6μm更佳。 The film thickness of the produced color filter is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.5 to 20 μm, preferably 0.5 to 6 μm. Better.
將著色感光性樹脂組合物塗佈於基板上,再藉由加熱乾燥(預烘烤處理,pre-bake)及/或減壓乾燥來去除掉溶劑等之揮發成份,即可得到平滑的乾燥後塗膜。 The colored photosensitive resin composition is applied onto a substrate, and then dried by heating (pre-bake) and/or under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth drying. Coating film.
以基板而言,可使用:石英玻璃、硼矽酸玻璃、氧化鋁矽酸鹽玻璃、表面塗佈有二氧化矽的鹼石灰(soda-lime) 玻璃等之玻璃基板;聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二醇酯(polyethylene terephthalate)等之樹脂基板;於矽、前述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。在上述等之基板上,也可以形成別的彩色濾光片層、樹脂層、電晶體、電路等。 For the substrate, quartz glass, borosilicate glass, alumina silicate glass, soda-lime coated with cerium oxide can be used. a glass substrate such as glass; a resin substrate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate; and aluminum, silver, silver/copper formed on the substrate / Palladium alloy film and the like. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates described above.
以塗佈方法而言,可舉例如:自旋式塗佈法(spin coating)、狹縫塗佈法(slit coating)、狹縫及自旋式塗佈法等。 The coating method may, for example, be a spin coating method, a slit coating method, a slit or a spin coating method.
施行加熱乾燥時的溫度,係以30~120℃為較佳、50~110℃為更佳。此外,以加熱時間而言,係以10秒鐘~60分鐘為較佳、30秒鐘~30分鐘為更佳。 The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Further, in terms of heating time, it is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.
當施行減壓乾燥時,係以在50~150Pa的壓力下、20~25℃的溫度範圍內進行為較佳。 When the drying under reduced pressure is carried out, it is preferably carried out at a temperature of from 50 to 150 Pa at a temperature of from 20 to 25 °C.
乾燥後塗膜的膜厚,並未特別予以限制,可依據所使用的材料、用途等而適當地予以調整。 The film thickness of the coating film after drying is not particularly limited and may be appropriately adjusted depending on the materials to be used, the use, and the like.
乾燥後塗膜,係藉由用以形成目標圖形的光罩來進行曝光。此時光罩上的圖形形狀並未特別予以限定,可使用對應目的用途之圖形形狀。 The film is applied after drying, and exposure is performed by a mask for forming a target pattern. At this time, the shape of the pattern on the photomask is not particularly limited, and a graphic shape corresponding to the intended use can be used.
以曝光所使用的光源而言,係以可產生250~450nm波長的光之光源為較佳。例如,可將未滿350nm的光,使用可截取出上述波長領域的濾波器(filter)予以截取出,或將436nm附近、408nm附近、365nm附近的光,使用可過濾出上述等波長領域的帶通濾波器(band-pass filter)來選擇性地予以濾出。具體而言,可舉例如:水銀燈、發光二 極體、陶瓷金屬鹵化燈(metal halide lamp)、鹵素燈等。 The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light having a wavelength of less than 350 nm can be taken out by using a filter capable of extracting the above-mentioned wavelength range, or light having a wavelength of about 435 nm, around 408 nm, and around 365 nm can be used to filter out the bands of the above-mentioned wavelength domains. A band-pass filter is selectively filtered out. Specifically, for example, a mercury lamp or a light-emitting lamp A polar body, a metal halide lamp, a halogen lamp, or the like.
為了能對曝光面全體進行均勻地平行光線照射,並可使光罩跟已形成有乾燥後塗膜的基板位於正確的位置,故係以使用光罩對準機(mask aligner)、步進機(stepper)等之裝置為較佳。 In order to uniformly illuminate the entire exposed surface of the exposure surface, and to position the reticle in the correct position with the substrate on which the dried coating film has been formed, a mask aligner and a stepper are used. A device such as a stepper is preferred.
曝光後,令其跟顯影液接觸,而使未曝光部被溶解、去除(亦即顯影),就可得到著色圖形。以顯影液而言,可舉例如:氫氧化鉀、碳酸氫鈉、氫氧化四甲銨等之鹼性化合物的水溶液。上述等之鹼性化合物的水溶液中之濃度,係以0.01~10質量%為較佳、0.03~5質量%為更佳。更進一步,顯影液也可以含有界面活性劑。 After the exposure, the exposed portion is brought into contact with the developer, and the unexposed portion is dissolved and removed (i.e., developed) to obtain a colored pattern. The developing solution may, for example, be an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate or tetramethylammonium hydroxide. The concentration in the aqueous solution of the above-mentioned basic compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may also contain a surfactant.
顯影方法也可以使用浸置式顯影法(puddle developing)、浸漬法(dipping)、噴塗法(spray)等。更進一步,在顯影時也可以將基板傾斜任意的角度。 The development method may also use puddle development, dipping, spray, or the like. Further, the substrate can be tilted at an arbitrary angle during development.
顯影後,係以施行水洗會較佳。 After development, it is preferred to perform a water wash.
再者,必要時亦可對應進行事後烘烤處理(post-bake)。事後烘烤處理的溫度,係以150~250℃為較佳、160~235℃為更佳。事後烘烤處理的時間,則以1~120分鐘為較佳、10~60分鐘為更佳。 Furthermore, post-bake processing may be performed correspondingly if necessary. The temperature after the post-baking treatment is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The time for post-baking treatment is preferably from 1 to 120 minutes, preferably from 10 to 60 minutes.
依據本發明的著色感光性樹脂組合物,尤其能夠以高產率製作出彩色濾光片。該彩色濾光片係非常有利於作為顯示裝置(例如:液晶顯示裝置、有機電致發光裝置、電子紙等)及固體攝影元件之彩色濾光片來使用。 According to the colored photosensitive resin composition of the present invention, in particular, a color filter can be produced with high yield. The color filter is very advantageous for use as a color filter for a display device (for example, a liquid crystal display device, an organic electroluminescence device, an electronic paper, etc.) and a solid-state imaging device.
以下列舉實施例,針對本發明進行更具體地說明。例中的「%」及「份」若未特別說明,皆指質量%及質量份而言。 The present invention will be more specifically described below by way of examples. In the examples, "%" and "parts" refer to both mass % and mass parts unless otherwise stated.
在具備冷卻管及攪拌裝置的燒瓶中,加入式(A0-1)所表示的化合物及式(A0-2)所表示的化合物之混合物(中外化成製)15份、三氯甲烷150份及N,N-二甲基甲醯胺8.9份,於攪拌下一面維持20℃以下、一面滴下加入氯化亞硫醯(thionyl chloride)10.9份。滴下終了後,升溫至50℃,於相同溫度下維持5小時而使反應之,之後冷卻至20℃。將冷卻後的反應溶液於攪拌下一面維持20℃以下、一面滴下加入2-乙基己基胺12.5份及三乙基胺22.1份的混合液。其後,於同溫度下攪拌5小時而使反應之。其次,將所得到的反應混合物利用旋轉蒸餾器(rotary evaporator)將溶劑蒸餾去掉後,加入少量的甲醇而劇烈地攪拌。將該混合物一面攪拌加入於離子交換水375份的混合液中,一面使結晶析出。將所析出的結晶過濾分離後,以離子交換水充分地予以洗淨,再於60℃下施行減壓乾燥,就可得到染料A1(染料A1)(式(A1-1)~式(A1-8)所表示的化合物之混合物)11.3份。 In a flask equipped with a cooling tube and a stirring device, a mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (manufactured by a method of external chemical conversion), 15 parts of chloroform, and 150 parts of chloroform and N were added. 8.9 parts of N-dimethylformamide, and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature at 20 ° C or lower while stirring. After the completion of the dropwise addition, the temperature was raised to 50 ° C, maintained at the same temperature for 5 hours to cause a reaction, and then cooled to 20 ° C. After the cooled reaction solution was maintained at 20 ° C or lower with stirring, 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 the same temperature for 5 hours. Next, the obtained reaction mixture was distilled off by a rotary evaporator, and a small amount of methanol was added thereto, followed by vigorous stirring. The mixture was stirred and added to a mixed liquid of 375 parts of ion-exchanged water to precipitate crystals. The precipitated crystals are separated by filtration, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain dye A1 (dye A1) (formula (A1-1) to formula (A1- 8) A mixture of the indicated compounds) 11.3 parts.
將式(1x)所表示的化合物20份及N-乙基-鄰-甲苯胺(和光純藥工業(股份有限)製)200份於遮光條件下進行混合,並將所得到的溶液於110℃下攪拌6小時。把所得到的反應液冷卻至室溫後,加入至水800份與35%鹽酸50份的混合液中,於室溫下攪拌1小時,有結晶析出。將所析出的結晶經吸引過濾後取得的殘餘部施行乾燥,即可得到式(1-31)所表示的化合物24份。產率為80%。 20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under a light-shielding condition, and the obtained solution was at 110 ° C. Stir under 6 hours. After cooling the obtained reaction liquid to room temperature, it was added to a mixed liquid of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The residue obtained by suction filtration of the precipitated crystals is dried to obtain 24 parts of the compound represented by the formula (1-31). The yield was 80%.
式(1-31)所表示的化合物之結構,係利用質量分析(LC;Agilent製1200型、MASS;Agilent製LC/MSD型)來予以確認。 The structure of the compound represented by the formula (1-31) was confirmed by mass spectrometry (LC; Model 1200, manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).
(質量分析)離子化模式=ESI+:m/z=[M+H]+ 603.4 Exact Mass:602.2 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 603.4 Exact Mass: 602.2
除了將N-乙基-鄰-甲苯胺改為換成N-丙基-2,6-二甲基苯胺以外,其餘步驟皆與合成例1相同,而得到式(1-39)所表示的化合物。 Except that N-ethyl-o-toluidine was changed to N-propyl-2,6-dimethylaniline, the other steps were the same as in Synthesis Example 1, and the formula (1-39) was obtained. Compound.
式(1-39)所表示的化合物之鑑定:(質量分析)離子化模式=ESI+:m/z=[M+H]+ 659.9 Exact Mass:658.9 Identification of the compound represented by formula (1-39): (mass analysis) ionization mode = ESI +: m / z = [M + H] + 659.9 Exact Mass: 658.9
在具備回流冷卻器、滴下漏斗及攪拌機的燒瓶內,以0.02L/分的速率通入氮氣以形成氮氣氛圍,加入乳酸乙酯 220份,一面攪拌一面加熱至70℃。其次,調製將甲基丙烯酸72份、丙烯酸7份、丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯(將式(I-1)所表示的化合物及式(II-1)所表示的化合物,以莫耳比50:50來混合)250份溶解於乳酸乙酯140份之溶液,將該溶解液使用滴下漏斗以4小時的時間滴下於保溫在70℃的燒瓶內。 In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at a rate of 0.02 L/min to form a nitrogen atmosphere, and 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Next, 72 parts of methacrylic acid, 7 parts 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 formula (II) were prepared. -1) The compound represented by mixing 50:50 at a molar ratio) 250 parts of a solution dissolved in 140 parts of ethyl lactate, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel. Inside.
另一方面,將已把聚合引發劑2,2’-偶氮雙(2,4-二甲基戊腈)30份溶解於乳酸乙酯95份而成的溶液,使用別的滴下漏斗以4小時的時間滴下於燒瓶內。當聚合引發劑的溶液完成滴下之後,於70℃下維持4小時,之後再冷卻至室溫,就可得到重量平均分子量Mw為7.0×103、分子量分佈為2.5、固形成份42%、固形成份酸值138mg-KOH/g的樹脂B1溶液。樹脂B1係具有以下所示之結構單元。 On the other hand, a solution obtained by dissolving 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate, and using another dropping funnel to 4 The hour was dripped into the flask. After the solution of the polymerization initiator was completed, it was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 7.0 × 10 3 , a molecular weight distribution of 2.5, a solid content of 42%, and a solid component. A resin B1 solution having an acid value of 138 mg-KOH/g. The resin B1 has the structural unit shown below.
在具備回流冷卻器、滴下漏斗及攪拌機的燒瓶內,以0.02L/分的速率通入氮氣以形成氮氣氛圍,加入乳酸乙酯220份,一面攪拌一面加熱至70℃。其次,調製將甲基丙烯酸10份、丙烯酸58份、丙烯酸3,4-環氧基三環[5.2. 1.02,6]癸酯(將式(I-1)所表示的化合物及式(II-1)所表示的化合物,以莫耳比50:50來混合)254份溶解於乳酸乙酯140份之溶液,將該溶解液使用滴下漏斗以4小時的時間滴下於保溫在70℃的燒瓶內。另一方面,將已把聚合引發劑2,2’-偶氮雙(2,4-二甲基戊腈)30份溶解於乳酸乙酯95份而成的溶液,使用別的滴下漏斗以4小時的時間滴下於燒瓶內。當聚合引發劑的溶液完成滴下之後,於70℃下維持4小時,之後再冷卻至室溫,就可得到重量平均分子量Mw為7.0×103、分子量分佈為2.5、固形成份41%、固形成份酸值136mg-KOH/g的樹脂B2溶液。樹脂B2係具有以下所示之結構單元。 In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at a rate of 0.02 L/min to form a nitrogen atmosphere, and 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Next, 10 parts of methacrylic acid, 58 parts 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 formula (II) were prepared. -1) the compound represented by mixing at a molar ratio of 50:50) 254 parts of a solution dissolved in 140 parts of ethyl lactate, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel. Inside. On the other hand, a solution obtained by dissolving 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate, and using another dropping funnel to 4 The hour was dripped into the flask. After the solution of the polymerization initiator was completed, it was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 7.0 × 10 3 , a molecular weight distribution of 2.5, a solid content of 41%, and a solid component. A resin B2 solution having an acid value of 136 mg-KOH/g. The resin B2 has the structural unit shown below.
在具備回流冷卻器、滴下漏斗及攪拌機的燒瓶內,以0.02L/分的速率通入氮氣以形成氮氣氛圍,加入乳酸乙酯220份,一面攪拌一面加熱至70℃。其次,調製將甲基丙烯酸84份、丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯(將式(I-1)所表示的化合物及式(II-1)所表示的化合物,以莫耳比50:50來混合)336份溶解於乳酸乙酯140份之溶液,將該溶解液使用滴下漏斗以4小時的時間滴下於保溫在70℃的燒瓶內。另一方面,將已把聚合引發劑2,2’-偶氮雙 (2,4-二甲基戊腈)30份溶解於乳酸乙酯95份而成的溶液,使用別的滴下漏斗以4小時的時間滴下於燒瓶內。當聚合引發劑的溶液完成滴下之後,於70℃下維持4小時,之後再冷卻至室溫,就可得到重量平均分子量Mw為8.0×103、分子量分佈為2.5、固形成份48%、溶液酸值50mg-KOH/g的樹脂B3溶液。若由上述的固形成份及溶液酸值來計算固形成份酸值,則為104mg-KOH/g。樹脂B3係具有以下所示之結構單元。 In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at a rate of 0.02 L/min to form a nitrogen atmosphere, and 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Next, 84 parts of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate (the compound represented by the formula (I-1) and the formula (II-1) were prepared. The compound shown was mixed at a molar ratio of 50:50. 336 parts of a solution dissolved in 140 parts of ethyl lactate, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel. On the other hand, a solution obtained by dissolving 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate, and using another dropping funnel to 4 The hour was dripped into the flask. After the solution of the polymerization initiator was completed, it was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 8.0 × 10 3 , a molecular weight distribution of 2.5, a solid content of 48%, and a solution acid. A resin B3 solution having a value of 50 mg-KOH/g. When the solid component acid value is calculated from the above solid content and the acid value of the solution, it is 104 mg-KOH/g. Resin B3 has the structural unit shown below.
在具備回流冷卻器、滴下漏斗及攪拌機的燒瓶內,以0.02L/分的速率通入氮氣以形成氮氣氛圍,加入乳酸乙酯305質量份,一面攪拌一面加熱至100℃。其次,調製將甲基丙烯酸90質量份、甲基丙烯酸苄酯210質量份溶解於乳酸乙酯140質量份之溶液,將該溶解液使用滴下漏斗以4小時的時間滴下於保溫在100℃的燒瓶內。另一方面,將已把聚合引發劑2,2’-偶氮雙(2,4-二甲基戊腈)30質量份溶解於乳酸乙酯225質量份而成的溶液,使用別的滴下漏斗以4小時的時間滴下於燒瓶內。當聚合引發劑的溶液完成滴下之後,於100℃下維持4小時,之後再冷卻至室溫,就可得到重量平均分子量Mw為1.2×104、分子量分佈 為2.2、固形成份30質量%、固形成份酸值154mg-KOH/g的樹脂B4溶液。樹脂B4係具有以下所示之結構單元。 In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at a rate of 0.02 L/min to form a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added thereto, and the mixture was heated to 100 ° C while stirring. Next, a solution in which 90 parts by mass of methacrylic acid and 210 parts by mass of benzyl methacrylate were dissolved in 140 parts by mass of ethyl lactate was prepared, and the solution was dropped into a flask kept at 100 ° C for 4 hours using a dropping funnel. Inside. 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, and using another dropping funnel It was dropped into the flask over 4 hours. After the solution of the polymerization initiator was dropped, it was maintained at 100 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.2 × 10 4 , a molecular weight distribution of 2.2, a solid content of 30% by mass, and solid form. A resin B4 solution having an acid value of 154 mg-KOH/g. Resin B4 has the structural unit shown below.
在合成例中所得到的樹脂之重量平均分子量(Mw)及數量平均分子量(Mn)的測定,係使用GPC法並利用以下的條件來進行。 The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example was carried out by the following conditions using the GPC method.
裝置:K2479((股份有限)島津製作所製) Device: K2479 (made by Shimadzu Corporation)
管柱(column):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:1.0mL/min Flow rate: 1.0mL/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(Toray(股份有限)製) Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (Toray (share limited) system)
利用上述所得到的聚乙烯換算出的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。 The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight converted from the polyethylene obtained above was used as the molecular weight distribution.
依據表1所示的組成,將各成份進行混合,就可得到著色感光性樹脂組合物。 According to the composition shown in Table 1, each component was mixed, and the colored photosensitive resin composition was obtained.
另外,在表1中的各成份係表示以下各物質。又,黏合劑樹脂(B)係以固形成份換算的質量份來表示。 In addition, each component in Table 1 shows the following each substance. Further, the binder resin (B) is represented by parts by mass in terms of solid content.
著色劑(A):(A-1);C.I.顏料藍15:6 Colorant (A): (A-1); C.I. Pigment Blue 15:6
著色劑(A):(A-2);染料A1 Colorant (A): (A-2); dye A1
著色劑(A):(A-3);式(1-39)所表示的化合物 Colorant (A): (A-3); a compound represented by formula (1-39)
黏合劑樹脂(B):(B-1);樹脂B1 Adhesive resin (B): (B-1); resin B1
黏合劑樹脂(B):(B-2);樹脂B2 Adhesive resin (B): (B-2); resin B2
黏合劑樹脂(B):(B-3);樹脂B3 Adhesive Resin (B): (B-3); Resin B3
黏合劑樹脂(B):(B-4);樹脂B4 Adhesive Resin (B): (B-4); Resin B4
聚合性化合物(C):(C-1);二季戊四醇六丙烯酸酯 (KAYARAD(註冊商標)DPHA;日本化藥(股份有限)製) Polymerizable compound (C): (C-1); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Kay (Pharmaceutical Co., Ltd.)
聚合引發劑(D):(D-1);N-苯甲酸基-1-(4-苯基硫基苯基)辛-1-酮-2-亞胺(IRGACURE(註冊商標)OXE 01;BASF公司製) Polymerization initiator (D): (D-1); N-benzoic acid-1-(4-phenylthiophenyl)oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF company)
聚合引發劑(D):(D-2);2-甲基-2-嗎啉代-1-(4-甲基硫基苯基)丙-1-酮(IRGACURE 907;BASF公司製) Polymerization initiator (D): (D-2); 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one (IRGACURE 907; manufactured by BASF Corporation)
聚合引發助劑(D1):2,4-二乙基噻噸酮(KAYACURE DETX-S;日本化藥(股份有限)製) Polymerization initiation aid (D1): 2,4-diethylthioxanthone (KAYACURE DETX-S; manufactured by Nippon Kayaku Co., Ltd.)
溶劑(E):(E-1);丙二醇一甲醚乙酸酯 Solvent (E): (E-1); propylene glycol monomethyl ether acetate
溶劑(E):(E-2);丙二醇一甲醚 Solvent (E): (E-2); propylene glycol monomethyl ether
溶劑(E):(E-3);乳酸乙酯 Solvent (E): (E-3); ethyl lactate
界面活性劑(F):(F-1);聚醚改質矽油(TORAY SILICON SH8400;Toray Dow Corning(股份有限)製) Surfactant (F): (F-1); Polyether modified eucalyptus oil (TORAY SILICON SH8400; Toray Dow Corning (limited by shares))
將2英吋(inch)角的玻璃基板(Eagle 2000;Corning公司製)依序利用中性洗潔劑、水及乙醇予以洗淨之後,乾燥之。再藉由自旋式塗佈法將著色感光性樹脂組合物塗佈於該玻璃基板上,接著置於潔淨烘爐中,在100℃下進行3分鐘的預烘烤處理。 A glass substrate (Eagle 2000; manufactured by Corning) having an angle of 2 inches was sequentially washed with a neutral detergent, water, and ethanol, and then dried. Further, the colored photosensitive resin composition was applied onto the glass substrate by a spin coating method, and then placed in a clean oven, and prebaked at 100 ° C for 3 minutes.
其次,浸漬於液溫25℃的顯影液(以質量分率而言,係為分別包含氫氧化鉀0.05%及丁基萘磺酸鈉0.2%的水溶液)中進行顯影,並以從基板的中心開始溶解完10mm部份之終了時間作為溶解時間。溶解時間若在20秒以下的話,溶解性就算良好。前述的著色感光性樹脂組合物即使是在 顯影時間很短的情況下,也可抑制殘渣等之顯影不良現象而能製作出著色圖形,故可謂產率非常高。其結果如表2所示。 Next, the developing solution immersed in a liquid temperature of 25 ° C (in terms of mass fraction, an aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalene sulfonate, respectively) was developed in the center of the substrate. The end time of the dissolution of the 10 mm portion was started as the dissolution time. When the dissolution time is 20 seconds or less, the solubility is good. The aforementioned colored photosensitive resin composition is even in When the development time is short, it is possible to suppress the development failure of the residue or the like and to produce a colored pattern, so that the yield is extremely high. The results are shown in Table 2.
於5cm角的玻璃基板(Eagle 2000;Corning公司製)上,將著色感光性樹脂組合物以自旋式塗佈法予以塗佈之後,於100℃下進行3分鐘預烘烤處理,而形成乾燥後塗膜。放冷後,令該已形成有乾燥後塗膜的基板跟石英玻璃製光罩之間間隔80μm,使用曝光機(TME-150RSK;Topcon(股份有限)製)於大氣氛圍下,以60mJ/cm2的曝光量(365nm基準)進行光照射。以光罩而言,係使用可形成100μm的線與間隙(line and space)圖形者。光照射後,將上述塗膜於25℃下浸漬於顯影液(以質量分率而言,係為分別包含氫氧化鉀0.05%及丁基萘磺酸鈉0.2%的水溶液)中60秒鐘進行顯影,水洗後,再於烘爐中進行230℃、30分鐘的事後烘烤處理,就可得到著色圖形。 The colored photosensitive resin composition was applied by a spin coating method on a glass substrate (Eagle 2000; manufactured by Corning) having a 5 cm angle, and then pre-baked at 100 ° C for 3 minutes to form a dry film. After the film. After cooling, the substrate having the dried coating film and the quartz glass mask were separated by 80 μm, and exposed to an atmosphere of 60 mJ/cm using an exposure machine (TME-150RSK; Topcon). The exposure amount of 2 (365 nm reference) was irradiated with light. In the case of a photomask, a line and space pattern which can form 100 μm is used. After the light irradiation, the coating film was immersed in a developing solution (in an amount of a mass fraction, an aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalenesulfon, respectively) at 25 ° C for 60 seconds. After development, washing with water, and then baking at 230 ° C for 30 minutes in an oven, a colored pattern can be obtained.
針對所得到的著色圖形,使用膜厚測定裝置(DEKTAK3;日本真空技術(股份有限)製)來測定膜厚。其結果如表2所示。 With respect to the obtained coloring pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.
針對所得到的著色圖形,使用掃描型電子顯微鏡(S-4000;(股份有限)日立High Technology製)來觀察形狀。若為下述(p1)所示的形狀(所謂的順錐度形狀)就打 ○,若為(p2)所示的形狀就打△,若為(p3)所示的形狀就打×。若為(p1)所示的形狀,則在著色圖形上沈積無機膜之際,就不容易於無機膜上產生龜裂及剝離。其結果如表2所示。 The shape of the obtained coloring pattern was observed using a scanning electron microscope (S-4000; manufactured by Hitachi High Technology Co., Ltd.). If it is the shape shown in the following (p1) (so-called straight tapered shape) ○ If it is the shape shown by (p2), it will be △, and if it is the shape shown by (p3), it will be ×. In the case of the shape shown by (p1), when an inorganic film is deposited on the colored pattern, cracking and peeling of the inorganic film are less likely to occur. The results are shown in Table 2.
針對所得到的著色圖形,使用測色機(OSP-SP-200;Olympus(股份有限)製)來測定分光,並使用C光源的特性函數來測定CIE的XYZ表色系中之xy色度座標(x,y)及三刺激值Y。若Y的值愈大,代表明亮度愈高。其結果如表2所示。 For the obtained coloring pattern, a color measuring machine (OSP-SP-200; Olympus Co., Ltd.) was used to measure the splitting, and the characteristic function of the C light source was used to measure the xy chromaticity coordinates in the XYZ color system of the CIE. (x, y) and tristimulus value Y. If the value of Y is larger, it means that the brightness is higher. The results are shown in Table 2.
除了將染料A1改為換成使用式(1-31)所表示的化合物以外,其餘步驟皆與實施例1~3相同,而分別得到著色感光性樹脂組合物。進行與前述相同的操作,確認了溶解性皆非常優異。進而得到明亮度及形狀皆優良的著色圖形。 The same procedure as in Examples 1 to 3 was carried out except that the dye A1 was changed to the compound represented by the formula (1-31), and a colored photosensitive resin composition was obtained. The same operation as described above was carried out, and it was confirmed that the solubility was extremely excellent. Further, a colored pattern excellent in both brightness and shape is obtained.
由上述的結果可確知,本發明的著色感光性樹脂組合物一方面具有優異的色性能及圖形形狀,另一方面在著色 圖形形成之際,對於顯影液的溶解性也非常高。因此可知,藉由本發明的著色感光性樹脂組合物,即可以高產率來製造出彩色濾光片。 From the above results, it is confirmed that the colored photosensitive resin composition of the present invention has excellent color properties and pattern shapes on the one hand, and coloring on the other hand. When the pattern is formed, the solubility to the developer is also very high. Therefore, it is understood that the colored filter can be produced in a high yield by the colored photosensitive resin composition of the present invention.
藉由本發明的著色感光性樹脂組合物,就可在著色圖形形成之際,令未曝光部對於顯影液具有高溶解性。 According to the colored photosensitive resin composition of the present invention, the unexposed portion can have high solubility to the developer when the colored pattern is formed.
Claims (5)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011049964 | 2011-03-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201243499A TW201243499A (en) | 2012-11-01 |
TWI566045B true TWI566045B (en) | 2017-01-11 |
Family
ID=46813466
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW101103847A TWI566045B (en) | 2011-03-08 | 2012-02-07 | Coloring the photosensitive resin composition |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6047885B2 (en) |
KR (1) | KR101929279B1 (en) |
CN (1) | CN102681345B (en) |
TW (1) | TWI566045B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102914943B (en) * | 2011-08-04 | 2018-01-12 | 住友化学株式会社 | Colored curable resin composition |
JP5776717B2 (en) * | 2013-03-18 | 2015-09-09 | コニカミノルタ株式会社 | Toner for developing electrostatic image, method for producing the same, and image forming method |
KR102375638B1 (en) * | 2014-07-29 | 2022-03-17 | 스미또모 가가꾸 가부시키가이샤 | Colored curable resin composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201022379A (en) * | 2008-10-28 | 2010-06-16 | Sumitomo Chemical Co | Method for producing colored composition |
TW201100486A (en) * | 2009-05-15 | 2011-01-01 | Toppan Printing Co Ltd | Coloring composition for color filter, color filter and liquid crystal display device using the same |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2460491A1 (en) * | 1974-12-20 | 1976-07-01 | Hoechst Ag | PROCESS FOR THE MANUFACTURING OF XANTHENE DYES |
JPH10148711A (en) * | 1996-11-20 | 1998-06-02 | Toyo Ink Mfg Co Ltd | Coloring composition for color filter, and color filter |
JP2002122987A (en) * | 2000-10-16 | 2002-04-26 | Kansai Paint Co Ltd | Negative photosensitive resin composition, negative photosensitive dry film, material obtained by using the composition and pattern forming method |
TW508985B (en) * | 2000-12-19 | 2002-11-01 | Kolon Inc | Method of using dry film photoresist to manufacture print circuit board |
JP4098550B2 (en) * | 2002-04-15 | 2008-06-11 | 富士フイルム株式会社 | Photosensitive resin composition and photosensitive transfer sheet |
JP2007156011A (en) * | 2005-12-02 | 2007-06-21 | Fujifilm Corp | Photosensitive resin composition for photo spacer, substrate with spacer, method for producing the same and liquid crystal display device |
JP2008024915A (en) * | 2006-06-23 | 2008-02-07 | Jsr Corp | Radiation-sensitive resin composition for use in spacer, spacer, and forming method thereof |
JP2008122924A (en) * | 2006-10-17 | 2008-05-29 | Jsr Corp | Radiation-sensitive resin composition for forming spacer, spacer and method for forming the same |
JP5205940B2 (en) * | 2006-12-22 | 2013-06-05 | 住友化学株式会社 | Photosensitive resin composition |
JP4748322B2 (en) * | 2007-03-01 | 2011-08-17 | Jsr株式会社 | Radiation-sensitive resin composition and method for forming spacer |
JP5137611B2 (en) * | 2007-03-28 | 2013-02-06 | 富士フイルム株式会社 | Colored curable resin composition, colored pattern forming method, colored pattern, method for producing color filter, color filter, and liquid crystal display element |
JP2009080194A (en) * | 2007-09-25 | 2009-04-16 | Fujifilm Corp | Polymerizable resin composition, transfer material, color filter and method for producing same, spacer for liquid crystal display device and method for producing the same, and liquid crystal display device |
JP2010015025A (en) * | 2008-07-04 | 2010-01-21 | Adeka Corp | Photosensitive composition containing specific photopolymerization initiator |
CN101625525B (en) | 2008-07-11 | 2013-06-12 | 住友化学株式会社 | Light-sensitive resin composition |
TWI464189B (en) * | 2008-11-14 | 2014-12-11 | Sumitomo Chemical Co | Hardened resin composition |
TWI475320B (en) * | 2009-02-13 | 2015-03-01 | Sumitomo Chemical Co | Coloring photo-seinsitive resin composition and color filter |
JP2010224204A (en) * | 2009-03-24 | 2010-10-07 | Sumitomo Chemical Co Ltd | Colored photosensitive resin composition |
TW201111447A (en) * | 2009-07-14 | 2011-04-01 | Sumitomo Chemical Co | Production method of pigment dispersion solution |
-
2012
- 2012-02-03 JP JP2012021776A patent/JP6047885B2/en active Active
- 2012-02-07 TW TW101103847A patent/TWI566045B/en active
- 2012-03-07 KR KR1020120023226A patent/KR101929279B1/en active IP Right Grant
- 2012-03-07 CN CN201210069251.6A patent/CN102681345B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201022379A (en) * | 2008-10-28 | 2010-06-16 | Sumitomo Chemical Co | Method for producing colored composition |
TW201100486A (en) * | 2009-05-15 | 2011-01-01 | Toppan Printing Co Ltd | Coloring composition for color filter, color filter and liquid crystal display device using the same |
Also Published As
Publication number | Publication date |
---|---|
JP2012198508A (en) | 2012-10-18 |
CN102681345A (en) | 2012-09-19 |
KR101929279B1 (en) | 2018-12-14 |
TW201243499A (en) | 2012-11-01 |
CN102681345B (en) | 2016-12-14 |
KR20120102531A (en) | 2012-09-18 |
JP6047885B2 (en) | 2016-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6713517B2 (en) | Red colored curable resin composition | |
TWI544035B (en) | Colored curable resin composition | |
TWI550347B (en) | Colored photosensitive resin composition | |
TWI733945B (en) | Colored curable resin composition, color filter formed from the colored curable resin composition and display device including the color filter | |
TWI578105B (en) | Coloring the photosensitive resin composition | |
TWI566041B (en) | Coloring the photosensitive resin composition | |
TWI566044B (en) | Coloring the photosensitive resin composition | |
TWI565759B (en) | Colored curable resin composition | |
TWI604271B (en) | Colored curable resin composition | |
TWI570507B (en) | Colored photosensitive resin composition | |
TWI566043B (en) | Coloring the photosensitive resin composition | |
TWI615680B (en) | Colored photosensitive resin composition | |
TWI575318B (en) | Coloring curable resin composition | |
TWI566045B (en) | Coloring the photosensitive resin composition | |
TW202204327A (en) | Phenothiazinyl compound and curable resin composition containing the same having excellent light resistance | |
JP2013050505A (en) | Colored photosensitive resin composition |