TW201243499A - Colored photosensitive resin composition - Google Patents
Colored photosensitive resin composition Download PDFInfo
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- TW201243499A TW201243499A TW101103847A TW101103847A TW201243499A TW 201243499 A TW201243499 A TW 201243499A TW 101103847 A TW101103847 A TW 101103847A TW 101103847 A TW101103847 A TW 101103847A TW 201243499 A TW201243499 A TW 201243499A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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Abstract
Description
201243499 四、指定代表圖: (一) 本案指定代表圖為:無。 (二) 本代表圖之元件符號簡單說明:無。 的化學式: 五、本案若有化學式時,請揭示最能顯示發明特徵 益 〇 4 « 六、發明說明: 【發明所屬之技術領域】 本發明係有關於一種著色感光性樹脂組合物。 【先前技術】 著色感光性樹脂組合物,係被廣泛應用於: 、.硬晶顯示 裝置、有機電致發光顯示裝置 '電漿顯示 命寻之顯示裝置 所使用的彩色濾光片的製造上。以此種著色感純樹脂组 合物而言,已知有:含有甲基丙烯酸及丙烯酸3 f環^美 三環[5. 2. 1. 〇2.6]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 )。 [專利文獻1]特開201 0-21 1 1 98號公報 【發明内容】 [發明所欲解決之課題] 習知以來皆知 用微影法來形成著 ’當將上述的著色感光性樹脂組合物利 色圖形之際,其未曝光部對於顯影液的 201243499 溶解性仍有無法充分地滿足需求之情形發生。 [用以解決課題之手段] 本發明係為提供以下[1 ]〜[6 ]所述物者。 [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: 來自曱基丙烯酸之結構單元、來自丙烯酸之結構單 元、以及來自可跟曱基丙烯酸和丙烯酸共聚合的單體之結 構單元。 [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。 [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、1〇〇質量%以下。 [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。 [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。 [6 ]顯示裝置,包括如[5 ]所述之彩色濾光片。 [發明的效果] 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。 201243499 【實施方式】 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: 來自曱基丙烯酸之結構單元、來自丙烯酸之結構單 元、以及來自可跟曱基丙烯酸和丙烯酸共聚合的單體之結 構單元。 本發明的著色感光性樹脂組合物,係含有著色劑 以著色劑(Α)而言,可舉例如:染料(Α1)及顏料(Α2),並以 為含有染料(A1)的著色劑較佳《以染料(a 1)而言,可舉例 如:油溶性染料、酸性染料、酸性染料之胺(ainine)鹽及酸 性染料之磺胺(SU 1 f onam i de)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N0TE(色染杜)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(az〇) 染料、蒽醌(anthraquinone)染料、三笨甲烷染料、咕噸 (xanthene)染料及醜菁(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。 具體而言,可舉例如下:C. I.溶劑黃(s〇ivent yellow)4(以下省略C. I.溶劑黃的敘述,僅列出號碼)、 201243499 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、18卜 207 、 218 、 222 、 227 、 230 ; 245 、 247 ; C. I.溶劑燈(solvent orange)2、7、11、15、26、56、 77 、 86 ; C. I.溶劑紫(solventviolet)ll、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)l、3、4、5、7、28、29、 32、33、34、35等之C. I.溶劑染料。 C. I.酸性黃(acid yellowM、3、7、9、U、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)l、4、8、14、17、18、26、27、 201243499 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(acidblue)l、7、9、15、18、22、23、25、 27 、 29 、 40 、 4卜 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)l、3、5、9、16、25、27、 28、41、50、58、63、65、80、104、105、106、109 等之 ‘ 38、 201243499 c. ι.酸性染料。 C. I.直接黃(direct yellow)2、33、34、35, 39、43、47、50' 54、58、68、69、70、71、86、93 95、 98、 102、 108、 109、 129、 136、 138、 141 ; C. I.直接紅(direct red)79、82、83、84、91、92 97、98、99、105、106、107、172、173、176、177、 181 、 182 、 184 ' 204 、 207 、 211 、 213 ' 218 、 220 、 222 、 232 、 233 、 234 、 241 、 243 ' 246 、 250 ; C. I.直接燈(direct orange)34、39、41、46、50 56 ' 57 ' 61 、 64 ' 65 ' 68 、 70 、 96 ' 97 ' 106 、 107 ; C. I.直接紫(direct violet)47、52、54、59、60 66、79、80、81、82、84、89、90、93、95、96、103、 C. I.直接藍(direct blue)l、2、6、8、15、22、25 4卜 57、71、76、77、78、80、8卜 84、85、86、90 94 、 95 ' 97 、 98 、 99 ' 100 、 101 、 106 、 107 、 108 、 113、 114、 115、 117、 119、 120、 137、 149、 150、 155 、 156 、 158 、 159 、 160 、 161 、 162 、 163 、 164 、 166 、 167 、 168 、 170 、 171 、 172 、 173 、 188 、 189 、 192、 193、 194、 195、 196、 198、 199、 200、 201、 203 、 207 、 209 、 210 、 212 、 213 、 214 、 222 、 225 、 228 、 229 、 236 、 237 、 238 、 242 、 243 、 244 、 245 、 247 、 248 、 249 、 250 、 251 、 252 、 256 、 257 、 259 、 268 、 274 、 275 、 293 ; C. I.直接綠(direct green)25、27、31 ' 32 、94、 ' 96 ' 179 > 221、 > 52 ' 、65、 104 ; 、40、 、93、 109、 153、 165、 190、 202、 226、 246、 260、 、34 ' 201243499 37、63、65、66、67、68、69、72、77、79、82 等之 C. I. 直接染料。 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)l、14、56、60 ; C. I.基本紅(basicred)l、10; C. I.基本藍(basic blue)l、3、5、7、9、19、21、 22、24、25、26、28、29、40、4卜 45、47、54、58、59、 60 、 64 、 65 、 66 、 67 、 68 ; C. I.基本綠(basicgreen)l;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) 1 6 ; C. I.活性紅(r e a c t i v e r e d) 3 6 ;等之C. I.活性染 料、 C. I.酸性媒介黃(mordant yellow )5、8、10、16、 20 、 26 、 30 、 3卜 33 、 42 、 43 、 45 、 56 、 6卜 62 、 65 ; C. I.酸性媒介紅(mordantred)l、2、3、4、9、11、12、 14 、 17 、 18 、 19 、 22 、 23 、 24 、 25 、 26 、 27 、 30 、 32 、 33 、 36、37、38、39、4卜 43、45、46、48、53、56、63、7卜 74 、 85 、 86 、 88 、 90 、 94 、 95 ; C. I.酸性媒介燈(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)l、2、4、5、7、14、 8 201243499 22、24、30、31、32、37、40 ' 41、44 ' 45、47、48、53 58 ; C. I.酸性媒介藍(mordant blue)l ' 2、3、7、8、9、12 13、15、16、19、20、21、22、23、24、26、30、3卜 32 ' 39、40、4卜 43、44、48、49、53、6卜 74、77、83、84 ; 、10 、 15 、 I.酸性媒介綠(mordant green) 1、3、4、 酸性媒 19、26、29、33、34 ' 35、4卜 43、53 等之 C. I. 介染料、 C. I.還原綠(vat green)i等之c. ΐ·還原染料等等。 以染料(Α1)而言’係以咕噸染料(Aa)為較佳。 咕B頓染料(Aa)係為含有具有咕噸骨幹之化合物的染 料。 卞 以咕嘲染料(Aa)而言,可舉例如:C. !.酸性紅51 52、87、92、94、289、388 ; C. I.酸性紫 9、3〇、1〇2 C. I.基本紅 1(若丹明 6G,Rhodamin6G)、2'3、 C· I.基本紅 1〇(若丹明 B,Rhodamiη B)、11 ·,c 酉曼性媒介紅 本紫 10、11、25 ; C. I.溶劑紅 218 ; 27 ; C· I.活性紅36(Rose Bengal B);磺醯若丹明 G(SuIforhodamine);特開201 0-32999號公報所揭露之咕 噸染料及特許第4492 760號所揭露之咕噸染料等。 以咕嘲染料(Aa)而言,係以使用含有 广八U )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)。佶田人 災用化合物(i) 時,相對於咕β頓染料(A a)的總量之化合物(1)的含有θ係、 201243499 50質量%以上較佳、7〇質量 上旯佳、90質量%以上特佳。 尤其疋’以實質上僅使用化 。初U )來作為咕噸染料Γ 較佳。201243499 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. Chemical formula: 5. If there is a chemical formula in this case, please reveal the characteristics of the invention. 益 4 4 6. Description of the Invention: [Technical Field of the Invention] The present invention relates to a colored photosensitive resin composition. [Prior Art] The colored photosensitive resin composition is widely used in the production of a color filter used in a hard crystal display device or an organic electroluminescence display device. In the case of such a color-sensing pure resin composition, a copolymer containing methacrylic acid and acrylic acid 3 f ring-tricyclic [5. 2. 1. 〇2.6] oxime ester is known as a coloring sensitivity of a resin. Resin composition (Patent Document 1). [Problem to be Solved by the Invention] It is known that lithography is used to form 'when the above-mentioned colored photosensitive resin is combined In the case of the profit-colored pattern, the unexposed portion of the unexposed portion of the developer may not sufficiently satisfy the demand for 201243499 solubility. [Means for Solving the Problem] The present invention provides the following items [1] to [6]. [1] The colored photosensitive resin composition 'includes: a colorant, a binder resin, a polymerizable compound, and a polymerization initiator; the binder resin is a binder resin including 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 mercaptoacrylic acid and acrylic acid. [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] The colored photosensitive resin composition according to the above [1], wherein the content of the copolymer is 10% by mass or more and 1% based on the content of the binder resin. Below mass%. [4] The colored photosensitive resin composition according to [1], [2] or [3], wherein the coloring agent is a coloring agent including a dye. [5] The color filter ' is formed of the colored photosensitive resin composition as described in [1], [2], [3] or [4]. [6] A display device comprising the color filter as described in [5]. [Effects of the Invention] 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. 201243499 [Embodiment] 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 a binder resin (B) It is a binder resin comprising a copolymer having the following structural units: a structural unit derived from methacrylic acid, a structural unit derived from acrylic acid, and a structural unit derived from a monomer copolymerizable with acryl acrylic acid and acrylic acid. The colored photosensitive resin composition of the present invention contains a coloring agent, and examples of the coloring agent include a dye (Α1) and a pigment (Α2), and a coloring agent containing the dye (A1) is preferred. Examples of the dye (a 1) include dyes such as an oil-soluble dye, an acid dye, an ainine salt of an acid dye, and a sulfonamide (SU 1 f onam i de) derivative of an acid dye, for example, color. The dyes described in the index (Color Index, published by The Society of Dyers and Colourists), that is, a compound having a hue other than a pigment, and a known dye described in N0TE (dye). Further, depending on the chemical structure, for example, an azo (az〇) dye, an anthraquinone dye, a tris-methane dye, a xanthene dye, and a phthalocyanine dye may be mentioned. The above dyes may be used singly or in combination of two or more. Among the above, 'the organic solvent soluble dye is preferred. Specifically, it can be exemplified as follows: CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, only the number is listed), 201243499 14' 15' 23' 24' 38' 62' 63' 68' 82' 94, 98' 99' 117' 162 ' 163 ' 167 ' 189 ; C · I. solvent red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 18 207, 218, 222, 227, 230; 245, 247; solvent solvent 2, 7, 11, 15, 26, 56, 77, 86; CI solvent violet (solventviolet) ll, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; 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, CI solvent dyes of 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. CI acid yellow (acid yellowM, 3, 7, 9, U, 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 l, 4, 8, 14, 17, 18, 26, 27, 201243499 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, 3 15, 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 acidblue l, 7, 9, 15, 18, 22, 23, 25, 27, 29, 40, 4, 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 (a Cid green) l, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. ' 38, 201243499 c. ι. Acid dye . CI direct yellow 2, 33, 34, 35, 39, 43, 47, 50' 54, 58, 68, 69, 70, 71, 86, 93 95, 98, 102, 108, 109, 129, 136, 138, 141; CI direct red (79, 82, 83, 84, 91, 92 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 181, 182, 184 ' 204, 207, 211, 213 '218, 220, 222, 232, 233, 234, 241, 243 '246, 250; direct direct orange 34, 39, 41, 46, 50 56 ' 57 ' 61 64 ' 65 ' 68 , 70 , 96 ' 97 ' 106 , 107 ; CI direct violet 47, 52, 54, 59, 60 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, CI direct blue, 2, 6, 8, 15, 22, 25 4, 57, 71, 76, 77, 78, 80, 8, 84, 85, 86, 90 94 , 95 ' 97 , 98 , 99 ' 100 , 101 , 106 , 107 , 108 , 113 , 114 , 115 , 117 , 119 , 120 , 137 , 149 , 150 , 155 , 156 , 158 , 159 , 160 , 161 , 162 , 163, 164, 166, 167, 168, 170, 1 71, 172, 173, 188, 189, 192, 193, 194, 195, 196, 198, 199, 200, 201, 203, 207, 209, 210, 212, 213, 214, 222, 225, 228, 229, 236, 237, 238, 242, 243, 244, 245, 247, 248, 249, 250, 251, 252, 256, 257, 259, 268, 274, 275, 293; CI direct green 25, 27 , 31 ' 32 , 94 , ' 96 ' 179 > 221 , > 52 ' , 65 , 104 ; , 40 , , 93 , 109 , 153 , 165 , 190 , 202 , 226 , 246 , 260 , , 34 ' 201243499 CI direct dyes of 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. CI disperse yellow 51, 54, 76; CI disperse violet 26, 27; CI disperse blue l, 14, 56, 60; CI basic red l, 10; CI Basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 4, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68; CI basic green l; etc. CI basic dye, CI reactive yellow 2, 76, 116; CI active orange 1 6 ; CI active red (reactivered 3 6 ; etc. CI reactive dyes, CI acid medium yellow (mordant yellow) 5, 8, 10, 16, 20, 26, 30, 3, 33, 42 , 43 , 45 , 56 , 6 , 62 , 65 ; CI acid medium red (moldantred) 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37 , 38, 39, 4, 43, 45, 46, 48, 53, 56, 63, 7 Bu 74, 85, 86, 88, 90, 94, 95; CI acid medium lamp (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 acid medium purple (mordant Violet)l,2,4,5,7,14,8 201243499 22,24,30,31,32,37,40 '41,44 '45,47,48,53 58 ; CI acid medium blue (mordant blue ) l ' 2, 3, 7, 8, 9, 12 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 3, 32 '39, 40, 4, 43, 44, 48, 49, 53, 6 b 74, 77, 83, 84 ; , 10 , 15 , I. acidic green 1, 3, 4, acidic medium 19, 26, 29, 33, 34 ' 35, 4, such as CI, 43, 53 and so on, CI, vat green, etc. c. ΐ· vat dyes, etc. In the case of the dye (Α1), it is preferred to use a xanthene dye (Aa). The 咕Bton dye (Aa) is a dye containing a compound having a xanthene backbone.而言 咕 染料 染料 dye (Aa), for example: C. !. Acid red 51 52, 87, 92, 94, 289, 388; CI acid purple 9, 3 〇, 1 〇 2 CI basic red 1 ( Rhodamine 6G, Rhodamin 6G), 2'3, C·I. Basic Red 1〇 (Rhodamiη B), 11 ·, c 酉曼性性红本紫10,11,25; CI Solvent Red 218 ; 27 ; C · I. Reactive Bengal B; Su for 丹 明 G ; ( ( ( ( ; ; ; ; ; 201 201 201 201 201 201 201 201 201 201 201 201 201 201 201 201 201 201 201 449 449 449 449 449 449 449 449 449 449 449 449 449 449 449 449 449 449 449 449 449 449 Xenon dyes, etc. In the case of the oxime dye (Aa), a dye containing a compound (hereinafter also referred to as "compound (1)") represented by K. The compound (1) can also be a tautomer thereof. In the case of the Putian human disaster compound (i), the compound (1) with respect to the total amount of the 咕β dye (A a) contains θ system, 201243499 50% by mass or more, 7 〇 quality, and 90 mass. More than %. In particular, 疋' is essentially only used. It is preferred that the initial U) is used as a xanthene dye.
ιΘ a(x6) (1) [式⑴中’ R 分別獨立地表示氫原子、碳數卜Μ 價飽和烴基或碳數6〜10的1價芳香族烴基;該芳香族煙基 所含有的氫原+,也可以用後述官能基來予以取代: 原子、一R8、一 〇U —CChH、一 CO2 -OR8、 C〇2R8 S〇3' -SR' SChH、一 S〇3~ M S〇2R8 、 - S〇3R8 或 S〇2NR9Rie。前述飽和烴基所含有的氫原子也可以用碳數 6~10的芳香族烴基或_素原子來予以取代,而該芳香族炉 基所含有的氫原子,亦可用碳數卜3的烧氧基來予以: 代;前述飽和烴基所含有的—CL—,也可以用_〇—、〜 C0—或—來予以取代。Rl&只2亦、可為同時形成含有 氮原子的環’ R及R4也可為同時形成含有氮原子的環。 R5係表示一〇H C〇2_M+、一CO# S〇3、一 SChH、一 SO; s〇3r8 或一s〇2nr9r10 C〇2h、 m係表示0〜5的整數。當m為2以上時,複數的κ 相同或相異。 R及R係分別獨立地表示氫原子或碳數i ~ 6的烷基。 M+係表示 1(RH)4、Na+或 K+。 10 201243499 X係表示ii素原子。 a係表示〇或1的整數。 R係表示碳數1 ~ 2 0的1價飽和煙基,該飽和烴基所含 有的氫原子’也可以用齒素原子來予以取代。 R係分別獨立地表示氫原子 '碳數1〜2 〇的1價飽和 烴基或碳數7〜10的芳烷基。 R及R1(1係分別獨立地表示氫原子、或碳數卜2〇的工 杨飽和fe基,該飽和烴基所含有的氫原子,也可以用羥基 或i素原子來予以取代;該飽和脂肪族烴基所含有的—Cl 也可以用一0 CO- 、一NH—或—NR8—來予以取 代,R及R亦可互相地結合而形成為含有氮原子的^ 〇 圓環之複數環。] .以中碳數6〜10的丨價芳香族烴基而言,可舉例 如:苯基、曱苯醯基(toiuyi)、二甲苯基(xylyl)、三甲笨 基(mesityl)、丙基苯基及丁基苯基等。 中碳數的!價芳香族煙基,以其取代基而 言’係以具有擇自由m〇3H、—SOr M+及—so峨|。 所構成的族群中至少1種者為較佳,並以具有擇自由—S〇3 r及—崎。所構成的族群中至幻種者為更佳。以此 情形的-s〇3-r而言,係以為—s〇r +叫較佳。 右為上述等之官能基’則從含有化合物⑴的本發明之著色 優異的彩色渡光片。’成極少產生異物、且耐熱性 針對以卩2㈣形成n及以“時形成之 11 201243499 環而s,可舉例如以下所列示者。 人 ,〇,〇 吒兮.¾ 以R〜R4、R8〜R1I中碳數卜20的1價飽和烴基而言可 舉例如.曱基、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、二十烷基等之碳數卜2〇 的烷基;環丙基、環戊基' 環己基、環庚基、環辛基、三 垓癸基等之碳數3~20的脂環式飽和烴基。 以一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 基及一十院氧基等。 以一C〇2R8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。 以一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。 以一so#而言,可舉例如:曱磺醯基(methylsulf〇nyl)、 乙石頁醯基、丁磺醯基、己磺醯基、癸磺醯基及二十烷磺醯 基。 以一SOW而言,可舉例如:甲氧磺醯基(meth〇xysulf〇nyl)、 己氧磺醯基、丙氧磺醯基、第3-丁氧磺醯基、己氧磺醯基 及二十烧氧確醯基。 以一s〇2NR9R!°而言,可舉例如:氨磺醯基(sulfam〇yl); N-曱基氨磺醯基、N-乙基氨磺醯基、N_丙基氨磺醯基、N_ (¾ 12 201243499 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-(卜乙基丙基)氨磺醯基' N_〇,卜二曱基丙基)氨 sSk基N(l,2-一甲基丙基)氨確酿基、N_(2,2-二甲基丙 基)氨磺醯基、N—G 一甲基丁基)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, 3一 二曱基丁基)氨磺醯基、N_庚基氨磺醯基、N_(卜甲基己基) 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)氨續醯基、Ν_(ι,5_二甲基)己基氨績 醯基、N-(l,l,2,2-四甲基丁基)氨磺醯基等之N_i取代氨 磺醯基; N,N-二甲基氨磺醯基、n,N-乙基曱基氨磺醯基、N,N_二乙 基氨磺醯基、N,N-丙基曱基氨磺醯基、n,N-異丙基曱基氨 石黃醯基、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-曱基丙基)氨續醯基、n,n -庚基甲基氨石黃 醯基等之N,N-2取代氨磺醯基等等。 又’關於R及R1。所表示的碳數1〜2 〇的1價飽和烴基, 該飽和组基所含有的氫原子,也可以用~ 或_素原子來 予以取代,s亥飽和烴基所含有的—CH2—,也可以用—〇—、 —C0一、一 NH —或—NR8—來予以取代。 R9及R1Q ’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。 13 201243499 - so; S〇3- so「r、—s〇3h _S〇3H 或 s〇2nhr9 r5 係以為—~c〇2H、_C()2R8 或S〇2NHR9較佳,並以為〜s〇2 更佳® m係以為1 ~ 4較# „ 以R6及h 為1或2則更佳。 石灭數1〜6的烷基而十, 列舉的烷基之中,碳數為1 6者 了舉例如:前述所 以R11中碳數7〜1〇 料 的方炫*基而言,可掇办丨, 笨乙基、笨丁基等。 了舉例如:苄基、 M+係為 +N(Rn)4 a或尺,並以a+m,d11、 以1〇r)4而言,俜 為N(R )4較佳。 % u 4個β11之中$ j 的1價飽和烴基為舫杜 王〉、2個為碳數5〜20 … 佳。又,4個r〗ι 2〇~80較佳、2〇〜6〇 的合計碳數係以為 時,Ο為上述等之^ #化合物⑴中存在有 著色感光性樹脂组合物化合物⑴的本發明之 光片。 ρ可形成異物極少的彩色濾 化合物(1 )係以為下滅 M A r " (2)中所表示的化合物(以下也 %為「化合物(2))輕# A人古#人 而以咕噸染料(Aa)而言,係以 為含有化合物(2)的毕粗毋& 心 4更佳。化合物(2)也可為其互變異 構體。使用化合物(2)瞎,μ *, 丹立艾共 人 、咕噸染料(Aa)中之化合物(2)的 3有里係以50質量%以上較佳、 量%以上特佳。尤P,、乂 上更佳、9〇質 /、疋以早獨使用化合物(2)來作為咕噸 染料(A a)特佳。 Γ® 14 (2)201243499Θ a (x6) (1) [In the formula (1), R independently represents a hydrogen atom, a carbon number divalent saturated hydrocarbon group or a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10; hydrogen contained in the aromatic group The original + can also be replaced by a functional group described below: atom, a R8, a 〇U-CChH, a CO2-OR8, a C〇2R8 S〇3'-SR' SChH, a S〇3~MS〇2R8, - S〇3R8 or S〇2NR9Rie. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a γ atom, and the hydrogen atom contained in the aromatic furnace group may be an alkoxy group having a carbon number of 3 To give: the above-mentioned saturated hydrocarbon group -CL-, can also be replaced by _〇-, ~ C0- or -. Rl & only 2, may also form a ring containing nitrogen atoms R and R4 may also form a ring containing a nitrogen atom. R5 represents an 〇H C〇2_M+, a CO# S〇3, an SChH, a SO; s〇3r8 or a s〇2nr9r10 C〇2h, and the m system represents an integer of 0 to 5. When m is 2 or more, the complex κ is the same or different. R and R each independently represent a hydrogen atom or an alkyl group having a carbon number of i to 6. The M+ system represents 1 (RH) 4, Na+ or K+. 10 201243499 X is a ii atom. a is an integer representing 〇 or 1. R is a monovalent saturated nicotine group having a carbon number of 1 to 20, and a hydrogen atom contained in the saturated hydrocarbon group can be substituted with a fang atom. R-series independently represent a hydrogen atom 'a monovalent saturated hydrocarbon group having 1 to 2 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. R and R1 (1) each independently represent a hydrogen atom or a carbon number of 2, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a hydroxyl group or an i atom; the saturated fat The -Cl contained in the group hydrocarbon group may be substituted by a 0 CO-, a NH- or -NR8-, and R and R may be bonded to each other to form a plural ring of a ring containing a nitrogen atom.] The valence aromatic hydrocarbon group having a carbon number of 6 to 10 may, for example, be a phenyl group, a toryl group, a xylyl group, a methylate group or a propylphenyl group. And butyl phenyl, etc. The carbon number of the aromatic smog group, in terms of its substituents, is selected to have at least 1 in the group consisting of m〇3H, -SOr M+ and -so峨|. The species is better, and it is better to use the genus of the genus of the singularity - S〇3 r and - saki. In this case, the -s〇3-r is considered to be -s 〇r + is preferred. The right is the functional group of the above, and the colored light-emitting sheet excellent in coloring of the present invention containing the compound (1) is produced. For the formation of n by 卩2 (4) and the formation of 11 201243499 ring by "time", for example, the following list is listed. Person, 〇, 〇吒兮.3⁄4 to R~R4, R8~R1I carbon number Examples of the monovalent saturated hydrocarbon group include a mercapto group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a heptyl group, and an octyl group. An alkyl group having a carbon number of 2-ethylhexyl, nonyl decyl, dodecyl, hexadecyl or eicosyl; cyclopropyl, cyclopentyl 'cyclohexyl, cycloheptyl An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclooctyl group or a tridecyl group. Examples of an OR8 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyl group. An oxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a ten-yard oxy group, etc. The mono-C 〇 2R8 may, for example, be a methoxycarbonyl group or an ethoxycarbonyl group. a propoxycarbonyl group, a 3-butoxycarbonyl group, a hexyloxycarbonyl group, an eicosyloxycarbonyl group, etc. Examples of a SR8 include a methylsulfanyl group, an ethylthio group, a butylthio group, and a hexylthio group. , thiol and eicosylthio. In the case of a so#, for example, methylsulf〇nyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, sulfonyl and eicosylsulfonyl. For SOW, for example, meth〇xysulf〇nyl, hexyloxysulfonyl, propoxysulfonyl, 3-butoxysulfonyl, hexyloxysulfonyl and Oxygen is confirmed to be a base. For a s〇2NR9R!°, for example, sulfam〇yl; N-mercaptosulfonyl, N-ethylsulfamoyl, N_ Propylsulfonyl, N_ (3⁄4 12 201243499 isopropylsulfonyl, N-butylsulfonyl, N-isobutylsulfonyl, N-butylsulfonamide, n - 3_butylsulfamoyl, N-pentylsulfonyl, N-(iethylpropyl)sulfamoyl 'N_〇, bis-dipropylpropyl) ammonia sSk-based N (l, 2-monomethylpropyl)Ammonia, N_(2,2-dimethylpropyl)sulfamoyl, N-G-methylbutylsulfonamide, N-(2-A Aminosulfonyl, N-(3-methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfonyl, N_(1,3-dimethyl Alkyl sulfonate 'N_(3,3,2-didecylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(b-methylhexyl)sulfonyl, N-(1,4-dimethylpentyl) Ammoxime, N-octylsulfamoyl, N-(2-ethylhexyl)arene, Ν_(ι,5-dimethyl)hexylamino, N-(l, N,i substituted sulfonamide, such as 1,2,2-tetramethylbutyl)sulfonamide; N,N-dimethylsulfamoyl, n,N-ethylmercaptosulfonyl, N,N-diethylammonsulfonyl, N,N-propyldecylsulfonyl, n,N-isopropylmercaptoguanidinyl, N,N-tert-butylmethylsulfazone N,N-N-butylethylsulfamoyl, N,N-bis(1-mercaptopropyl)arene, n,n-heptylmethylcarbamate, etc. 2 replaces amsulfoxinyl and the like. Also, about R and R1. The monovalent saturated hydrocarbon group having a carbon number of 1 to 2 Å, and the hydrogen atom contained in the saturated group may be substituted with a ~ or a γ atom, and the -CH 2 - contained in the saturated hydrocarbon group may also be used. Replace with -〇-, -C0-, one-NH- or -NR8-. R9 and R1Q' 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 ones listed below. 13 201243499 - so; S〇3- so "r, -s〇3h _S〇3H or s〇2nhr9 r5 is considered to be -~c〇2H, _C()2R8 or S〇2NHR9 is better, and thinks ~s〇2 Better ® m is considered to be 1 ~ 4 compared to # „ R6 and h are preferably 1 or 2. The number of carbon atoms in the alkyl group is 1 to 6 and 10, and among the alkyl groups listed, the number of carbon atoms is 16, for example, the above-mentioned formula R11 has a carbon number of 7 to 1 Do it, stupid ethyl, stupyl butyl, etc. For example, a benzyl group, an M+ system is +N(Rn)4a or a ruler, and a+m, d11 and 1〇r)4 are preferable, and 俜 is N(R)4. Among the four β11, the j-valent monovalent saturated hydrocarbon group of $j is 舫Duwang>, and the two are carbon number 5~20. In addition, the present invention of the present invention in which the coloring photosensitive resin composition compound (1) is present in the above-mentioned compound (1) is the same as the total number of carbon atoms in the range of 4 to 6 in the range of 2 to 6 Light film. ρ can form a color filter compound (1) with a minimum of foreign matter, and is a compound represented by (2) (hereinafter also referred to as "compound (2)) light #A人古#人以咕吨In the case of the dye (Aa), it is more preferred to contain the compound (2), and the compound (2) is also a tautomer thereof. The compound (2) 瞎, μ*, Dan Li is used. In the case of the compound (2) of the Ai's people and the xanthene dye (Aa), it is preferably 50% by mass or more, more preferably more than 5% by weight, especially P, 乂, 9 〇, 疋It is particularly good to use compound (2) as a xanthene dye (A a) in the early days. Γ® 14 (2)201243499
R24 · 心.R23 (xa [式(2)中,R21 〜、 係为別獨立地表 6〜10的1價芳香族烴基;該芳#;^風原子、—R或碳數 也可以用後述夫、工基所含有的氫原子, ςπΗ …基來予以取代…抓so「r+、 SO3H ' — SDoP26 -V-' n OU3 Μ — ύυ3Κ 或—s〇2NHR26。 χβ係表示南素原子。 al係表示〇或1的整數。 複 係表示〇〜5的整|& 數的〜同或相異。 為2以上的整數時R24 · Heart. R23 (xa [In the formula (2), R21 〜 is a monovalent aromatic hydrocarbon group of Tables 6 to 10 independently; the aryl#; ^ wind atom, -R or carbon number can also be used later The hydrogen atom contained in the work base is replaced by a ςπΗ ... group. So, "r+, SO3H' - SDoP26 -V-' n OU3 Μ - ύυ3Κ or -s〇2NHR26. χβ is a ruthenium atom. 〇 or an integer of 1. The complex system represents the same or different integers of 〇~5. When it is an integer of 2 or more
Ma+係表示+ N(R27)4、Na+或 K+。 R 係表示一S〇3- ' —ςη,- iwa + d2 Q3 M 、1〇3Η 或 s〇2NHR26。 >27 係表示碳數卜20的1價飽和烴基。 基 係分別獨立地表示碳數㈣的1價飽和烴基或节 MR f中碳數6〜1〇的1價芳香族烴基 如:跟I?1 』口 1舉例 R〜R中方香族烴基所列舉出之官能基相同者。 其中’以R21~R24的組合而言,較佳者為:P及R23主 其且〜、碳數6〜10的1價芳香族烴基;該芳 、、基所含有的氫原子,也可以用—so「、〜 〜S〇3H、— S〇3R26 或—8〇2〇1?26來 3 、 R21及取代更佳者則為: 為氲原子,且r22及r24為碳數6〜1〇 Α 1貝方香族 15 201243499 ι基,a方香族烴基所含有的 ^ _C〇 NUP20 . 乳原子也可以用—S〇rM + 或s〇2nhr來予以取代。R2 從今右仆入此 右為上迹專之官能基,則 。⑵的本發明之著色感純 看’即可形成耐熱性優異的彩色滤光片。… 以R26及R”中碳數卜20^價飽和 如:…中飽和烴基所列舉出之官能基7舉例 當 R 1〜R24 為一R26 時,—R2> \ 甲基或乙基較佳。 ‘以分別獨立地為氣原子、 以-S〇3R26 及—S〇2NHR2e 沾八± M Τ < Κ而吕,係以為碳數3〜20 的分支鏈狀烷基較佳、碳數 12的为支鏈狀烷基更佳、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)的者色感光性樹脂組 物的彩色濾光片。 &來看,即可形成極少產生異 M8+ 係為 +N(R27)4、Na+ 式 + Μ或Κ ,並以+N(R2、為較佳。 以N(R27)4而言,係以4個R27 士 個R之中至少2個為碳數5〜20 的1價飽和烴基為較佳。7 9n 佳又,4個R27的合計碳數係以為 20〜80較佳、20〜60更祛。人 备化合物(2)中存在有+N(R27)4The Ma+ system represents + N(R27)4, Na+ or K+. R represents an S〇3-'-ςη, -iwa + d2 Q3 M , 1〇3Η or s〇2NHR26. >27 represents a monovalent saturated hydrocarbon group of carbon number. The base system independently represents a monovalent saturated hydrocarbon group having a carbon number (d) or a monovalent aromatic hydrocarbon group having a carbon number of 6 to 1 Å in the rhythm of the MR f. For example, the ring of the aromatic hydrocarbon group of R 1 to R 1 is exemplified. The functional groups are the same. In the combination of R21 to R24, preferred are: P and R23, and a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10; and a hydrogen atom contained in the aryl group or the group may be used. —so“,~~S〇3H, —S〇3R26 or —8〇2〇1?26 to 3, R21 and the more preferred ones are: 氲 atoms, and r22 and r24 are carbon numbers 6~1〇 Α 1 Bayfang fragrant 15 201243499 ι, a _C〇NUP20 contained in a square aromatic hydrocarbon group. The milk atom can also be replaced by -S〇rM + or s〇2nhr. R2 is now right from here. In the case of the above-mentioned functional group, the color perception of the present invention (2) can be formed as a color filter which is excellent in heat resistance.... It is saturated with carbon number in R26 and R", such as: The functional group 7 exemplified for the saturated hydrocarbon group is exemplified by the fact that when R 1 to R24 are a R26, -R2>\methyl or ethyl is preferred. 'is independently a gas atom, with -S〇3R26 and -S〇2NHR2e 八8± M Τ < Κ 吕 ,, is a branched chain alkyl group having a carbon number of 3 to 20, preferably having a carbon number of 12 It is more preferably a branched alkyl group and a 2-ethylhexyl group. When R26 is a functional group such as the above, a color filter of a photosensitive resin composition containing the compound (2) is used. & look, it can form very little difference M8 + is +N (R27) 4, Na + + Μ or Κ, and +N (R2 is preferred. For N (R27) 4, It is preferable that at least two of the four R27 and R are a monovalent saturated hydrocarbon group having a carbon number of 5 to 20, and the total carbon number of the four R27 is preferably 20 to 80, more preferably 20 to 60.祛. There is +N(R27)4 in the compound (2).
時’R 若為上述等之官妒Α ο I 吕月b基’則從含有化合物(2)的本發 明之者色感光性樹脂組合物氺善 |。物來看,即可形成極少產生異物 的彩色濾光片。 以化合物⑴而言,可舉例如:下述式(卜式。— 3_表示的化合物。另外,在下述式中,Ra係表示碳數 Μ的1價飽和煙基’並以為碳數的分支鏈狀烧基 更佳、2_乙基己基則特佳°在上述等物質之中,又以C. I. 16 201243499 酸性紅2 8 9的石黃胺化合物、「τ I.酸性紅289的4級康趟、 C. I·酸性紫102的磺胺仆入仏 、及虱虞 級氨鹽為較s c. h酸性紫102的4 式(丨—丨) "員的化合物而言,可舉例如:如 厂式。—8)、式(1— ln七斗,, 物等。 )或式(丨―12)所表示的化合In the case of the above-mentioned official ο I 吕 吕 吕 I I 吕 吕 吕 吕 吕 吕 吕 吕 从 吕 从 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In terms of matter, a color filter that generates little foreign matter can be formed. In the compound (1), for example, a compound represented by the following formula (abbreviation: -3_), and in the following formula, a Ra system represents a monovalent saturated nicotinyl group having a carbon number of ' and a branch having a carbon number The chain-shaped alkyl group is more preferable, and the 2-ethylhexyl group is particularly preferred. Among the above substances, the hydrofluorin compound of CI 16 201243499 acid red 289 is used, and the τ I. acid red 289 grade 4 Kang The sulfonamide oxime and the sulfonium-grade ammonium salt of 趟, C. I·Acid Violet 102 are compounds of the formula (丨-丨) of the s c. h Acid Violet 102, for example: Such as the factory type. - 8), the formula (1 - ln seven buckets,, things, etc.) or the formula (丨 - 12)
ho3sHo3s
(1-6) 17 201243499(1-6) 17 201243499
(1-9) ho3s(1-9) ho3s
S〇3S〇3
(1-13) (1-10)(1-13) (1-10)
ΛΛ
S〇3 (1-15)S〇3 (1-15)
A (1-14)A (1-14)
(1-16) rs 18 201243499(1-16) rs 18 201243499
AA
(1-20) (1-19)(1-20) (1-19)
(1-22)(1-22)
(1-21)(1-21)
(1-23) 19 201243499(1-23) 19 201243499
示的化合物(以下也稱為「化合物(3) 「 物(3)也可為其互變異構體。使」)的染支 ㈤中之化合物⑺的含有量係以;;The compound (hereinafter also referred to as "the compound (3) "the substance (3) may also be a tautomer thereof.") is contained in the dye (5) of the compound (7);
所表 化合 染料 、7〇 (3) 20 201243499 [式(3)中,R及R32係分別獨立地表示碳數卜1〇的烷基。 R及R34係分別獨立地表示碳數!〜4的烷基、碳數i 的 烷硫基(alkyl sulfanyl)或碳數丨~4的烷磺醯基(alkyl sulf/nyi)。广及亦可為同時形成含有氮原子的環,π 及R34也可為同時形成含有氮原子的環。 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R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。 以R31及R32所表示的碳數卜1〇的烷基而言,可舉例 如:曱基、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】~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。 以R33及R34所表示的碳數丨~4的烷硫基(alkyl sulfanyl)而言,可舉例如:曱硫基、乙硫基、丙硫基、丁 硫基及異丙硫基。 以R33及R34所表示的碳數卜4的烷磺醯基Ulkyl sulfonyl)而言,可舉例如:曱磺醯基、乙磺醯基、丙磺醯 基、丁確醯基及異丙續隨基。 R及R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Η的烧基較佳,並以為甲 基則更佳。 Ρ及q係以分別獨立地為〇〜2的整數較佳,並以為丄 或2更佳。 21 201243499 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 rs 為較佳。The compound dye, 7〇 (3) 20 201243499 [In the formula (3), R and R32 each independently represent an alkyl group having a carbon number of 1 。. The R and R34 series independently represent the carbon number! An alkyl group of ~4, an alkyl sulfanyl group having a carbon number i or an alkyl sulf/nyi having a carbon number of 丨4. It is also possible to form a ring containing a nitrogen atom at the same time, and π and R34 may simultaneously form a ring containing a nitrogen atom. The P and Q systems each independently represent an integer of 0 to 5. When p is 2 or more, the plural Rs may be the same or different from each other; when q is 2 or more, the plural R34s may be the same or different from each other. Examples of the alkyl group having a carbon number represented by R31 and R32 include a mercapto group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a second-butyl group, and a third group. - butyl, hexyl, 2-ethylhexyl, decyl, decyl and the like. The alkyl group having a carbon number of ~4 represented by r33 and R34 may, for example, be a functional group having a carbon number of 4 among the alkyl groups listed above. Examples of the alkyl sulfanyl having a carbon number of 丨4 represented by R33 and R34 include a sulfoniumthio group, an ethylthio group, a propylthio group, a butylthio group and an isopropylthio group. The alkanesulfonyl group of the carbon number represented by R33 and R34 may, for example, be a sulfonyl group, an ethylsulfonyl group, a propyl sulfonyl group, a butyl sulfhydryl group, and an isopropanium. base. R and R are preferably each independently a methyl group, an ethyl group, a propyl group or an isopropyl group. R33 and R34 are preferably those having a carbon number of ruthenium, and more preferably a methyl group. Preferably, Ρ and q are each independently an integer of 〇 〜 2, and are preferably 丄 or 2. 21 201243499 The compound (3) may, for example, be a compound represented by the formula (1 - 31) to the formula (1 - 43), respectively. Among them, the compound rs represented by the formula (1 - 31) to the formula (1 - 40) is preferred from the viewpoint of excellent solubility in an organic solvent.
201243499201243499
iim x 11U 1 Γ cli> L Γ 1 I11V R_H/C」、田岡化學工業(股份有限)製之 等)。又,亦可利用市售的咕噸染料作為起始原料,而參考 特開2 0 1 0 - 3 2 9 9 9號公報來進行合成。 著色劑(A)也可以含有顏料(A2)。 以顏料而言,並未特別予以限制,可使用公知的原料, 如色彩索弓I (Color Index,The Society of Dyers andIim x 11U 1 Γ cli> L Γ 1 I11V R_H/C", Tiangang Chemical Industry (share limited), etc.). Further, it is also possible to use a commercially available xanthene dye as a starting material, and to carry out the synthesis in accordance with JP-A-2000-1593. The colorant (A) may also contain a pigment (A2). In the case of pigments, it is not particularly limited, and known materials such as Color Index, The Society of Dyers and can be used.
Co 1 our i s t s出版)中分類於顏料的化合物,可舉例如: C.The compound classified in the pigment in Co 1 our i s t s publication, for example: C.
[.顏料黃(pigment yell ow)l、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; 23 201243499 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(pigmentblue)15、15:3、15:4、15:6、 6 0等之藍色顏料; C· I.顏料紫(pigmentvi〇iet)l、l9、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 ye 1 i〇w)23、25等之棕色顏料; C· I ·顏料黑(pi gment b 1 ack) 1、7等之黑色顏料等等。 其中,係以使用以下顏料為較佳:c. i.顏料黃i38、 139、150 ; C. I.顏料紅 177、209、242、254 ; C. I η 顏料綠 料紫23; C· I.顏料藍15: 3、15: 6以及C. 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.丨·顏料藍丨5 : 6 顏料紅242、C· I.顏料紅177、c, I顏 顏料黃150以及C. I.顏料黃138。藉由 料紅 254、C. I. 料綠 58、C. I. 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。 也可以將2種以上合併 上述等之顏料可以單獨使用 使用之。 處理 顏料在必要時也可以對應施予以下處理 、使用導入有酸性基或鹼性基的顏料衍 :松脂(rosin) 生物等之表面 201243499 :理、利用高分子化合物等對顏料表面進行之接枝( 處理、利用硫酸微粒化法等之微粒化處理;或者是,用以 t除雜質之使用有機溶劑及水等的洗淨處理、藉由離 換法等去除離子性雜質之去除處理等等。 顏料係以粒徑均句者為較佳。藉由令其含有顏料分散 劑來進行分滅理,就可得到_在溶液Μ現均勻地分 散狀態之顏料分散液。 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、聚醋系'、聚胺系、丙稀系等: 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:κρ(信越化學工業(股份有限)製)、 F1〇ren(共榮社化學(股份有限)製)、S〇lspers(Zeneca(股 份有限)製)、EFKA(CIBA公司製)、Ajisper(味之辛[.pigment yell ow l,3,12,13,14,15,16' 17 , 20 , 24 ' 31 , 53 , 83 ' 86 , 93 , 94 , 109 , 110 , 117 , 125 , 128 Yellow pigments of 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; CI pigment orange 13, 31 ' 36, 38, 40, 42, 43 Orange pigments such as 51, 55, 59, 61, 64, 65, 71, 73; 23 201243499 C. I·pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168 Red pigments such as 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264 '265; CI pigment blue (pigmentblue) 15, 15:3, 15:4, 15:6, 60% blue pigment; C·I. pigment purple (pigmentvi〇iet) l, l9, 23, 29, 32, 36, 38, etc. purple pigment; CI pigment green (Pigment green) 7, 36, 58, etc. Green pigment; CI pigment brown (pigment ye 1 i〇w) 23, 25, etc. brown pigment; C · I · pigment black (pi gment b 1 ack) 1, 7, etc. black pigment and so on. Among them, the following pigments are preferably used: ci pigment yellow i38, 139, 150; CI pigment red 177, 209, 242, 254; C. I η pigment green violet 23; C · I. pigment blue 15: 3 , 15: 6 and C. 7, 36, 58. The pigment used in the coloring photosensitive resin composition of the present invention is preferably a pigment containing at least one of the group consisting of the following pigments: c. 丨·Pigment Blue 丨 5 : 6 Pigment Red 242, C·I. Pigment Red 177, c, I Pigment Yellow 150 and CI Pigment Yellow 138. By using the above-mentioned pigments, it is easy to optimize the penetration spectrum, and the chemical resistance is also improved by the red color 254, C.I. green color 58 and C.I. It is also possible to combine two or more kinds of the above-mentioned pigments, which can be used alone. When necessary, the treatment pigment may be subjected to a corresponding treatment, and a pigment derived from an acidic group or a basic group may be used: a surface of a rosin organism, etc. 201243499: grafting of a pigment surface by using a polymer compound or the like (Processing, microparticulation treatment using a sulfuric acid micronization method, or the like, or a washing treatment using an organic solvent and water for removing impurities, removing a ionic impurity by a separation method, or the like. It is preferable that the pigment is a uniform particle size. By subjecting it to a pigment dispersant, it is possible to obtain a pigment dispersion in which the solution is uniformly dispersed in the solution. For example, a cationic type, an anionic type, a nonionic type, an amphoteric type, a polyester type ', a polyamine type, an acryl type, etc.: a surfactant, etc. The above-mentioned pigment dispersing agent can be used individually, too. Two or more types may be used in combination. The pigment dispersant may, for example, be the following product name: κρ (Shin-Etsu Chemical Co., Ltd.), F1〇ren (Kyoeisha Chemical Co., Ltd.) ), S〇lspers (Zeneca parts (shares limited) Ltd.), EFKA (CIBA Ltd.), Ajisper (Ajinomoto oct
FuTechn。(股份有限)製)、Disperbyk(BYK化學公司製) 等。 當使用顏料分散劑時,其使用量係以相對於顏料 (A2曰)1〇。貝里伤而έ i。。質量份以下較佳,並以為& 質量份以上、5〇質量份以下更佳。顏料分散劑的使用量若 在上述賴内,就可得到均勾的分散狀態之顏料分散液。 乂著色d (A)而§,係以同時含有染料(Ai)及顏料(A2) 者為較佳°此時’染料(A1)及顏料(A2)的含有量比率 )(A2))若以質置基準而言,係以1 ·· 99〜99 : 1為較 佳3 · 97〜90 . 1 〇則更佳。藉由維持上述的比例就可使 25 201243499 得穿透光譜的最適化變得容易,所得到 杉色濾光片也會 在對比、明亮度、耐熱性、耐藥品性箄 寺万面具有優異的傾 向〇 特別是’當以本發明的著色感光性 衝知組合物作為藍 色者色感光性樹脂組合物來進行々周拉 , 时,以著色劑(A)而 言,係以含有咕嘲染料及藍色顏料的著色劑為較佳,並以 含有㈣染料及c. U負料藍15:6的著色劑為更佳。咕 喝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,:1〇為較佳、3:97〜70:3()更佳、3:9^〇\ 特佳、5U0:70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遽光片。 著色劑⑴的含有量係相對於著色感光性樹脂组合物 中的固形成份而言’以5〜60質量%較佳、8,質量%更佳、 10~50質量%特佳、12~3()質量 — 蔷― 里/〇則最佳。者色劑(A)的含有 =右洛在前述範圍内’就可以得到作為彩色渡光片時所期 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 伤^色據光片。在此處所述及的固形成份,係指本發明 的者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 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。 #月的著色感光性樹脂組合物係包括黏合劑樹脂 ’黏合劑樹脂⑻係為包括具有以下結構單元的共聚物 26 201243499 (B1)(以下也稱為共聚物(Bi))之黏合劑樹脂:來自甲基@ 烯酸之結構單元、來自丙烯酸之結構單元、以及來自 J跟 甲基丙烯酸和丙烯酸共聚合的單體(χ)(以下稱為「單體 (X)」)之結構單元。 以單體(X)而言,除了可跟甲基丙烯酸及丙烯酸進行共 聚合’且為跟曱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si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(但是跟丙烯酸及曱基丙烯酸不相同 也稱為「(b)」); 下 (c)其他可共聚合的單體(但是跟丙烯 酸、(a)及(b)不同)(以下也稱為「(c)」)。 以(a)所具有的碳數2~4的環狀醚結構而言,可舉 ^環氧乙院(oxirane)環、氧雜環丁烧(Qxetane)環及 氫咳喃(tetrahydi~〇furan)環。就(a)來說,係以為具有 數2〜4的環狀喊結構及(曱基)丙稀酿氧基之單體較佳。 另外,在本說明書中’「(甲基)丙稀酸」係表示擇 由丙烯k及甲基㈣gt所構成的族群中至少^種者。「( 基)丙烯醯基」及「(甲基)丙烯酸酯」等之表述方式 表同樣的意義。 ¥氧乙烧基及乙烯性不飽 (al)」)、具有氧雜環丁 以(a)而言,可舉例如:具有 和鍵結之單體(al)(以下也稱為 27 201243499 烷基及乙烯性不飽和鍵結之單體(a2)(以下也稱為 「U2)」)、具有四氫糠基 不飽和鍵結之單體(a3)(以下也稱為「⑽」)等。 U1)可舉例如:具有環氧化結構的直鏈狀或分支鍵狀 脂肪族不飽和烴及乙稀性不飽和鍵結結構之單體 以下也摇為1、 、 t _ )」),以及具有環氧化結構的 脂環式不飽和烴及L,法,14 τ # β , 烯14不飽和鍵結之單體(al-2)(以下 也稱為「(al-2)」)。 以⑷υ而言’可舉例如:(甲基)丙烯酸環氧丙醋、 召―甲基(甲基)丙烯酸環羞兩*>= 〇 « 那敞%氧丙酯、万—乙基(甲基)丙烯酸 環氧丙醋、環氧丙基乙烯 ^乙烯基卞基裱氧丙醚、間 ~乙稀基节基環氧丙越、對-乙烯基节基環氧丙趟、α-甲 卜 α τ丞間-乙烯基苄基環 氧丙越、卜甲基-對-乙稀基节基環氧丙越、2,3-雙(環氧 丙基氧甲基)笨乙烯、2 4_雔 、衣乳 ’ 4又(¾乳丙基氧甲基)苯乙烯、 .2’5-雙(環氧丙基氧甲美 氧甲基)本乙烯、2,6-雙(環氧丙基氧甲基) 本乙締、A 3, 4-三(環氧丙基負 氧丙基氧甲幻笨乙描 ,3,5_三(環 嫌 烯2,3,6 —三(環氧丙基氧甲基)苯乙 ,,-二(環氧丙基氧罕基)苯乙 基氧甲基)笨乙稀等。 一(%氧丙 以(al-2)而言,可叛如l ]9 . . 了舉例如:乙烯基環己烯單氧化物、 丄’2 ί衣氣基-4 —乙说技 η . , 烯基核己烷(例如:CEL oxide 2000, 業(奴伤有限)製)、3, 4-環氧基環己基(甲基) 丙烯酸甲酯(例如.Γ】 ^ ; yclomer Α400,Daicel 化學工業(股 rs 28 201243499 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(11)所表示的化合物等。FuTechn. (share limited) system, Disperbyk (manufactured by BYK Chemical Co., Ltd.), etc. When a pigment dispersant is used, it is used in an amount of 1 Å with respect to the pigment (A2?). Berry hurt and έ i. . The mass part is preferably the following, and it is more preferably equal to or more than 5 parts by mass. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a dispersed state can be obtained.乂Coloring d (A) and §, preferably containing both dye (Ai) and pigment (A2). At this time, the ratio of the content of dye (A1) and pigment (A2) (A2)) For the quality reference, it is preferably 1 ·· 99~99 : 1 is preferably 3 · 97~90 . 1 〇 is better. By maintaining the above ratio, it is easy to optimize the penetration spectrum of 25 201243499, and the obtained color filter is excellent in contrast, brightness, heat resistance, and chemical resistance. In particular, when the coloring photosensitive composition of the present invention is used as a blue color photosensitive resin composition, the coloring agent (A) contains a smear dye. A coloring agent of a blue pigment is preferred, and a coloring agent containing (4) a dye and c. U negative blue 15:6 is more preferable. The ratio of the content of the simmering dye and the blue pigment is preferably 3:97,:1 、, 3:97 to 70:3 (), and 3:9 〇 □ Good, 5U0:70 is the best. By making the above-mentioned coloring agent contain the above-described content, a blue color calender having a high brightness can be obtained. The content of the colorant (1) is preferably from 5 to 60% by mass, more preferably from 8% by mass, more preferably from 10 to 50% by mass, particularly preferably from 12 to 3%, based on the solid content of the colored photosensitive resin composition. Quality - 蔷 - 里 / 〇 is the best. The content of the toner (A) = dextro is within the above range 'is the spectral and color concentration expected as a color light-emitting sheet' and can be obtained by adding the necessary amount of binder resin and polymerization to the composition. The compound can form a mechanical strength that is very damaging. The solid content as referred to herein means the total amount of components other than the solvent removed from the color photosensitive resin composition of the present invention. The content of each component in the solid component and the solid component can be measured by a known analytical means such as liquid chromatography or gas chromatography. The coloring photosensitive resin composition of #月 includes a binder resin 'Binder resin (8) is a binder resin including a copolymer 26 201243499 (B1) (hereinafter also referred to as copolymer (Bi)) having the following structural unit: A structural unit derived from methyl@enoic acid, a structural unit derived from acrylic acid, and a structural unit derived from a monomer (hereinafter referred to as "monomer (X)") in which J is copolymerized with methacrylic acid and acrylic acid. The monomer (X) is not particularly limited as long as it is copolymerizable with methacrylic acid and acrylic acid and is not the same as the mercaptoacrylic acid and the acrylic acid, and may, for example, be: (a) An unsaturated compound having a cyclic Si structure having a carbon number of 2 to 4 (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, unlike acrylic acid and methacrylic acid, it is also called "(b)"); (c) other copolymerizable monomers (but different from acrylic acid, (a) and (b)) (hereinafter also referred to as " (c)"). The cyclic ether structure having a carbon number of 2 to 4 which is contained in (a) may be an oxirane ring, an oxetane ring (Qxetane) ring or a hydrogen cough (tetrahydi~〇furan). )ring. In the case of (a), it is preferred that the monomer having a ring-shaped structure of 2 to 4 and a (fluorenyl) acryloxy group be preferred. In the present specification, "(meth)acrylic acid" means at least one of the group consisting of propylene k and methyl (tetra) gt. The expressions of "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning. (Ethyl ethoxide and ethylenic (al)"), and oxetane, (a), for example, a monomer having a bond (al) (hereinafter also referred to as 27 201243499 alkane) a monomer (a2) (hereinafter also referred to as "U2)") having an ethylenically unsaturated bond, a monomer (a3) having a tetrahydroindenyl group unsaturated bond (hereinafter also referred to as "(10)"), etc. . U1), for example, a monomer having a linear or branched bond aliphatic unsaturated hydrocarbon having an epoxidized structure and an ethylenically unsaturated bonded structure is also shaken as 1, and t _ )"), and has An epoxidized alicyclic unsaturated hydrocarbon and an L, a method, a 14 τ #β, an alkene 14 unsaturatedly bonded monomer (al-2) (hereinafter also referred to as "(al-2)"). In the case of (4) ', for example, (meth)acrylic acid propylene vinegar, ―-methyl (meth) acrylate ring shame two *>= 〇« that open oxypropyl propyl ester, 10,000-ethyl (A Acrylic acid propylene vinegar, epoxy propyl vinyl ^ vinyl fluorenyl oxime ether, m-ethylene thiophene epoxide, p-vinyl ketone epoxide, α-ab Αττ丞-vinylbenzylepoxypropanoid, methyl-p-ethylene-based epipepene, 2,3-bis(glycidoxymethyl) stupid ethylene, 2 4_雔, Lacquer '4 again (3⁄4 propyl propyloxymethyl) styrene, .2'5-bis(glycidoxy methoxymethylmethyl) vinyl, 2,6-bis(epoxypropyl oxymethyl) Base) Benyi, A 3, 4-tri(epoxypropyl-n-oxypropyloxy-oxygen), 3,5_three (cyclohexene 2,3,6-tris(epoxypropyloxy) Methyl) phenylethyl,, -di(epoxypropyloxyhanyl)phenethyloxymethyl) stupid ethylene, etc. One (% oxypropyl to (al-2), can be rebellious l]9 . For example: vinyl cyclohexene monooxide, 丄'2 ί, 气, -4-, 乙, 乙, 乙: CEL oxide 2000, industry (limited by slave), 3, 4-epoxycyclohexyl (meth) acrylate (for example, Γ) ^ ; yclomer Α400, Daicel Chemical Industry (share rs 28 201243499 limited ), 3,4-epoxycyclohexyl (meth) acrylate methyl ester (for example: Cyclomer M100, manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the following formula (I), and formula (11) The compound shown and the like.
d) (Π) [式(I)及式(II)中,Γ及V係分別獨立地表示氫原子、或 碳數1〜4的烷基,該烷基所含有的氫原子,也可以用羥基 來予以取代。 二土 X及X係分別獨立地表示單鍵結、——、* — V — -、*-Rc-S-、*-rc-nh-。 係录不%i數1〜6的亞烷基( *係表示跟氧原子之結合鍵 以碳數卜4的院基而言,可舉例如:甲基、 丙基、異丙基、正丁基、第2_ 丁基 '第3_ 丁基等厂正 以將氫原子用歸取代的燒基而言可舉例如… 基、卜羥乙基、2-羥乙美、Ί〜π .羥曱 叛乙基、卜羥丙基、2_羥丙基 基、卜經基小f基乙基、2_ 3 & 〇 ^ 1 Τ基乙基、1-羥 2-羥丁基、3-羥丁基、4_羥丁基等。 基、 以r及π而言,較佳者為:氣原子、甲基 卜經乙基、2-經乙基等;更佳者 甲基、 以亞烷基而言,可兴#丨、 飞原子、曱基。 基、亞丙-1,3-基、亞丁 _丨4其 兑乙暴亞兩〜1,2、d) (Π) [In the formulae (I) and (II), the hydrazine and the V-system each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be used. The hydroxyl group is substituted. The two soil X and X series independently represent a single bond, -, * - V - -, *-Rc-S-, *-rc-nh-. An alkylene group having a %i number of 1 to 6 is not listed (* is a combination of a bond with an oxygen atom and a carbon number of 4, and examples thereof include a methyl group, a propyl group, an isopropyl group, and a n-butyl group. The base, the 2nd butyl '3th butyl group, etc., may be exemplified by a base group substituted with a hydrogen atom, for example, a base, a hydroxyethyl group, a 2-hydroxyethyl group, a Ί~π. Ethyl, hydroxypropyl, 2-hydroxypropyl, propyl-f-ethyl, 2_3 & 〇^ 1 decylethyl, 1-hydroxy 2-hydroxybutyl, 3-hydroxybutyl, 4 - hydroxybutyl group, etc., in terms of r and π, preferred are: a gas atom, a methyl group through an ethyl group, a 2-ethyl group, etc.; more preferably a methyl group, in the case of an alkylene group,可兴#丨, flying atom, 曱基. Base, propylene-1,3-yl, butyl _ 丨 4, which is against the violent two ~ 1,2
基等。 ,4'基、亞戊-1,5-基、亞己、H 29 201243499 以χ1及r而言,較佳者為:單鍵結、亞甲基、亞乙基、 *一CH2—〇 — (*係表示跟氧原子之結合鍵)基、*〜CH2CH21、 —基;更佳者為:單鍵結、*一ch2ch2—〇—基。2 2〜0 以式⑴所表示的化合物而言’可舉例如 (卜1)〜式(卜15)所表示的化合物等。其中較佳者為:土 (1)式(I 3)式(I ~ 5) ' 式(I — 7)、式(I _ 9 )或式(I -11;〜 式(I 15)所表不的化合物。更佳者為:式(卜1)、式(卜?)、 式(1-9)或式(1-15)所表示的化合物。 一 0Base. 4', pentylene-1,5-yl, hexylene, H 29 201243499 In terms of χ1 and r, preferred are: single bond, methylene, ethylene, *CH2—〇— (* indicates a bond with an oxygen atom), *~CH2CH21, a group; more preferably: a single bond, *-ch2ch2-〇-based. 2 2 to 0 The compound represented by the formula (1) is, for example, a compound represented by (1) to (Bu 15). The preferred ones are: soil (1) (I 3) (I ~ 5) ' Formula (I-7), Formula (I _ 9 ) or Formula (I -11; ~ Formula (I 15) A compound which is not. More preferably, it is a compound represented by the formula (Bu 1), the formula (Bu?), the formula (1-9) or the formula (1-15).
Η2〇=〇Η—C h2C=CH-C—〇—C2H4- η2ο=〇η-έ—0—ch2 丫 ί H 〇议 y V 0-3) H2C=CH-C—〇—c2H4^|nJ*^T jj || H 2C=C H - 0 C 4 — rvp 9h3 〇 0 ^ ^0-5) H2C=c—C—〇—c2H,S"""" H2C=CH-C—ο—c2h4-〇Η2〇=〇Η—C h2C=CH-C—〇—C2H4- η2ο=〇η-έ—0—ch2 丫ί H y y V 0-3) H2C=CH-C—〇—c2H4^|nJ *^T jj || H 2C=CH - 0 C 4 — rvp 9h3 〇0 ^ ^0-5) H2C=c—C—〇—c2H,S"""" H2C=CH-C-ο —c2h4-〇
ch3〇 H2C=C—C-〇-c2H4- ch3o CH2〇H 0 -c—〇Ch3〇 H2C=C—C-〇-c2H4- ch3o CH2〇H 0 -c—〇
h2c=c—c—0 H2C=C—C-O-CH H2C=C一c-o-c2h4 ch3o I II h2c=c一c_〇—c2h4—〇H2c=c—c—0 H2C=C—C—O—CH H2C=C—c-o-c2h4 ch3o I II h2c=c-c_〇—c2h4—〇
c2h5〇 u ^ I II H2C=C—c—o C2H4OH o HjC =C---C—0 (1-15) 以 式(Π)所表示的化合物而言可舉例如··以下式 rs 30 201243499 (11-1)~式(11-15)所表示的化合物等。其中較佳者為:式 (11-1)、式(II-3)、式(II-5)、式(11-7)、式(II-9)或式 (11-11)〜式(11-15)所表示的化合物。更佳者為:式 (11-1)、式(I1-7)、式(I1-9)或式(11-15)所表示的化合物。 h2c=ch-c-o-ch2C2h5〇u ^ I II H2C=C—c—o C2H4OH o HjC=C---C—0 (1-15) The compound represented by the formula (Π) may, for example, be the following formula: rs 30 201243499 (11-1)~ A compound represented by the formula (11-15). Preferred among them are: formula (11-1), formula (II-3), formula (II-5), formula (11-7), formula (II-9) or formula (11-11)-form ( 11-15) Compounds indicated. More preferably, it is a compound represented by the formula (11-1), the formula (I1-7), the formula (I1-9) or the formula (11-15). H2c=ch-c-o-ch2
H2C=CH-C—0H2C=CH-C—0
ch30 I II h H2C=C——C 一O—C2H4—NCh30 I II h H2C=C——C—O—C2H4-N
H2C=C—C-O-C2H4H2C=C-C-O-C2H4
c2h4oh 0 一1 II h2c=c-c—0 C2H50C2h4oh 0 -1 II h2c=c-c-0 C2H50
CH30 I II h2c=c—c 一 o—c2h4—oCH30 I II h2c=c-c one o-c2h4-o
上述式(1)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 卜 此外’上述等化合物也可以任意 的比率混合使用之。當溫人佔田全Q . 田此分使用時’其混合比例若以莫耳 比而言’係以式(I):式(丨丨、瓦nr r ^The compound represented by the above formula (1) 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 the Wenren Zhantian Quan Q. When the field is used, the mixing ratio is in the case of Mohr ratio, and the formula (I): formula (丨丨, 瓦nr r ^
Ui)為 5. 95〜95: 5 較佳、10: 90〜90: 10更佳、20 : 80〜80: 20則特佳。 31 201243499 以具有氧雜環丁燒基及乙埽性不飽和 而吕’係以為具有氧雜 I早體U2) 體較佳。以土及(甲基)丙烯醯氧基之單 平乂住川2)而s,可舉例如: 早 基甲基氧雜環Um I "基丙稀酿氧 土 3~丙稀醯氧基甲基 烷、3-乙基-3-f基丙,说酼备# 丞τ丞氧雜環丁 丙烯醯氧基甲基氧雜環丁烷、3_乙 丙烯醯氧基甲基氧雜環 基3- ,^抑 衣丁烷3 一甲基_3-甲基丙烯醯氧基 基氧雜環丁烧、3 -甲美-q * 甲基3-丙烯醯氧基乙基氧雜環丁烷、3_ 氧基乙基氧雜環丁烧等 乙基I甲基丙稀醯氧基乙基氧雜環丁烧、3—乙基_3_丙稀 醯1某己基1雜搭-r .a λ* 以八有四氫糠基及乙稀性不飽和鍵結之單體㈤)而 言,係以為具有四氫糠基及(甲基)丙烯醯氧基之單體較佳。 乂( a 3)而。具體來說可舉例如:丙稀酸四氫糠酯(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。 就(a)來說,若從可更進一步地提高所得到的彩色濾光 片之财熱性、耐藥品性等信賴度的觀點來看,係以(al)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(al-2)為更佳。 以(b)而言,具體來說可舉例如:丁烯酸、鄰_、間-、 對-乙烯基笨曱酸等之不飽和一元羧酸類; 馬來酸(maleic acid)、富馬酸(fumaric acid)、擦康 酸(citraconic acid)、中康酸(mesaconic acid)、衣康酸 (itaconic acid)、3-乙稀酜酸(3 - vinyl phthalic acid)、 4-乙稀献酸(4-¥1叩1口111;11311〇:3€^(1)、3,4,5,6-四氫酞Ui) is 5. 95~95: 5 is better, 10: 90~90: 10 is better, 20: 80~80: 20 is especially good. 31 201243499 It is preferred to have an oxetan group and an ethylenic unsaturated group, and the lysine group has an oxo I early body U2). The soil and the (meth) propylene oxime oxime singly singly singly 2) and s, for example: early methyl oxo-heterocyclic Um I " propylene ethoxylate 3~ propylene oxime Methyl alkane, 3-ethyl-3-f-propyl, said 酼##丞τ丞 oxetan propylene methoxymethyl oxetane, 3-ethyl propylene methoxymethyl oxane 3-, ^ ̄ butyl butane 3 monomethyl _ 3- methacryl oxiranyl oxetane, 3-methyl-q* methyl 3-propenyloxyethyl oxetane Ethyl, 3-oxyethyloxetane, etc. Ethyl I methyl propyl oxiranoxyethyl oxetane, 3-ethyl _3 propyl hydrazine 1 hexyl 1 hetero-r-r. a λ* A monomer having a tetrahydroindenyl group and a (meth)acryloxy group is preferable in terms of an octatetrahydroindenyl group and a ethylenically unsaturatedly bonded monomer (5).乂 (a 3) instead. Specific examples thereof include tetrahydrofurfuryl acrylate (for example, Viscoat V# 150' manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like. In the case of (a), it is preferable to further improve the reliability of the obtained color filter such as the heat resistance and the chemical resistance. Further, from the viewpoint of improving the storage stability of the colored photosensitive resin composition, (al-2) is more preferable. Specific examples of (b) include unsaturated monocarboxylic acids such as crotonic acid, o-, m-, p-vinyl alum, and the like; maleic acid, fumaric acid (fumaric acid), citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-ethylic acid ( 4-¥1叩1 port 111; 11311〇: 3€^(1), 3,4,5,6-tetrahydroanthracene
32 201243499 酸、1,2, 3, 6-四氫酞酸 '二甲基四氫酞酸、1,4-環己炫二 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-稀、5,6 -二叛基雙環[2. 2. 1]庚-2-稀、5 -緩基-5-曱基雙環[2, 2. 1]庚-2-烯、5-羧基-5-乙基雙環[2. 2. 1] 庚-2-烯、5-羧基-6-曱基雙環[2. 2. 1]庚-2-烯、5_缓基 -6-乙基雙環[2. 2. 1]庚-2-稀等之含有叛基的雙環不飽和 化合物類; 馬來酸酐、檸康酸針、衣康酸針、3 -乙稀醜酸針、4 -乙稀酞酸針、3, 4, 5, 6 -四氫欧酸酐、1,2, 3, 6 -四氫醜酸針、 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ί白酸單[2-[(2-(曱基)丙稀酿基)氧]乙基]酉旨 (mono-2-((meth)acryloyl〇xy)ethyl succinate)、 1,2-環 己烷二曱酸單[2[(2-(曱基)-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-(羥曱基)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。 就(c)來說,可舉例如:(曱基)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、(曱基)丙烯酸2-乙基己酯、 (曱基)丙烯酸十二烷酯、(甲基)丙烯酸月桂酯、(甲基)丙 33 201243499 稀酸十八醯酯、(甲基)丙稀酸環戊酯、(曱基)丙稀酸環己 酯、(曱基)丙烯酸2-甲基環己酯、(曱基)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:(曱基)丙烯酸二環戊酯)、 (曱基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷酯、(甲基) 丙烯酸烯丙酯、(曱基)丙烯酸炔丙酯、(曱基)丙烯酸苯酯、 (甲基)丙烯酸萘酯、(曱基)丙烯酸苄酯等之(曱基)丙烯酸 酯類; (曱基)丙烯酸2-羥乙酯、(曱基)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- 稀、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. “庚-卜烯、5-(2,-羥 基乙基)雙環[2. 2. 1]庚-2-烯、5-曱氧基雙環[2. 2. 1] 庚-2-稀、5-乙氧基雙環[2· 2. ”庚-卜烯、5,6_二羥基雙 J哀[2. 2. 1]庚-2-烯、5, 6-二(羥甲基)雙環[2. 2. 1]庚-2-稀、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-稀、5-羥基-5-曱基雙環[2. 2. 1;]庚-2_烯、5_羥基 _5_乙基雙環[2· 2· 1]庚-2-烯、5-羥曱基-5-曱基雙環[2. 34 201243499 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. Π庚-2-烯、5,6-雙(環己氧基羰基)雙環[2. 2. 1]庚-2- 稀等之雙環不飽和化合物類; Ν-苯基馬來酸酐縮亞胺(N-pheny 1 maleimide)、Ν-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-馬來酸酐縮亞胺苯曱酸酯(]^-811(:(:丨11丨111丨(171-3-maleimidebenzoate)、N-破珀醯亞胺基-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、間一甲基笨乙烯、對—曱 基苯乙烯、乙烯基曱苯、對-曱氧基苯乙烯、丙烯腈 (acrylonitrile)、曱基丙烯腈、氣乙烯、偏氣乙烯 (vinylidene chloride)、丙稀醢胺(acrylamide)、曱基丙 烯醯胺、乙酸乙烯(vinyl acetate)、1,3-丁二烯、異戊二 烯(13〇?^1^)、2,3-二曱基-1,3-丁二稀等。 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、ν -苄基馬來酸 酐縮亞胺、雙環[2. 2. 1]庚-2-烯等。 以共聚物(B1)而言,若從所得到的彩色濾光片之明亮 35 201243499 度的觀點來看,ϋ以含有·來自曱基丙稀酸之結構單元、 來自丙烯酸之結構單元、以及(a)的共聚物為較佳。 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 在以下的範圍内較佳: 來自曱基丙烯酸之結構單元:1〜54莫耳%(更佳為卜45 莫耳%); 來自丙細酸之結構單元: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6〇~90 莫耳%)。 更進一步,來自甲基丙稀酸之結構單元及來自丙稀酸 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。 共聚物(B1)之結構單元的比率,若位於上述的範圍 内’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。 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, 1 972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。 具體而言,係將甲基丙烯酸或丙烯酸及單體(χ)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 201243499 由通入氮氣來取代氡氣,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(過氧化笨醯等);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 為本發明的者色感光性樹脂組合物的溶劑(E)之溶劑等。 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。 共聚物(B1),也可以含有下式(ΙΠ)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(χ)之結構 單元。 α32 201243499 Acid, 1,2,3,6-tetrahydrofurfuric acid 'dimethyltetrahydrofurfuric acid, unsaturated dicarboxylic acid such as 1,4-cyclohexyl dicarboxylic acid; methyl-5-original Alkane-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-diene, 5,6-di-reradylbicyclo[2.2.1]hept-2-diene, 5-缓-5-mercaptobicyclo[2, 2. 1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2. 2. 1]hept-2-ene, 5-carboxy-6-indole a bicyclic unsaturated compound containing a ruthenium group such as a bicyclo[2.2.1]hept-2-ene, a 5-keto-6-ethylbicyclo[2.2.1]hept-2-ene; Toxic anhydride, citraconic acid needle, itaconic acid needle, 3-ethylene sulphuric acid needle, 4-ethylene citrate needle, 3, 4, 5, 6-tetrahydroauic anhydride, 1, 2, 3, 6 - Tetrahydro sulphate needle, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc., unsaturated dicarboxylic anhydrides; -[(2-(indenyl)propyl aryl)oxy]ethyl] 酉 (mono-2-((meth)acryloyl〇xy)ethyl succinate), 1,2-cyclohexanedicarboxylic acid mono[ a polyvalent carboxylic acid having a valence of 2 or more such as 2[(2-(indenyl)-1-oxo-2-propenyloxy)ethyl]hexahydrophthalate) Acid-unsaturated mono[[(2-methylpropenyl)oxy]alkyl]ester; as in α-(hydroxyindenyl)acrylic acid, unsaturated acrylates containing hydroxyl groups and carboxyl groups in the same molecule Wait. (c), for example, (mercapto) methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (methyl) 3rd butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, (methyl) propyl 33 201243499 octadecyl benzoate, (Methyl)cyclopentyl acrylate, (cyclo)acrylic acid cyclohexyl ester, (mercapto)acrylic acid 2-methylcyclohexyl ester, (mercapto)acrylic acid tricyclic [5. 2. 1. 02 '6] 癸-8-ester (common name referred to in the technical field: dicyclopentanyl (meth) acrylate), dicyclopentyloxy (meth) acrylate, (meth) acrylate Ring [5· 2. 1. 02'6] 癸-8-ester (known in the art as: (fluorenyl) dicyclopentanyl acrylate), (mercapto)isobornyl acrylate, Adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (mercapto) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (fluorenyl) (meth) acrylates such as benzyl acrylate and the like; (hydroxy) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; maleic acid; a dicarboxylic acid diester such as diethyl ester, diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1 Hept-2-diluted, 5-ethylbicyclo[2. 2·1]hept-2-ene, 5-hydroxybicyclo[2. 2. 1]hept-2-ene, 5-hydroxymethylbicyclo[2] 2. "Hept-Butene, 5-(2,-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-nonyloxybicyclo[2.2.1]hept-2-ene , 5-ethoxybicyclo[2· 2. ”hept-epene, 5,6-dihydroxy double J. [2. 2. 1]hept-2-ene, 5,6-di(hydroxymethyl) Bicyclo[2. 2. 1]hept-2-di, 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-pyrene, 5-hydroxy-5-fluorenylbicyclo[2. 2. 1 ;]hept-2-ene, 5-hydroxyl-5-ethylbicyclo[2·2·1]hept-2-ene, 5-hydroxyindolyl-5-fluorenylbicyclo[2. 34 201243499 2·1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2·2·1]g 2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6- Double (3 butyloxycarbonyl)bicyclo[2. 2. Πhept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-dicyclic Unsaturated compounds; N-pheny 1 maleimide, Ν-cyclohexyl maleic anhydride imide, N-benzyl maleic anhydride imide, N-amber Amino-3-maleic anhydride imide benzoate (]^-811(:(:丨11丨111丨(171-3-maleimidebenzoate), N-破珀醯imino-4-malay Anhydride butyl amide, N-succinimide-6-maleic anhydride imidate, N-succinimide-3-maleic anhydride acetimidate, N-(9 - acridinyl) dicarbonyl ruthenium imine derivatives such as N-(9-acridinyl) maleimide; styrene, α-methylstyrene, m-methyl stupid ethylene, - mercaptostyrene, vinyl anthracene, p-nonyloxystyrene, acrylonitrile, mercapto acrylonitrile, ethylene, vinylidene chloride, propylene Acrylamide, mercapto acrylamide, vinyl acetate, 1,3-butadiene, isoprene (13〇?^1^), 2,3-dimercapto-1,3 - Ding Ershou and so on. Among the above, among the above, from the viewpoints of copolymerization reactivity and heat resistance, the following are preferred: styrene, vinyl toluene, N-phenyl maleic anhydride, N-cyclohexyl horse An anhydride imide, ν-benzyl maleic anhydride imide, bicyclo[2.2.1]hept-2-ene, and the like. In the case of the copolymer (B1), from the viewpoint of the brightness of the obtained color filter 35 201243499 degrees, the ruthenium contains a structural unit derived from mercaptoacrylic acid, a structural unit derived from acrylic acid, and The copolymer of a) is preferred. 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) in the copolymer (B1), 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 45 mol%); structural unit derived from propionic acid: 1 to 54 Ear% (more preferably 1 to 45 mol%); structural unit derived from monomer (X): 55 to 98 mol% (more preferably 6 to 90 mol%). Further, the total amount of the structural unit derived from the methyl methic acid and the structural unit derived from the acrylic acid is '2 to 55 mol%, preferably 15%, in the entire structural unit constituting the copolymer (B1). ~50% Molar is better. 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. For the copolymer (B1), for example, the "Experimental Method for Polymer Synthesis" (Taijin Takayuki's "Publication of the Stock Exchange (Shares Limited) Chemicals, 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. Specifically, a predetermined amount of methacrylic acid or acrylic acid and a monomer, a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and then, for example, by using nitrogen gas instead of helium gas at 201243499, Deoxidation atmosphere, while stirring, heating and keeping warm. 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 (such as abbreviated peroxide); in the solvent, any solvent which can dissolve each monomer can be used, and a solvent (E) which is a color photosensitive resin composition of the present invention described later can also be used. ) Solvents, etc. 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. 'The manufacturing steps of the colored photosensitive resin composition of the present invention can be simplified. The copolymer (B1) may contain a structural unit represented by the following formula (ΙΠ) and/or a structural unit represented by the formula (IV) as a structural unit derived from a monomer (χ). α
OH 〇人。OH 〇人.
(III) [式(m)及式(IV)中,1^及係分別獨立地表示氫原子或 37 201243499 甲基。Re及V係分別獨立地表示氫原子或碳數^的烷基。 以R及Rs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 為風原子或甲基較佳。 例如,當共聚物(B1)為含有式(m)所表示的結構單元 時,利用跟上述相同的方法來得到曱基丙烯酸均聚物或曱 基丙烯酸跟單體(X)之共聚物,就可以藉由把式(uia)所表 示的化合物加成於來自曱基丙烯酸之羧基上,而得到含有 式(I π)所表示的結構單元之共聚物(B丨)。 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曱 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曱基丙烯酸之羧基上,而得到含有 式(III)所表示的結構單元的共聚物(B1)。 〇^°ν 〇<χΛκ9 (Ilia) (IVa) [式(Ilia)及式(iVa)中,r & Rg係表示跟前述相同者。] 即使當共聚物(B1)係含有以式(Ι〗丨)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 構早7L時’來自各個結構單元的比率係以在上述的範圍内 較佳。 當共聚物(Β1)為含有式(m)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, 38 201243499 以5〜80莫耳%較 係在構成共聚物(B1)的全結構單元中 佳、15〜70莫耳更佳。 式(III)所表示的結構單元及/或式 〇〇 W 1 v )所表示的結構 單元之含有比率若在上述的範圍内,則 ⑺者色感光性樹脂組 合物的保存穩定性、顯影性及靈敏度’ 及以及衫色濾光片的 耐溶劑性、耐熱性及機械性強度的平 丁河就會有變良好的傾 向。 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/曱基丙烯酸/丙烯酸共聚物、 丙烯酸3,4-環氧基三環[5. 2. i· 〇2.”癸酯/甲基丙烯酸/ 丙烯酸共聚物、(甲基)丙烯酸環氧丙醋/(曱基)丙烯酸节醋 /甲基丙烯酸/丙烯酸共聚物、(甲基)丙烯酸環氧丙酯/笨乙 細/曱基丙細酸/丙稀酸共聚物、丙稀酸—環氧美二環[5 2. 1. 02’6]癸酯/N-環己基馬來酸酐縮亞胺/曱基丙烯酸/丙 烯酸共聚物、3-甲基-3-(曱基)丙烯醯氧基曱基氧雜環丁烷 /苯乙烯/曱基丙烯酸/丙烯酸共聚物、(曱基)丙烯酸苄酯/ 曱基丙烯酸/丙烯酸共聚物、苯乙烯/甲基丙烯酸/丙烯酸共 聚物、令(曱基)丙烯酸環氧丙酯跟(曱基)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(曱基) 丙烯酸環氧丙酯跟(曱基)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(曱基) 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/曱基丙烯酸/丙烯酸共 39 201243499 聚物、笨乙烯/曱基丙烯酸/丙烯酸共聚物、以及丙烯酸3,4_ 環氧基三環[5. 2. 1. 〇2’6]癸酯/曱基丙烯酸/丙烯酸共聚 物較佳。 共聚物(B1)的聚笨乙烯換算之重量平均分子量係以 3,000〜1 00,000 較佳、5 000〜5〇 〇〇〇 更佳、5 〇〇〇〜3〇 〇〇〇 特佳’尤其以5,〇〇〇〜18,〇〇〇特佳、5,000〜1 2,000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。 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(Μη)],係以為1·卜6較佳、1. 2〜4更佳。 共聚物(Β1)的酸值,係以為50〜180mg-KOH/g較佳、 60~170mg-KOH/g 更佳 ' 1〇〇〜i5〇mg-KOH/g 特佳。在此處, 酸值係為用以中和樹脂1 g所必要的氮氧化鉀的量(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。 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,除了需為驗可 溶性樹脂以外’並未特別予以限定,可舉例如:曱基丙烯 酸及單體(X)之共聚物;丙烯酸及單體(X)之共聚物;曱基 丙婦酸或丙烯酸及(a)之共聚物;(a)及(b)之共聚物;甲基 丙烯酸或丙浠酸及(b)之共聚物;(b)及(c)之共聚物;(a) 及(b)及(c)之共聚物;令(曱基)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)跟曱基丙稀酸及 is 40 201243499 /或(b)及(c)之共聚物進行加成反應,再進而使其反應變成 酸針的樹脂等。具體來說,可舉例如:特開20 1 0-224204 號公報中所揭示的作為鹼可溶性樹脂之樹脂等。 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:曱基丙烯酸或丙烯酸及(3)之共聚物、甲基丙烯酸 或丙烯馱及(c)之共聚物。黏合劑樹脂藉由令共聚物(bi) ㈣含有上述等之樹脂’可使其未曝光部對於顯影液具有 间度的,合解11,且使所得到的著色圖形的形狀變得良好, 故較佳。 樹脂(B2)的聚笨乙稀換算之重量平均分子量係以 3,000〜50,_較佳、5,_〜3〇,〇〇〇^圭、5,剛15,_ 特佳。 樹脂的分子量分佈[重量平均分子量㈣/數量平 均分子量⑽],係以為i.卜6較佳、12〜4更佳。 樹脂(B2)的酸值’係以為5〇,〇mg —_/g較佳、 60~17〇mg-KOH/g 更佳、9(M6〇mg_K〇H/g 特佳 樹_若為前述的樹脂’特別是當跟共聚物⑽組 °使用時,未曝光料於顯料的溶解性就會很高,所得 到的著色圖形之殘膜率及硬度也會有提高的傾向。 共聚物(Β1)的含有量,係相對於勒合劑樹脂⑻的總量 而W質量%較佳,,。 心 量%特佳、30~50質量%最佳。 ⑺買 41 201243499 共聚物(B1)的含有量若位於上述範圍内,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。 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、以及曱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:15〜7〇質量 曱基丙烯酸或丙烯酸及(c)之共聚物:15〜7〇質量 以下更佳: 共聚物(B1) : 25〜50質量%、 曱基丙烯酸或丙烯酸及(a)之共聚物:25~5〇質量%、 甲基丙烯酸或丙烯酸及(c)之共聚物:25~5〇質量%。 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。 本發明的著色感光性樹脂組合物係包括聚合性化入物 (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:具有聚八 性的乙烯性不飽和鍵結之化合物等,並以例如:(甲基) 烯酸酯化合物為較佳。 两 其中,以聚合性化合物(C)而言’又以具有3個以上的 乙稀性不飽和鍵結之聚合性化合物為較佳。以此種類的聚 42 201243499 合性化合物而言,可舉例如:三羥甲基丙烷三(曱基)丙烯 酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基) 丙稀酸酯、一季戊四醇六(甲基)丙稀酸醋、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、 二(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、己内酯改質季戊 四醇四(曱基)丙烯酸酯、己内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。 聚合性化合物(c)的重量平均分子量’係以在15〇以 上、2, 900以下較佳、250〜1,50〇以下更佳。 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、13〜6〇質 里更佳、17〜55質量%則特佳。聚合性化合物之含有量 若位於前述的範圍β ’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。 本發明的著色感光性樹脂組合物係包括聚合引發劑 (D)。 43 201243499 以别述的聚合引發劑⑻而言’凡是可利用㈣用來 產生活性自由基及/或酸等而使聚合性化合物⑹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。 以聚合引發劑⑻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,纟以含有擇自由院基苯酮 (alkyl Phenone)化合物、三嗪化合物(triazine)、醯基氧 化膦(acyl Ph〇Sphine oxide)化合物 '將㈤㈤化合物以 MWCbiimidazole)化合物所構成的族群中至少丨種 者的聚合引發劑為更佳’而含有月亏化合物及院基笨酮化合 物的聚合引發劑則特佳。 前述院基苯酮化合物,係為具有下式⑽)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。 〇rV、(d2) QfV〇% (d3) 以具有式(d2)所表示的部份結構之化合物而言,可舉 例如.2-曱基-2-嗎啉代4-(4-曱基硫基笨基)丙+酮' 2_ 二甲基氨基-1-(4-嗎啉代笨基)_2_苄基丁酮、2_(二甲 基氨基)-2-[(4-甲基苯基)甲基]_卜[4_(4 —嗎啉代基)苯基] 丁卜鲷等。也可以使用1RGACURE(註冊商標)369、907及 379(以上為BASF公司製)等之市售產品。 以具有式(d3)所表示的部份結構之化合物而言,可舉 44 201243499 如:2 ~經基一 2 -甲盈 1 ^ 4^ 土 1—本基丙-1-酮、2-經基曱其 -H4-(2-羥基乙氧基)苯基]丙]—酮、卜羥基環己義: 酮、2-經基-2-甲基_卜(4_異丙基苯基)丙_卜_等之寡= 物α,α: __乙氧基笨乙_、节基三甲基'缩_等。Α /從靈敏度的觀點來看,以上述烧基苯綱化合物而言, 係以為具有式(d2)所表示的部份結構之化合物較佳、 為2-曱基-2-嗎琳代_卜(4_甲基硫基苯基)丙—卜調及/ 甲基氨基+(4-嗎啉代苯基)-2-节基丁 +酮更佳。— 以上述三嗓化合物而言’可舉例如:2,[雙 基).(4—甲氧基苯基)切-三嗓、2,[雙(三: 基)_6普曱氧基萘基)-u,5-三嗔、2,4—雙(:= 基)+胡椒基]’3,5_三嗪、2,[雙(三氯甲基) 基苯乙烯基)-1,3,5-=唪、2 4 # 甲虱 —桑2,4-雙(三氯甲基)__6_[2 曱基2_基)則-H5-三.、2,4-雙(三氣 基)-6-[2-(呋喃-2-基)醚3 5 一 ’、甲 某…” j 鞑」U,5-二嗪、2,4-雙(三氯 基)—H2-U-二乙基氨基i甲基苯基㈣] 2’4-雙(二氯甲基)_6_[2 — (3,4_二甲氧基苯 三嗪等。 」i,七b- :乂上述醯基氧化膦化合物而言,可舉例如:2 甲基本酿二苯基氧化脈笼 — … #。也可使肖刪〔_卜主冊商 標)819(BASF公司製)等之市售產品。 I主冊商 上述蔣化合物係為具有下式⑷)所表 化合物。以下,*係用以表示鍵結處。卩構之 45 201243499(III) [In the formula (m) and the formula (IV), the 1 and the lines each independently represent a hydrogen atom or 37 201243499 methyl group. Re and V each independently represent a hydrogen atom or an alkyl group having a carbon number. Examples of the alkyl group having 1 to 6 carbon atoms in R and Rs include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. In the case of Re and Rg, it is preferred to use a wind atom or a methyl group. For example, when the copolymer (B1) is a structural unit represented by the formula (m), 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 (B丨) containing a structural unit represented by the formula (I π) can be obtained by adding a compound represented by the formula (uia) to a carboxyl group derived from methacrylic acid. Further, when the copolymer (B1) is a structural unit represented by the formula (IV), a copolymer of methacrylic acid homopolymer or mercaptoacrylic acid and a 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 mercaptoacrylic acid. 〇^°ν 〇<χΛκ9 (Ilia) (IVa) [In the formula (Ilia) and the formula (iVa), r & Rg means the same as the above. Even when the copolymer (B1) contains a structural unit represented by the formula (?) and/or a structural unit represented by the formula (IV) as a structure from the monomer (X) 7 L early] The ratio of the structural units is preferably within the above range. When the copolymer (Β1) is a structural unit represented by the formula (m) and/or a structural unit represented by the formula (IV), the ratio of the structural unit of the above, 38 201243499 is 5 to 80 mol%. It is preferably 15 to 70 moles in the total structural unit constituting the copolymer (B1). When the content ratio of the structural unit represented by the formula (III) and/or the structural unit represented by the formula 1W 1 v ) is within the above range, the storage stability and developability of the (7) color photosensitive resin composition And the sensitivity and the solvent resistance, heat resistance and mechanical strength of the color filter will tend to be good. Specific examples of the copolymer (B1) include 3'4-epoxycyclohexylmethyl (meth)acrylate/mercaptoacrylic acid/acrylic acid copolymer, and 3,4-epoxy acrylate. Tricyclic [5. 2. i· 〇2." oxime ester / methacrylic acid / acrylic acid copolymer, (meth) acrylic acid propylene vinegar / (mercapto) acrylic vinegar / methacrylic / acrylic copolymer, (meth)acrylic acid propyl acrylate / stupid fine / mercaptopropionic acid / acrylic copolymer, acrylic acid - epoxide ring [5 2. 1. 02'6] oxime ester / N- Cyclohexyl maleic anhydride imide/mercaptoacrylic acid/acrylic acid copolymer, 3-methyl-3-(indenyl) propylene fluorenyloxy oxetane/styrene/mercaptoacrylic acid/acrylic acid copolymer , (fluorenyl) benzyl acrylate / mercapto acrylic / acrylic copolymer, styrene / methacrylic / acrylic copolymer, (meth) propylene acrylate and benzyl (meth) methacrylate / methacrylic acid /Acrylic copolymer copolymerized resin, bis(decyl) propylene acrylate and trimethyl decyl acrylate / styrene / methacrylate / A resin obtained by addition reaction of an acrylic copolymer, a glycidyl acrylate (meth) acrylate and a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / methacrylic acid / acrylic acid copolymer a reaction resin, etc. Among them, benzyl (meth) acrylate / methacrylic acid / acrylic acid 39 201243499 polymer, stupid ethylene / mercapto acrylic / acrylic copolymer, and 3,4_ epoxy acrylate Tricyclo[5. 2. 1. 〇2'6] decyl ester / methacrylic acid / acrylic acid copolymer is preferred. The copolymer (B1) has a weight average molecular weight of 3,000 to 10,000, preferably 3,000 to 10,000,000. 5 000 ~ 5 〇〇〇〇 better, 5 〇〇〇 ~ 3 〇〇〇〇 佳 佳 ' Especially 5, 〇〇〇 ~ 18, 〇〇〇 佳 佳, 5,000 ~ 1 2,000 best. In the above range, the solubility of the unexposed portion in the developer is high. The residual film ratio and hardness of the obtained colored pattern tend to increase. The molecular weight distribution of the copolymer (B1) [weight average molecular weight (mw) ) / number average molecular weight (Μη)], is considered to be 1 · Bu 6 is better, 1. 2 More preferably, the acid value of the copolymer (Β1) is preferably from 50 to 180 mg-KOH/g, more preferably from 60 to 170 mg-KOH/g, more preferably 1 〇〇 to i5 〇 mg-KOH/g. Here, the acid value is a measured value of the amount (mg) of potassium oxynitride necessary for neutralizing 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution. B) A resin other than the copolymer (B1) (hereinafter also referred to as "resin (B2)") may be contained. The resin (B2) is not particularly limited as long as it is required to be a soluble resin, and examples thereof include a copolymer of mercaptoacrylic acid and a monomer (X); a copolymer of acrylic acid and a monomer (X); a copolymer of thioglycolic acid or acrylic acid and (a); a copolymer of (a) and (b); a copolymer of methacrylic acid or amidic acid and (b); and a copolymer of (b) and (c) a copolymer of (a) and (b) and (c); a resin obtained by addition reaction of (meth)acrylic acid and/or (b) a copolymer of (a) and (c); (a) A resin which is subjected to an addition reaction with a mercapto-acrylic acid and an copolymer of (40) and (c), and further reacts the resin into an acid needle. Specifically, for example, a resin which is an alkali-soluble resin disclosed in Japanese Laid-Open Patent Publication No. H20-224204, and the like. Among them, 'better is: copolymer of methacrylic acid or acrylic acid and (a) copolymers (a) and (b), copolymer of (a) and (b) and (c), methacrylic acid or acrylic acid And (c) a copolymer, and a copolymer of (b) and (c); more preferably: a copolymer of methacrylic acid or acrylic acid and (3), methacrylic acid or acrylonitrile, and (c) copolymerization Things. The binder resin can make the unexposed portion of the copolymer (bi) (4) contain the above-mentioned resin, so that the unexposed portion has an interval with respect to the developer, and the shape of the obtained colored pattern is improved, so that the shape of the obtained colored pattern is good. Preferably. The weight average molecular weight of the resin (B2) in terms of polystyrene is 3,000 to 50, _ preferably 5, _ to 3 Å, 〇〇〇^, 5, just 15, _. The molecular weight distribution of the resin [weight average molecular weight (four) / number average molecular weight (10)] is preferably i. The acid value of the resin (B2) is 5 〇, 〇mg - _ / g is better, 60 ~ 17 〇 mg - KOH / g is better, 9 (M6 〇 mg_K 〇 H / g Tejia tree _ if the foregoing When the resin is used in particular with the copolymer (10) group, the solubility of the unexposed material in the raw material is high, and the residual film ratio and hardness of the obtained colored pattern tend to increase. The content of the copolymer is preferably W mass% based on the total amount of the binder resin (8), and is preferably 30% to 50% by mass. (7) Buy 41 201243499 The content of the copolymer (B1) When it is in the above range, the solubility of the unexposed portion in the developing solution is improved, so that the yield of the colored pattern is improved. When the content of the copolymer (B1) is less than the above range, the developability of the effect of the present invention In particular, the binder resin (B) is copolymerized with a copolymer (B1), methacrylic acid or acrylic acid and (a), and methacrylic acid or acrylic acid and (c). The composition of the material is preferred. The content in this case is preferably as follows: Copolymer (B1): 15 to 70 Amount of %, methacrylic acid or acrylic acid and copolymer of (a): 15 to 7 〇 mass of methacrylic acid or acrylic acid and copolymer of (c): 15 to 7 〇 or less by mass: copolymer (B1): 25 ~50% by mass, copolymer of methacrylic acid or acrylic acid and (a): 25 to 5% by mass, copolymer of methacrylic acid or acrylic acid and (c): 25 to 5% by mass. Adhesive resin (B) In the combination of the above, the solubility of the unexposed portion in the developer is improved, and the colored pattern of the excellent shape can be formed. The colored photosensitive resin composition of the present invention includes the polymerizable composition (c). The polymerizable compound (c) is a compound obtained by polymerizing an active radical, an acid or the like generated from the polymerization initiator (d), and examples thereof include a compound having a polyoctagonal ethylenically unsaturated bond, and the like. Further, for example, a (meth) enoate compound is preferred. Among them, a polymerizable compound having three or more ethylenically unsaturated bonds is preferred as the polymerizable compound (C). For this type of poly42 201243499 conjugate compound For example, trimethylolpropane tri(indenyl)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(methyl) acrylate, pentaerythritol hexa(methyl) acrylate vinegar, Tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol 九 (meth) acrylate, bis(2-(methyl) propylene oxime Ethoxyethyl)trimeric isocyanate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, Propylene glycol is modified with dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetrakis(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. The weight average molecular weight ' of the polymerizable compound (c) is preferably 15 Å or more, 2,900 or less, more preferably 250 〜1, 50 Å or less. The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 6 Å, and 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition. Very good. When the content of the polymerizable compound is within the above range β 'hardening, it is sufficient to complete, and the residual film ratio during development is increased upward, and the undercut of the colored pattern is less likely to occur. It is preferable that the sexuality tends to be good. The colored photosensitive resin composition of the present invention comprises a polymerization initiator (D). In the case of the polymerization initiator (8), which is not mentioned, any compound which can be used for the polymerization of the polymerizable compound (6) by using (4) to generate an active radical and/or an acid can be used without particular limitation. A known polymerization initiator. In the case of the polymerization initiator (8), a compound which generates an active radical by the action of light is preferred, and the compound contains an alkyl Phenone compound, a triazine compound, and a ruthenium. A acyl phosphine (acyl Ph〇Sphine oxide) compound's (5) (5) compound with a MWCbiimidazole) compound in a group of at least a quinone of a polymerization initiator is better, and contains a polymer of a monthly-depleted compound and a ketone-based compound The agent is especially good. The above-mentioned ketone ketone compound is a compound having a partial structure represented by the following formula (10)) or a partial structure represented by the formula (d3). In the above-mentioned partial structure, the benzene ring may have a substituent. 〇rV, (d2) QfV〇% (d3) For the compound having a partial structure represented by the formula (d2), for example, 2-mercapto-2-morpholino-4-(4-fluorenyl) Thiophenyl) propyl + ketone ' 2 - dimethylamino-1-(4-morpholino) 2-benzylbutanone, 2-(dimethylamino)-2-[(4-methylbenzene) Methyl)-[Bu[4_(4-morpholino)phenyl]butyrate and the like. Commercial products such as 1RGACURE (registered trademark) 369, 907, and 379 (above, BASF Corporation) can also be used. In the case of a compound having a partial structure represented by the formula (d3), it can be exemplified by 44 201243499, for example, 2 to 2, and 2, and 2, and 1 to 4, 4, 4, and 1 Based on its -H4-(2-hydroxyethoxy)phenyl]propanone-one, hydroxycyclohexyl: ketone, 2-yl-2-methyl-bu (4-isopropylphenyl)丙_卜_等的寡 = substance α, α: __ ethoxy group stupid _, benzyl trimethyl condensed _ and so on. Α / From the viewpoint of sensitivity, in the case of the above-mentioned alkyl benzene compound, it is preferred that the compound having a partial structure represented by the formula (d2) is 2-mercapto-2- 琳 琳 代(4-Methylthiophenyl)propane- and /methylamino+(4-morpholinophenyl)-2-pyrylbutan-1-one are more preferred. — in the case of the above triterpenoid compound, for example: 2, [diyl). (4-methoxyphenyl)-triterpene, 2, [bis(tri:yl)-6pyridinylnaphthyl )-u,5-trimium, 2,4-bis(:=yl)+piperonyl]'3,5-triazine, 2,[bis(trichloromethyl)styryl)-1,3 ,5-=唪, 2 4 #甲虱-桑 2,4-bis(trichloromethyl)__6_[2 fluorenyl 2_yl)--H5-III., 2,4-double (tri-gas) -6-[2-(furan-2-yl)ether 3 5 a', A..." 鞑"U,5-diazine, 2,4-bis(trichloro)-H2-U-di Alkyl i-methylphenyl(tetra)] 2'4-bis(dichloromethyl)_6_[2 - (3,4-dimethoxybenzenetriazine, etc.) i, seven b-: anthracene thiol oxidation The phosphine compound may, for example, be a 2-methyl-branched diphenyl oxidized vein cage--#. It is also possible to use a commercially available product such as 819 (manufactured by BASF Corporation). I The main bookmaker The above-mentioned Chiang compound is a compound having the following formula (4)). Hereinafter, * is used to indicate the bond.卩之之 45 201243499
χ S (dD 幸 * 可舉例如:N-苯曱酸基-1-(4- 以上述肟化合物而言 苯甲酸基-1-(4-苯基硫 甲酸基-1-(4 -苯基硫基笨 、N-乙酸基-l-[9-乙基 本基硫基本基)丁- -綱_2 -亞胺、 基笨基)辛-1-酮-2-亞胺、N-笨 基)_3'•環戊基丙-1-嗣_2 -亞胺 -6 基 基 -(2-曱基苯曱酿基)’十坐_3_基]乙_卜亞胺、乙酸 1 [9乙基6 {2-曱基-4-(3, 3-二甲基-2,4-二噁環戊 甲基乳)笨甲醯基卜9H-咔唑一3_基]乙+亞胺、N_乙酸基 -l-[9-乙基-6 —(2一甲基苯曱醯基)_9h_咔唑—3_基卜環戊 基丙+亞胺、N-苯甲酸基+[9-乙基+(2-甲基苯曱醯 基)-9H-咔唑-3-基]-3-環戊基丙烷_丨_酮_2_亞胺等。也可 以使用嶋議(註冊商標)⑽Q1、叫以上為 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+(4_笨基硫基苯基)丁 一卜酮-2-亞胺、N-苯甲酸基—丨―(4_苯基硫基苯基)辛_丨_酮 I亞胺以及N-苯甲酸基+(4—苯基硫基苯基環戊基 丙1酮-2-亞胺。若使用上述等之肟化合物,特別是在將 本毛明的者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遽光片。 以雙咪唑化合物而言,可舉例如:2,2,_雙(2—氣苯 基)-釦4 ,5,5’ -四笨基雙咪唑、22’ _雙(23_二氯苯 基)-4’4, ,5, 5’ -四苯基雙咪唑(例如,請參照特開平 6一75372號公報、特開平6-75373號公報等)、2, 2,_雙(2_ 46 201243499 亂本基)-4’4,,5,5,_四笨基雙咪唑、22,_雙(2氣苯 基4’4 ,5’5’ -四(烷氧基笨基)雙咪唑、2, 2,-雙(2_ 氣苯基)4’4 ,5, 5’ _四(二烷氧基苯基)雙咪唑、2,2,一 雙(2-軋本基)_4,4’ ,55’ _四(三烷氧基苯基)雙咪唑(例 如μ參照特公昭48-38403號公報、特開昭62-1 74204號 公報)、將4,4, ,5,5, _位的苯基以烷氧基羰基來取代的 米坐化5物(例如,請參照特開平7 _ 1 〇 913號公報)等。較 佳者為.2,2’ ~雙(2-氣苯基)_4,4,,5,5,-四苯基雙咪 2’2 雙(2, 3 -二氯笨基)-4, 4’ ,5, 5’ -四苯基雙咪 唾 坐2’2雙(2, 4-二氯苯基)-4, 4’ ,5, 5’ -四笨基雙咪唑 等。 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、笨 偶因異丁醚等之苯偶因化合物;二笨曱酮 (benzophenone)、鄰-苯醯苯甲酸甲酯、4一苯基二笨甲酮、 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, 6-三曱基二苯甲酮等之二苯 甲酮化合物 ’ 9,10 -菲 S昆(9,10-phenanthrenequinone)、2-乙基蒽醌(2-ethyl anthraquinone)、获醌(camph〇rqUinone) 等之S昆化合物;10-丁基-2-氣吖咬嗣(i〇-butyl-2-chloro acridone)、苯偶醯(benzi 1)、苯基乙醛酸甲酯、環戊二稀 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。 以藉由光來產生酸的酸產生劑而言,可舉例如:4 -經 47 201243499 基笨基二曱基鎳化物對-甲笨磺酸鹽、4-羥基笨基二甲基疏 化物氫六氟銻酸鹽、4-乙醯氧基苯基二甲基鎳化物對—甲苯 續酸鹽、4-乙醯氧基苯基甲基苄基锍化物氫六氟銻酸鹽、 三苯基疏化物對-甲苯磺酸鹽、三苯基銃化物氫六氟銻酸 鹽、二苯基碘鏽對-甲苯磺酸鹽、二苯基碘鏽氫六氟銻酸鹽 專之錄鹽(onium salt)類, 對甲苯確酸硝基苄酯(nitrobenzyl tosylate)類,對甲苯 績酸本偶因醋(benzoin tosylate)類等。 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1〇〇質量份而言,為〇卜⑽ 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内,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。 本發明的著色感光性樹脂組合物可更包括聚合引發助 劑0)1)。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—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。 以聚合引發助劑(D1)而言,可舉例如:胺化合物、烷 氧基心(3 11^〇又7 3111:1^3。61^)化合物、噻噸酮(1:1:1丨(^邮1^〇1^) 化D物、羧酸化合物等,其中並以噻噸酮化合物為較佳。 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 基氨基苯甲酸乙酯、 、4 -二曱基氨基苯曱酸曱酯、4_二曱 4-二曱基氨基笨甲酸異戊酯、苯甲酸 Γδ 48 201243499 2-二甲基氨基乙醋、4-二甲基氨基苯甲酸2_乙基己醋鲁 :甲基對甲苯胺、4,4’ -雙(二甲基氨基)二苯甲酮(通稱為 未希勒酮(Mahler,sketone))、44,…雙(二乙基氨基) 二笨甲,、4’4’ -雙(乙基甲基氨基)二笨二等,其:又 以-雙(二乙基氨基)二苯甲酮為較佳。也可以使用 .F(保土谷化學工業(股份有限)製)等之市售產品。 以上述烷氧基蒽化合物而言,可舉例如:9,1〇_二甲氧 基葱、2-乙基-9,10-二甲氧基葱、9,…二乙氧基蕙、2_ 乙基-9’1〇 —二乙氧基葱、9]。—二丁氧基惹、2_乙基—91。_ 二丁氧基蒽等。 以上述㈣酮化合物而言,可舉例如:2_異丙基㈣ 嗣、4-異丙基嗟仙、2,[二乙基㈣_、2,[二氣㈣ 酮、I -氣-4-丙氧基嗟'>頓§)§]等。 以上述羧酸化合物而言,可舉例% :苯硫基乙酸、甲 基笨硫基乙酸、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、^甲氧基苯硫基 :酸、氯苯硫基乙酸、二氣苯硫基乙酸、N—苯基氨基乙酸、 笨氧基乙酸、萘基硫代乙酸、"基氨基乙酸、萘氧基乙 酸等。 聚合引發助劑(D1),可單獨使用’也可將2種以上合 併使用之。 s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1〇〇質 置份而言,為〇.卜30質量份較佳、卜2〇質量份則更佳。 49 201243499 聚合引發助劑(D1)的量若位於前述的範圍内’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。 本發明的著色感光性樹脂組合物係以含有溶劑(E)為 較佳。 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.醋溶劑(於分子内含有—C00--但不含一0—的溶劑)、 喊溶劑(於分子内含有一〇—、但不含—C00—的溶劑)、醚 酉曰溶劑(於分子内含有一C〇〇—及一 〇—的溶劑)、酮溶劑(於 刀子内含有一C0—、但不含—c〇〇—的溶劑)、醇溶劑(於分 子内含有0H、但不含一〇—、— c〇—及_ c〇〇—的溶劑)、 方香族烴溶劑、醯胺溶劑、二甲亞砜(dimethyl sulf〇xide) 等。 以酷溶劑而言’可舉例如:乳酸曱酯、乳酸乙酯、乳 义丁 i曰、2 -羥基異丁酸曱酯、乙酸乙酯、乙酸正丁酯、乙 次異丁酯 '乙酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙 8曰丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙 鲖馱丙酯、乙醯乙酸曱酯、乙醞乙酸乙酯、環己醇乙酸酯、 7 ~丁 内醯胺(7 -butyrolactum)等。 以峻〉谷劑而s ’可舉例如:乙二醇一曱醚、乙二醇一 麵、乙一醇一丙喊、乙二醇—丁喊、二乙二醇一甲醚、 乙一醇一***、一乙二醇一 丁趟、丙二醇一甲醚、丙二 醇—***、丙二醇一丙醚、丙二醇一 丁醚、3_甲氧基—卜 丁醇、3-曱氧基-3-甲基丁醇、四氫呋喃、四氫吡喃 50 201243499 (tetrahydropyran)、1,4-二噁烷(1,4-dioxane)、二乙二 醇二甲喊、二乙二醇二乙酬1、二乙二醇甲***、二乙二醇 二丙醚、二乙二醇二丁醚、笨甲醚(anis〇le)、笨*** (phenetole)、曱基笨甲_等。 以崦醋溶劑而言’可舉例如:甲氧基乙酸曱酯、曱氧 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_曱氧基丙酸乙酯、3一乙 氧基丙酸曱酯、3 -乙氧基丙酸乙酯、2一甲氧基丙酸曱酯、 2-甲氧基丙酸乙醋、2-曱氧基丙酸丙酯、2_乙氧基丙酸甲 S旨' 2-乙氧基丙酸乙酯' 2~曱氧基_2-甲基丙酸曱酯、2-乙氧基-2-甲基丙酸乙酯、3-甲氧基丁基乙酸酯、3-曱基-3-甲氧基丁基乙酸酯、丙二醇—甲越乙酸酯、丙二醇一乙驗 乙酸酯、丙二醇一丙峻乙酸酯、乙二醇一甲酿乙酸酯、乙 二醇一***乙酸酯、二乙二醇—***乙酸酯、二乙二醇一 丁醚乙酸酯等。 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(is〇ph〇r〇ne)等。 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。 以芳香族烴溶劑而言,可舉例如:笨、甲苯、二曱苯、 均三甲苯(mesitylene)等。 以酿胺溶劑而言,可舉例如:N,N一二甲基曱醯胺 (N,N-dimethylf0rmamide) 、 N,N一二甲替乙醯胺(N,N_ 51 201243499 d i methyl acetamide)、N-曱基。比 口各炫酮(N-methyl pyrrol i done) 等。 上述等之溶劑’可單獨使用’也可將2種以上合併使 用之。 上述的溶劑之中’若從塗佈性、乾燥性等觀點來看, 係以在latm下之沸點為ι2〇β(:以上、i8〇〇c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 酉曰、丙一醇一甲醚、3_乙氧基丙酸乙酯、乙二醇一曱醚、 一 一醇一甲越、二乙二醇一***、3-甲氧基丁基乙酸酯、 3-甲氧基-1-丁醇、4-羥基_4一甲基_2_戊酮、N N_: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、 一丙一醇曱醚.乙酸酯、乳酸乙酯、3-甲氧基丁基乙酸酯、 3_甲氧基+丁醇、3乂氧基丙酸乙醋等。 者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,卩7〇~95質 量%為較佳、75〜92質量%為更佳。換言之,著色感光性樹 月曰,、且。物的固形成份係以為質量%較佳、8七質量% 更佳。⑻的含有量若在前述的範圍内’於塗佈時的平 坦性就會變得良好,卜k 匕外’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: 在本發明的著色咸去 巴α先性樹脂組合物中,也可以更包括 有界面活性劑(F)。sy 么n 以界面活性劑而言,可舉例如:石夕χ S (dD 幸* can, for example, be N-benzoic acid-1-(4- benzoic acid-1-(4-phenylthiocarboxylic acid-1-(4-phenyl) in the above hydrazine compound Sulfur-based, N-acetoxy-l-[9-ethylcarbylsulfanyl)butyl-yl-2-imine, pyridyl)oct-1-one-2-imine, N-styl )_3'•cyclopentylpropan-1-indole-2-imine-6-yl-(2-mercaptobenzoquinone) 'ten sitting_3_yl}b-imine, acetic acid 1 [9 Ethyl 6 {2-mercapto-4-(3,3-dimethyl-2,4-dioxacyclopentylmethyl milk), benzoyl sulfonyl 9H-carbazole-3-yl]ethylamine , N-acetoxy-l-[9-ethyl-6-(2-methylphenylhydrazino)_9h_carbazole-3-ylbucyclopentylpropane+imine, N-benzoic acid group+[ 9-ethyl+(2-methylphenylindenyl)-9H-indazol-3-yl]-3-cyclopentylpropane_丨-keto-2-imine, etc. It can also be used (registered Trademarks) (10) Q1, the above is a company-made product, and N_1919 (made by ADEKA). Among them, the following are preferred: N-benzoic acid + (4 - phenylthiophenyl) butanone-2-imine, N-benzoic acid - hydrazine - (4 phenyl) Thiophenyl) octyl ketone I imine and N-benzoic acid + (4-phenylthiophenylcyclopentylpropanone-2-imine. If the above-mentioned hydrazine compound is used, When the photosensitive color resin composition of the present invention is prepared into a blue colored photosensitive resin composition, a high-density color calender sheet can be obtained. Examples of the bisimidazole compound include 2, 2, _ bis (2-phenylene)-deducted 4,5,5'-tetraphenyldiimidazole, 22'-bis(23-dichlorophenyl)-4'4, ,5, 5'-four Phenylbiimidazole (for example, refer to JP-A-6-75372, JP-A-6-75373, etc.), 2, 2, _double (2_46 201243499 chaotic base)-4'4,, 5, 5 , _ tetraphenyl diimidazole, 22, _ bis (2 gas phenyl 4' 4 , 5 ' 5 ' - tetra (alkoxy phenyl) diimidazole, 2, 2, - bis (2 - phenyl) 4 '4,5, 5' _tetrakis(dialkyloxyphenyl)bisimidazole, 2,2, one pair (2-rolled base)_4,4',55' _ (Trialkyloxyphenyl) bisimidazole (for example, JP: JP-A-48-38403, JP-A-62-1 74204), and phenyl group at the 4, 4, 5, 5, and _ positions. The rice which is substituted by the oxycarbonyl group (for example, refer to JP-A-7- 1 〇 913), etc. Preferably, it is .2, 2' ~ bis(2-phenylphenyl)_4, 4, , 5,5,-tetraphenyl bis-mercapto 2'2 bis(2,3-dichlorophenyl)-4, 4',5, 5'-tetraphenyl bis-pyrene sitting 2'2 double (2, Further, the polymerization initiator (D) may, for example, be benzoin or benzene, and 4-dichlorophenyl)-4,4',5,5'-tetraphenylidene diimidazole. a benzoin compound such as acetophenone, benzoin ether, benzoin isopropyl ether or acetoin isobutyl ether; benzophenone, methyl o-benzoquinone, 4-benzene Dimethylene ketone, 4-phenylhydrazine-4,-methyldiphenyl sulfide, 3, 3,, 4, 4' _tetra (3 butyl peroxycarbonyl) benzophenone, 2, 4 , 6-trimercaptobenzophenone and other benzophenone compounds ' 9,10 - phenanthrenequinone, 2-ethyl anth Raquinone), S-Kun compound obtained from camph〇rqUinone, etc.; 10-butyl-2-chloro acridone, benzi 1 (benzi 1), phenyl b Methyl aldehyde acrylate, titanium pentanocene 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. Examples of the acid generator which generates an acid by light include, for example, 4 - through 47 201243499, a thiophene hydride, a 4-hydroxyphenyl hydride, a 4-hydroxyphenyl hydride. Hexafluoroantimonate, 4-acetoxyphenyl dimethyl nickelate p-toluene hydrochloride, 4-acetoxyphenylmethylbenzyl telluride hydrohexafluoroantimonate, triphenyl Hydrate p-toluenesulfonate, triphenylphosphonium hexafluoroantimonate, diphenyl iodine rust p-toluene sulfonate, diphenyl iodine rust hexafluoroantimonate Salts, nitrobenzyl tosylate, benzoin tosylate, etc. The content of the polymerization initiator (D) is preferably 1 part by mass based on 1 part by mass of the total of the binder resin (B) and the polymerizable compound (C). The quality is better. When the content of the polymerization initiator (D) is within the above range, the color pattern can be formed with high sensitivity, so that the exposure time can be shortened and the yield can be improved. The colored photosensitive resin composition of the present invention may further comprise a polymerization initiating aid 0) 1). 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 which promotes polymerization of a polymerizable compound which initiates polymerization by a polymerization initiator, or is called a sensitizer. The polymerization initiation aid (D1) may, for example, be an amine compound, an alkoxy core (3 11^〇7 3111:1^3.61^) compound, thioxanthone (1:1:1丨). (^ mail1^〇1^) A compound D, a carboxylic acid compound, etc., wherein a thioxanthone compound is preferred. Examples of the above amine compound include triethanolamine 'methyldiethanolamine, three different Ethyl propionamine aminobenzoate, decyl 4-dimercaptoaminobenzoate, isoamyl 4-diindole-4-didecylaminobenzoate, Γδ 48 benzocane benzoate Ethyl vinegar, 4-dimethylaminobenzoic acid 2-ethylhexanoic acid: methyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as not Hildenone (Mahler, Sketone)), 44, ... bis(diethylamino) dimethane, 4'4'-bis(ethylmethylamino) diphthyl, etc., which is again - bis(diethylamino) The benzophenone is preferably used, and a commercially available product such as .F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used. The alkoxy oxime compound may, for example, be 9,1 〇 dimethyl dimethyl hydride. Oxygen onion, 2-ethyl-9,10-dimethoxy Onion, 9, ... diethoxy hydrazine, 2 - ethyl-9'1 〇 - diethoxy onion, 9] - dibutoxy ketone, 2 - ethyl - 91. _ dibutoxy oxime, etc. The above (4) ketone compound may, for example, be 2 - isopropyl (tetra) oxime, 4-isopropyl phthalocyanine, 2, [diethyl (tetra) _, 2, [diqi (tetra) ketone, I - gas-4 - Propoxy 嗟 '> Dun §) §] and so on. In the above carboxylic acid compound, for example, phenylthioacetic acid, methyl stearylacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxy Phenylthioacetic acid, methoxy phenylthio: acid, chlorophenylthioacetic acid, di-phenylthioacetic acid, N-phenylaminoacetic acid, stupidoxyacetic acid, naphthylthioacetic acid, " Glycine, naphthyloxyacetic acid, and the like. The polymerization initiation aid (D1) may be used singly or in combination of two or more. When the polymerization initiator (D1) of the above-mentioned or the like is used, the amount thereof is based on the total amount of the binder component (B) and the polymerizable compound (c). 30 parts by mass is preferred, and 2 parts by mass is more preferred. 49 201243499 If the amount of the polymerization initiation aid (D1) is within the above range, the coloring pattern can be formed with high sensitivity, so that the yield of the colored pattern can be improved. The colored photosensitive resin composition of the present invention preferably contains a solvent (E). The solvent (E) is not particularly limited, and a solvent which is generally used in the field can be used. For example, 'can be selected from the solvents listed below. The vinegar solvent (containing -C00-- but not containing a solvent in the molecule), shouting solvent (containing a sputum in the molecule - but not a solvent containing -C00-), an ether oxime solvent (a solvent containing a C 〇〇 - and a hydrazine in the molecule), a ketone solvent (containing a C0 - in the knives, but not containing - c 〇〇) Solvent), alcohol solvent (solvent containing 0H in the molecule but no mono-, - c〇- and _c〇〇), scented hydrocarbon solvent, guanamine solvent, dimethyl sulfoxide 〇xide) and so on. In the case of a cool solvent, for example, decyl lactate, ethyl lactate, lactobutyl hydrazide, 2-hydroxyisobutyrate decyl ester, ethyl acetate, n-butyl acetate, beta-isobutyl acrylate acetate Ester, isoamyl acetate, butyl propionate, ethyl isopropyl 8-butyrate butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl propyl acetate, decyl acetate Ethyl acetate, cyclohexanol acetate, 7-butyrolactum, and the like. </ br> </ br> </ br> </ RTI> can be exemplified by: ethylene glycol monoterpene ether, ethylene glycol side, ethylene glycol monopropylene, ethylene glycol - dibutyl, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether , monoethylene glycol monobutyl hydride, propylene glycol monomethyl ether, propylene glycol-diethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-butanol, 3-decyloxy-3-methylbutanol , tetrahydrofuran, tetrahydropyran 50 201243499 (tetrahydropyran), 1,4-dioxane (1,4-dioxane), diethylene glycol dimethyl sulfonate, diethylene glycol diacetate 1, diethylene glycol Ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anis ether, phenetole, sulfhydryl and the like. In the case of a vinegar solvent, for example, decyl methoxyacetate, ethyl decyloxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxy Methyl propyl propionate, ethyl 3-methoxypropionate, decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, decyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, 2-ethoxypropane acid, S-ethyl 2-ethoxypropionate 2~ decyloxy-2-methylpropanoate Ester, ethyl 2-ethoxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-mercapto-3-methoxybutyl acetate, propylene glycol-methyl acetic acid Ester, propylene glycol-acetate acetate, propylene glycol-propyl acetate, ethylene glycol monoacetate, ethylene glycol monoethyl ether acetate, diethylene glycol-diethyl ether acetate, diethylene glycol Alcohol monobutyl ether acetate and the like. The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-butanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl group. _2_pentanone, cyclopentanone, cyclohexanone, isophorone (is〇ph〇r〇ne) and the like. The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol or glycerin. Examples of the aromatic hydrocarbon solvent include stupid, toluene, diphenylbenzene, mesitylene, and the like. In the case of the amine solvent, for example, N,N-dimethylf0rmamide, N,N-dimethylacetamide (N,N_51 201243499 di methyl acetamide), N-mercapto. N-methyl pyrrol i done and so on. The above solvents may be used singly or in combination of two or more. Among the above-mentioned solvents, from the viewpoints of applicability, drying property, and the like, an organic solvent having a boiling point of 1 m 2 :β (hereinafter, i8 〇〇 c or less) is preferable. It is: propylene glycol monomethyl ether acetate, acetaminophen, propanol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monoterpene ether, mono-l-methyl-e-glycol, diethylene glycol Ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-butanone, N N_: methylcarbamide, etc. They are: propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, monopropanol oxime ether, acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy+butanol The content of the solvent (E) in the photosensitive resin composition is 卩7〇~95 based on the total amount of the colored photosensitive resin composition of the present invention. The mass % is preferably 75 to 92% by mass. More preferably, the coloring photosensitive tree is 着色, and the solid content of the material is preferably 7% by mass, more preferably 8% by mass. (8) Within the aforementioned range' The flatness at the time of coating becomes good, and when the color filter is formed, since the color density does not become insufficient, the display characteristics become good: In the present invention, The coloring salty barrage alpha pre-resin composition may further include a surfactant (F). sy n n In the case of a surfactant, for example, Shi Xi
本界面活性劑、氯系A 活… ’舌性劑及具有氟原子之石夕系界面 /舌性劑寻。上述等物質, 了為於側鏈上具有聚合性基者。 201243499 以石夕系界面活性劑而言’可舉例如:具有矽氧烧鍵結 之界面活性劑等。具體而言’可舉例如:T〇Ray SILIC0N(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( Tor ay Dow Corning(股份有限)製);κρ 321、 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(M〇mentiveThe surfactant, chlorine-based A... linguistic agent and a stone-based interface with a fluorine atom/tongue agent. The above substances are those having a polymerizable group in the side chain. 201243499 In the case of the Shiyue surfactant, for example, a surfactant having an oxygen-oxygen bonding bond or the like can be mentioned. Specifically, for example, T〇Ray SILIC0N (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 (Tor ay Dow Corning) (share limited) system; κρ 321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 TSF4460(M〇mentive
Performance Materials Japan 聯合公司製)等。 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:fu〇rad(註冊 商標)FC430、同系列FC431C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);ft〇p(註 冊商標)EF301、同系列EF303、同系列EF351、同系列 EF352C三菱Materials電子化成(股份有限)製); SURFL0N(註冊商標)S38卜同系列S382、同系列sci(n、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。 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。具體而古, 可舉例如:MEGAFAC(註冊商標)R08、同系列BL2〇、同系列 F475、同系列F477、同系列F433(DIC(股份有限)製)等。 53 201243499 上述專之界面活性劑’ 4以單獨使用’也可以將2種 以上合併使用之。 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,以〇. 〇〇1質量%以上、〇. 2質量 〇/〇以下為較佳,〇· 002質量%以上、0. 1質量%以下更佳,〇. 〇1 質量%以上、〇· 05質量%以下則特佳。另外,在上述的含有 量之内’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内,彩色濾光片的平坦性就 會變得良好。 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。 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、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ο〗)' 浴劑(E)、界面活性劑(F)及其他成份來進行調製。 當含有顏料(A2)時,係以將顏料(A2)預先跟溶劑(E) 卩伤或王。卩進行混合,直到令顏料的平均粒徑達到為 °’2_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⑻的-部份或全部。在所得到的顏料分散 液中#殘存的成份等依據要變成的既定濃度來予以混 54 201243499 合’就可調製出本發明目的的著色感光性樹脂組合物。 當含有染料(A1)時’㈣(A1)係以預先溶解於溶劑⑻ 的一部份或全部來調製成溶液較佳。該溶液係以利用孔徑 〇· 〇卜Ιμιπ左右的過濾器來進行過濾較佳。 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0·0Η0μι„左右的過濾器來進行過濾較佳。 以使用本發明的著色感光性樹脂組合物來形成彩色渡 光月的著色圖形之方法而言,可舉例如:微影法、喷墨法 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。 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 〇·1〜30_,並以為〇 5〜2〇_較佳、〇.5~6⑽更佳。 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。 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) 55 201243499 玻璃等之破璃基板;聚碳酸酯、聚曱基丙烯酸甲酯、聚對 笨一曱 k 乙二醇酯(polyethylene terepht ha late)等之樹 月曰基板,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。 以塗佈方法而言’可舉例如:自旋式塗佈法(spin C〇ating)、狹縫塗佈法(slit coating)、狹縫及自旋式塗 佈法等。 把行加熱乾燥時的溫度,係以3 〇〜丨2 〇。匚為較佳、5 〇〜i丄〇 C為更佳。此外’以加熱時間而言,係以1 〇秒鐘〜6 〇分鐘 為較佳、3 0秒鐘〜3 0分鐘為更佳。 當施行減壓乾燥時’係以在5〇〜15〇Pa的壓力下、2〇〜25 °C的溫度範圍内進行為較佳。 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。 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。 以曝光所使用的光源而言,係以可產生25〇 45〇⑽波 長的光之光源為較佳。例如,可將未滿35〇nm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、4〇8nm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 f i丨忟〇來選 擇性地予以渡出。具體而言,可舉例如:水銀燈、發光二 56 201243499 極體、陶瓷金屬齒化燈(metal halide lamp)、_素燈等。 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 allgner)、步進機(stepper) 等之裝置為較佳。 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i ]如虱氧化卸、碳酸氫納、氫氧化四曱録等之驗性化 口物的水溶液。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、〇. 〇3〜5質量%為更佳。更進一 步’顯影液也可以含有界面活性劑。 方法也可以使用浸置式顯影法(pudd 1 e deve 1 op i ng)、 /又/貝法(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。 顯影後,係以施行水洗會較佳。 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°C為較佳、160〜235。〇 為更佳。事後烘烤處理的時間,則以卜丨2〇分鐘為較佳、 10-60分鐘為更佳。 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 …頁示裝置(例如:液晶顯示裝置、有機電致發光裝置、電子 爪等)及固體攝影元件之彩色濾光片來使用。 [實施例] 57 201243499 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 0 [合成例1 ] 在具備冷卻管及搜拌t置的燒瓶中,加入式(A(M)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、三氣曱& 150份及N,N_二甲基甲醯胺8 9 份,於搜拌下-面維持2rc以下、一面滴下加入氣化亞硫 醯(thionyl Chloride)l〇.9份。滴下終了後,升溫至5〇 °C,於相同溫度下維持5小時而使反應之,之後冷卻至2〇 °c。將冷卻後的反應溶液於攪拌下一面維持2〇它以下、一 面滴下加入2-乙基己基胺12. 5份及三乙基胺221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(r〇tary evaporator)將溶劑蒸餾去掉後,加入少量的曱醇而劇烈地 攪拌。將該混合物一面攪拌加入於離子交換水3 7 5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6 〇 〇c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。Performance Materials Japan Co., Ltd.). The above-mentioned fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specifically, for example, fu〇rad (registered trademark) FC430, the same series FC431C 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); ft〇p (registered trademark) EF301, the same series EF303, the same series EF351, the same series EF352C Mitsubishi Materials Electronic Chemicals Co., Ltd.; SURFL0N (registered trademark) S38 Butong Series S382, the same series sci (n, the same series SC105 (Asahi Glass Co., Ltd.); E5844 ((share limited) Daikin Fine Chemical Research The above-mentioned fluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a siloxane coupling or a fluorocarbon chain, etc. Specifically, for example, MEGAFAC (for example) Registered trademark) R08, the same series BL2〇, the same series F475, the same series F477, the same series F433 (DIC (share limited) system, etc. 53 201243499 The above-mentioned special surfactant '4 can be used alone' can also be used Combined above The content of the surfactant (F) is 〇. 质量1% by mass or more, 〇. 2 〇/〇 or less, based on the total amount of the colored photosensitive resin composition of the present invention. Preferably, 〇· 002% by mass or more and 0.1% by mass or less are more preferably 〇. 〇1% by mass or more, 〇·05% by mass or less is particularly preferable. Further, within the above-mentioned contents, 'not included The content of the pigment dispersant is such that the content of the surfactant (F) is within the above range, and the flatness of the color filter is improved. In the colored photosensitive resin composition of the present invention, if necessary Various additives (hereinafter also referred to as "other components") well known in the art as exemplified below may be added: fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers' light. A stabilizer, a chain transfer agent, etc. The colored photosensitive resin composition of the present invention includes, for example, a colorant (A), a binder resin, a polymerizable compound (c), and a polymerization initiator (D) 'and Re-correspond The mixture is prepared by mixing a polymerization initiator (E), a bath (E), a surfactant (F), and other components. When the pigment (A2) is contained, the pigment (A2) is pre-treated with the solvent (E) or the king. The hydrazine is mixed until the average particle diameter of the pigment reaches a degree of °'2_ or less, and it is preferably further dispersed by using a beads-mill. At this time, if necessary, a part or all of the above-mentioned pigment dispersant and binder resin (8) may be added in combination. The coloring photosensitive resin composition which is the object of the present invention can be prepared by mixing the components remaining in the obtained pigment dispersion liquid according to a predetermined concentration to be obtained. When the dye (A1) is contained, (4) (A1) is preferably prepared by dissolving a part or all of the solvent (8) in advance. This solution is preferably filtered by a filter having a pore size of about 〇·〇卜Ιμιπ. The colored photosensitive resin composition prepared and mixed as described above is preferably filtered by a filter having a pore diameter of about 0·0 Η 0 μm. The colored photosensitive resin composition of the present invention is used to form a color light-emitting moon. The method of the coloring pattern may be, for example, a lithography method, an inkjet method, or the like. 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. On the resin layer (for example, a layer of a different colored photosensitive resin composition is formed on the substrate), the volatile component such as a solvent is removed (dried) to form a dried coating film, and the film is allowed to be dried by a photomask. The colored layer is exposed and developed. In the above lithography method, if a mask is not used during exposure and/or development is not performed, a cured product of the dried coating film as a colored coating film can be formed. The colored pattern and the colored coating film can be used to form a color filter. The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on materials, uses, and the like. The whole is, for example, 〇·1 to 30 _, and is preferably 〇5 to 2 〇 _ preferably 〇. 5 to 6 (10). The colored photosensitive resin composition is applied onto a substrate and dried by heating (prebaking) Bake, pre_bake) and / or dry under reduced pressure to remove volatile components such as solvents, you can get a smooth dry film. For the substrate, 'can be used: quartz glass, borosilicate glass, alumina tannic acid Salt glass, soda-lime coated with cerium oxide 55 201243499 Glass substrate such as glass; polycarbonate, polymethyl methacrylate, poly-p-g-glycol (polyethylene) a metal slab substrate such as terepht ha late), an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate, and other color filter layers may be formed on the substrate. A resin layer, a transistor, a circuit, etc. The coating method may be, for example, a spin coating method, a slit coating method, a slit, and a spin type. Coating method, etc. The temperature at the time of heating and drying is 3 〇~丨2 〇. Preferably, 5 〇~i丄〇C is better. In addition, in terms of heating time, it is preferably 1 sec to 6 〇 minutes, preferably 30 seconds to 30 minutes, more preferably. It is preferable to carry out the pressure drying at a pressure of 5 Torr to 15 Torr Pa at a temperature of 2 Torr to 25 ° C. The film thickness of the coating film after drying is not particularly limited and may be used depending on the use. The material, the use, and the like are appropriately adjusted. The film after drying is exposed by a photomask for forming a target pattern. At this time, the shape of the pattern on the mask is not particularly limited, and the corresponding purpose can be used. Graphic shape. For the light source used for exposure, a light source capable of generating light of 25 〇 45 〇 (10) wavelength is preferred. For example, light of less than 35 〇 nm can be cut out using a filter that can take out the above-mentioned wavelength range, or light in the vicinity of 436 nm, around 4 〇 8 nm, and around 365 nm can be filtered out. A band-pass filter (band_pass fi丨忟〇) in the wavelength field is selectively used. Specifically, for example, a mercury lamp, a light-emitting diode 56 201243499, a metal halide lamp, and a metal halide lamp are used. A lamp or the like. In order to uniformly illuminate the entire exposed surface, and to position the reticle in the correct position with the substrate on which the dried coating film has been formed, a mask allgner is used. A device such as a stepper or the like is preferred. After exposure, it is brought into contact with the developer, and the unexposed portion is dissolved & removed (i.e., developed) to obtain a colored pattern. And an aqueous solution of an aqueous solution of an alkaline compound such as ruthenium oxide, sodium hydrogencarbonate or tetrahydrogen hydride. The concentration of the alkaline compound in the above aqueous solution is 0. 01 to 10% by mass. For better, 〇. 〇3 5 mass% is more preferable. Further, the developer may also contain a surfactant. The method may also use an immersion development method (pudd 1 e deve 1 op i ng), / / dipping, spray coating ( Further, the substrate may be inclined at an arbitrary angle during development. It is preferable to perform water washing after development. Further, 'post-bake may be performed correspondingly if necessary. The temperature of the baking treatment is preferably 150 to 250 ° C, preferably 160 to 235. The enthalpy is better. The time for the post-baking treatment is preferably 2 〇 minutes, more preferably 10-60 minutes. 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 as a page display device (for example, a liquid crystal display device, organic electroluminescence) [Embodiment] 57 201243499 The following examples are given to illustrate the present invention. The "%" and "parts" in the example are not Special instructions 0% by mass and part by mass [Synthesis Example 1] A mixture of a compound represented by the formula (A(M) and a compound represented by the formula (A0-2) is added to a flask equipped with a cooling tube and a t-feed. (Chinese and foreign chemical system) 15 parts, three gas 曱 & 150 parts and N, N dimethyl carbamide 8 9 parts, under the search and the surface to maintain 2 rc or less, while adding vaporized sulfoxide (thionyl) Chloride) 9 parts. After the completion of the dropwise addition, the temperature was raised to 5 ° C, and the reaction was continued at the same temperature for 5 hours, followed by cooling to 2 ° C. The cooled reaction solution was kept under stirring for 2 Torr, and a mixture of 2-ethylhexylamine 12.5 parts and 221 parts of triethylamine was added dropwise. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Next, after the obtained reaction mixture was distilled off by a rotary evaporator, a small amount of methanol was added thereto and vigorously stirred. The mixture was stirred while being 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 6 ° C to obtain dye A1 (dye A1) (formula (A1-1) to formula (A) 3份。 A1-8) a mixture of the compounds shown) 11. 3 parts.
(A0-1) (A0-2) 58 201243499(A0-1) (A0-2) 58 201243499
[合成例2] 將式(lx)所表示的化合物2〇份及1乙基—鄰、甲〜 (和光純藥工業(股份有限)製)2 〇 〇份於遮光條件下進= 合’並將所得到的溶液於11〇t下搜掉6小時。把所= 的反應液冷卻至室溫後,加人至水W份與35%鹽酸^份 的混合液中’於室溫下攪拌i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go%。 59 201243499[Synthesis Example 2] 2 parts of the compound represented by the formula (lx) and 1 ethyl-ortho-methyl group (manufactured by Wako Pure Chemical Industries, Ltd.) 2 parts are placed under the light-shielding condition = The resulting solution was searched for 6 hours at 11 Torr. After the reaction solution was cooled to room temperature, it was added to a mixture of W part of water and 35% of hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to crystallize. 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 is go%. 59 201243499
式(1-31)所表示的化合物之結構,係利用質量分析 (LC ; Agilent 製 12〇〇 型、MASS ; Agilent 製 LC/MSD 型) 來予以確認。 (質量分析)離子化模式=ESI+ : m/z= [M+ H]+ 603. 4The structure of the compound represented by the formula (1-31) was confirmed by mass analysis (LC; Agilent's 12-inch type, MASS; Agilent's LC/MSD type). (mass analysis) ionization mode = ESI + : m / z = [M + H] + 603. 4
Exact Mass : 602.2 [合成例3] 除了將N-乙基-鄰—曱苯胺改為換成N_丙基-2,6-二曱 基苯胺以外,其餘步驟皆與合成例i相同,而得到式(丨_39) 所表示的化合物。Exact Mass : 602.2 [Synthesis Example 3] except that N-ethyl-o-anisidine was changed to N-propyl-2,6-dimercaptoaniline, the other steps were the same as in Synthesis Example i. A compound represented by the formula (丨_39).
式(1 - 3 9)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 gIdentification of the compound represented by formula (1 - 39): (mass analysis) ionization mode = ESI + : m / z = [M + H] + 659 g
Exact Mass : 658.9 [合成例4 ] 在具備回流冷卻器、滴下漏斗及搜拌機的燒瓶内Exact Mass : 658.9 [Synthesis Example 4 ] In a flask equipped with a reflux cooler, a dropping funnel and a mixer
0· 02L/分的速率通入氮氣以形成氮氣氛圍,加 X 八礼酸乙酯 60 201243499 22〇份,—面攪拌一面加熱至7(TC。其次,調製將曱基丙 烯酸72份、丙烯酸7份、丙烯酸3, 4—環氧基三環[5. 2 i 〇 ]癸酯(將式(1_1)所表示的化合物及式(II-1)所表示的 化合物,以莫耳比50 : 5〇來混合)25〇份溶解於乳酸乙酯 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。(:的燒瓶内。 0 H2C=CH_C—0At a rate of 0·02 L/min, nitrogen gas was introduced to form a nitrogen atmosphere, and X octoate ethyl ester 60 201243499 22 parts was added, and the surface was heated to 7 (TC) while stirring. Next, 72 parts of methacrylic acid and acrylic acid 7 were prepared. And a compound represented by the formula (1_1) and a compound represented by the formula (II-1) in a molar ratio of 50:5. 〇 混合 mixed) 25 parts of a solution dissolved in 140 parts of ethyl lactate, the solution was dropped using a dropping funnel over a period of 4 hours in a flask maintained at 70 ° (0 H2C = CH_C - 0)
H2C=CH-C—0H2C=CH-C—0
II (Π-1) ㈢ V '0 ΗII (Π-1) (3) V '0 Η
另一方面,將已把聚合引發劑2,2,_偶氮雙(2,弘二 曱基戊腈)30份溶解於乳酸乙醋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内。當聚合引發劑 的溶液完成滴下之後,於70它下維持4小時,之後再冷卻 至室溫,就可得到重量平均分子量^為7 0xl03、分子^ 分佈為2.5、固形成份42%、固形成份酸值138mg_K = /g = 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 a polymerization initiator 2,2,-azobis(2, bis-indolyl valeronitrile) in 95 parts of ethyl lactate was used, and another dropping funnel was used for 4 hours. Time was dropped into the flask. After the completion of the dropwise addition of the solution of the polymerization initiator, it was maintained at 70 for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight of 70×10 3 , a molecular distribution of 2.5, a solid content of 42%, and a solid component acid. The value 138 mg_K = /g = resin B1 solution. The resin B1 has the structural unit shown below.
[合成例5 ] 在具備回流冷卻器、滴下漏斗 次撹拌機的燒瓶内,w 0.02L/分的速率通入氮氣以形成氮氣氛 ^ 固 加入乳酸乙酿 220份,一面攪拌一面加熱至7〇 。甘 U C其次,調製將甲基厌 烯酸10份、丙烯酸5 8份、丙烯酸q 4 _ ‘ ’4_%氧基三環[5. 2 61 201243499 1 · ο ]癸酯(將式(1 _ 1)所表示的化合物及式(11 _丨)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°C的燒瓶内。另一方面,將已把聚合引 發劑2,2’ _偶氮雙(2,4-二甲基戊腈)3〇份溶解於乳酸乙 酯95份而成的溶液,使用別的滴下漏斗以4小時的時間滴 下於燒瓶内。當聚合引發劑的溶液完成滴下之後,於7〇艽 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7.0χ103、分子量分佈為25、固形成份41%、固 形成份酸值136mg-KOH/g的樹脂Β2溶液。樹脂β2係具有 以下所示之結構單元。[Synthesis Example 5] In a flask equipped with a reflux condenser and a dropping funnel secondary mixer, nitrogen gas was introduced at a rate of 0.02 L/min to form a nitrogen atmosphere, and 220 parts of lactic acid was added thereto, and the mixture was heated to 7 Torr while stirring. . Gan UC followed by preparation of 10 parts of methyl anaenoic acid, 5 8 parts of acrylic acid, q 4 _ ' '4_% oxytricyclo[5. 2 61 201243499 1 · ο ] decyl ester (1 _ 1 The compound represented by the formula and the compound represented by the formula (11 _丨) are mixed in a molar ratio of 50:50) 254 parts of a solution dissolved in 140 parts of ethyl lactate, and the solution is used in a dropping funnel for 4 hours. The time was dropped in a flask kept at 70 °C. On the other hand, a solution obtained by dissolving 3 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate was used, and another dropping funnel was used. It was dropped into the flask over a period of 4 hours. After the solution of the polymerization initiator was dropped, it was maintained at 7 Torr for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 7.0 χ 103, a molecular weight distribution of 25, a solid content of 41%, and a solid component acid. A resin Β2 solution having a value of 136 mg-KOH/g. The resin β2 has the structural unit shown below.
[合成例6] 在具備回流冷卻器 、滴下漏斗及攪拌機的燒瓶内,以 0 02L/分的速率通入氮氣以形成氮氣氛圍,加入乳酸乙 220份,一面攪拌一面加熱至7〇<>c。 其次’調製將甲基丙 稀酸84份、丙稀酸3, 4 —環氧基三環[5. 2· i 〇26]癸醋(將 式(1-1)所表示的化合物及式(IH)所表示的化合物,以莫 耳比50: 50來混合)336份溶解於乳酸乙醋14〇份之溶液, 將該溶解液使用滴下漏斗 °匚的燒瓶内。另_方面, 以4小時的時間滴下於保溫在7〇 將已把聚合引發劑2, 2’ _偶氮雙 62 201243499 (2, 4-二甲基戊腈)3〇份溶解於乳酸乙酯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内。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8〇χ 1 03、分子量分佈為2. 5、固形成份48%、溶液酸值5〇mg K〇H/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。[Synthesis Example 6] 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 lactic acid B was added thereto, and the mixture was heated to 7 Torr while stirring; ;c. Next, 'modulate 84 parts of methyl methacrylate, 3, 4 - epoxy tricyclo [5. 2 · i 〇 26] vinegar of acrylic acid (the compound represented by formula (1-1) and formula ( The compound represented by IH) was mixed at a molar ratio of 50:50. 336 parts of a solution dissolved in 14 parts of ethyl lactic acid was used, and the solution was placed in a flask which was dropped into a funnel. On the other hand, the polymerization initiator 2, 2' _ azo double 62 201243499 (2, 4-dimethylvaleronitrile) 3 hydrazine was dissolved in ethyl lactate at 4 Torr in 4 hours. A solution of 95 parts was dropped into the flask over a period of 4 hours using another dropping funnel. When the solution of the polymerization initiator is completed, it is dropped at 70. (: maintaining for 4 hours, and then cooling to room temperature, the weight average molecular weight Mw is 8 〇χ 10 03, the molecular weight distribution is 2.5, the solid content is 48%, and the acid value of the solution is 5 〇 mg K 〇 H / The resin B3 solution of g is 104 mg-KOH/g when the solid component acid value is calculated from the above-mentioned solid component and solution acid value. Resin B3 has the structural unit shown below.
[合成例7 ] 在具備回流冷卻器、滴下漏斗及攪拌機的燒瓶内 0. 02L/分的速率通人氮氣以形成氮氣氛圍,加人乳酸乙酷 305質里份,-面授拌—面加熱至⑽。c。其次,調製將甲 基丙烯19G貝量份、甲基丙烯酸爷8旨21 酸乙酉旨⑽質量份之溶液,將該溶解液使用滴下漏:二[Synthesis Example 7] In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, a nitrogen gas atmosphere was introduced at a rate of 0.02 L/min to form a nitrogen atmosphere, and a lactic acid was added to the 305 mass fraction, and the surface was heated to the surface. (10). c. Next, a solution of 19 G of the amount of methyl propylene and a solution of (10) parts by mass of the methacrylic acid were prepared, and the solution was dropped using the solution:
小時的時間滴下於俘、'田A 、保/皿在100 C的燒瓶内。另一方面,將 已把聚合引發杳if 9 9, . 2, 2 ''偶氮雙(2, 4-二甲基戊腈)30質量 份溶解於乳酸乙酯225 Z ^為$伤而成的溶液,使用別的滴下 漏斗以4小時的日年09 ^ __ a f間滴下於燒瓶内。當聚合引發劑的溶液 元成滴下之後,於^〗η。y 於1 00 C下維持4小時,之後再冷卻至室 溫,就可得到曹吾 里十均y刀子量Mw為1. 2x1 04、分子量分佈 63 201243499 為2.2、固形成份30質量%、固形成份酸值154mg-K0H/g 的樹脂B4溶液。樹脂B4係具有以下所示之結構單元。The hour was dripped into the cap, 'Tian A', and the dish was placed in a 100 C flask. On the other hand, 30 parts by mass of the polymerization-initiated 杳if 9 9, .2, 2 '' azobis(2,4-dimethylvaleronitrile) has been dissolved in ethyl lactate 225 Z ^ The solution was dropped into the flask using another dropping funnel between 4 hours of the year 09 ^ __ af. When the solution element of the polymerization initiator is dropped, it is η. y is maintained at 1 00 C for 4 hours, then cooled to room temperature, and the amount of Mw of Caowuli's ten y knife is 1. 2x1 04, molecular weight distribution 63 201243499 is 2.2, solid content is 30% by mass, solid component acid value 154 mg-K0H/g of a resin B4 solution. 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(M w)及數 量平均分子量(Μη)的測定’係使用GPC法並利用以下的條 件來進行。 裝置:Κ 2 4 7 9 ((股份有限)島津製作所製)The measurement of the weight average molecular weight (M w) and the number average molecular weight (?η) of the resin obtained in the synthesis example was carried out by the following conditions using the GPC method. Device: Κ 2 4 7 9 ((share limited) Shimadzu Manufacturing Co., Ltd.)
管柱(column) : SHIMADZU Shim-pack GPC-80MColumn (column) : SHIMADZU Shim-pack GPC-80M
管柱溫度:40°CColumn temperature: 40 ° C
溶劑:THF(四氫吱喃) 流速:1 · OmL/miη 檢測器:RI 校正用標準物質:TSK STANDARD p〇lystyrene F_4〇、 F 4、F-288、A-2500、A-500 (Tor ay (股份有限)製) 旦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。 [實施例1〜6及比較例J] 就可得到 依據表1所示的組成,將各成份進行混合 著色感光性樹脂組合物。 64 201243499 單位(份) 實施例 bh f 1 2 3 4 5 6 著色劑(Α) (A-ir 30 30 30 30 30 30 3 (A-2) 8 8 8 (A-3) 8 8 8 丙烯系分散劑 12 12 12 12 12 12 黏合劑樹脂(Β) (固形成份換算) (B-1) 13 13 13 13 (Β-ϋ) 13 13 13 13 (Β-3) 13 13 13 13 (Β-4) 14 14 14 14 14 14 聚合性化合物(C) (C-l) 60 60 60 60 60 60 聚合引發劑(D) (D-l) 12 12 12 12 12 12 9 (D-2) 6 6 6~ 6 6 6 ^ 聚合引發助劑(D1) (Dl-1) 10 10 10 10 in 10 溶劑(Ε) (E-l) 188 188 188 188 188 188 1 U-以 191 191 191 191 191 191 2 (E-3) 674 674' 674 674 674 674 —1 界面活性劑(F) (F-l) 0.18 0.18 _0.18 Φ ΑϊϊΙ? -r 0.18 Kiit ΧΛι 1 / 0.18 0.18 丄 U(A-1)係將丙烯系分散劑以及丙二蒼1? ^ W 4 *Τλ\ "wT Ο 黏 另外,在表1中的各成份係表示以下各物質。又 合劑樹脂⑻係以固形成份換算的質量份來表示。 著色劑(A) : (A-1) ; c Τ ^ ,, ^ 染料A1 式(1-39)所 # - & λ ^尸7表不的化合物 ^ U丨.顏料藍15 : 6 著色劑(A) : (A-2) 著色劑(A) : (A-3)Solvent: THF (tetrahydrofuran) Flow rate: 1 · OmL/miη Detector: RI calibration standard material: TSK STANDARD p〇lystyrene F_4〇, F 4, F-288, A-2500, A-500 (Tor ay (Production Limited) The ratio of the weight average molecular weight and the number average molecular weight (Mw/Mn) converted from the polyethylene obtained above was used as the molecular weight distribution. [Examples 1 to 6 and Comparative Example J] The compositions shown in Table 1 were obtained, and the respective components were mixed to color the photosensitive resin composition. 64 201243499 Unit (parts) Example bh f 1 2 3 4 5 6 Colorant (Α) (A-ir 30 30 30 30 30 30 3 (A-2) 8 8 8 (A-3) 8 8 8 Propylene Dispersant 12 12 12 12 12 12 Adhesive resin (Β) (converted solids) (B-1) 13 13 13 13 (Β-ϋ) 13 13 13 13 (Β-3) 13 13 13 13 (Β-4 14 14 14 14 14 14 Polymerizable compound (C) (Cl) 60 60 60 60 60 60 Polymerization initiator (D) (Dl) 12 12 12 12 12 12 9 (D-2) 6 6 6~ 6 6 6 ^ Polymerization initiation aid (D1) (Dl-1) 10 10 10 10 in 10 Solvent (Ε) (El) 188 188 188 188 188 188 1 U-to 191 191 191 191 191 191 2 (E-3) 674 674 ' 674 674 674 674 —1 Surfactant (F) (Fl) 0.18 0.18 _0.18 Φ ΑϊϊΙ? -r 0.18 Kiit ΧΛι 1 / 0.18 0.18 丄U(A-1) is a propylene-based dispersant and propylene 1? ^ W 4 *Τλ\ "wT Ο Viscosity In addition, each component in Table 1 represents the following substances. The mixture resin (8) is expressed by mass parts in terms of solid content. Colorant (A) : ( A-1) ; c Τ ^ ,, ^ Dye A1 Formula (1-39)# - & λ ^Nuts 7 No compound ^ U Pigment Blue 15: 6 colorant (A): (A-2) a colorant (A): (A-3)
黏合劑樹脂(B) : (By);樹脂M 黏合劑樹脂(B): (B〜2);樹脂β2 黏合劑樹脂(B”(B〜3);樹脂β3 黏合劑樹脂⑻:(“);樹脂B4 聚合性化合物(C) n ;二 一字戍四醇六丙烯酸 65 201243499 (KAYARAD(註冊商標)DPHA ;日本化藥(股份有限)製) 聚合引發劑(D) : (D-l) ; N-苯甲酸基-1-(4-苯基硫基 苯基)辛-卜酮-2-亞胺(IRGACURE(註冊商標)〇χΕ 01 ; BASF 公司製) 聚合引發劑(D) : (D-2) ; 2-甲基-2-嗎啉代-1-(4-曱基 硫基笨基)丙-1-酮(IRGACURE 907 ; BASF公司製) 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) 溶劑(E): (E-1);丙二醇一甲趟乙酸酯 溶劑(E) : (E-2);丙二醇一甲醚 溶劑(E) : (E-3);乳酸乙酯 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) <溶解性評價> 將2英吋(inch)角的玻璃基板(Eagle 2〇〇〇 ; 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綠樹脂組合物塗佈 於該玻璃基板上,接著置於潔淨烘爐中,在lOOt下進行3 分鐘的預共烤處理。 其次,浸潰於液溫25°C的顯影液(以質量分率而言, 係為分別包含氫氧化卸U5%及丁基萘績酸鈉G 2%的水溶 液)中進行顯影’並以從基板的中心開始溶解完i。關部份 之終了時間作為溶解時間。溶解時間若在2()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 66 201243499 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。 <著色圖形之製作> 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1 0 0 °C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80μιη,使用曝光機(TME-150RSK; Topcon(股 份有限)製)於大氣氛圍下’以6〇mJ/cm2的曝光量(365nm基 準)進行光照射。以光罩而言,係使用可形成丨〇〇|Jin的線與 間隙(1 ine and space)圖形者。光照射後,將上述塗膜於 25 C下浸潰於顯影液(以質量分率而言,係為分別包含氫氧 化鉀0.05%及丁基萘績酸納〇2%的水溶液)中秒鐘進行 顯影’水洗後,再於烘爐中進行23〇ΐ ' 3〇分鐘的事後烘 烤處理’就可得到著色圖形。 <膜厚測定> 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。 <著色圖形形狀評價> 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 狀右為下述(Pi)所示的形狀(所謂的順錐度形狀)就打 67 201243499 〇, 打X 0 際, 所示 右為(P2)所不的形狀就打△,若為 若Ar u 勹〖p3)所示的形狀就 ^ ^ B 鬮形上沈積無機膜之 坑不谷易於無機膜上產生龜裂及剝 。 π離。其結果如表2Adhesive Resin (B): (By); Resin M Adhesive Resin (B): (B~2); Resin β2 Adhesive Resin (B" (B~3); Resin β3 Adhesive Resin (8): (") Resin B4 polymerizable compound (C) n ; diammine tetraol hexa acrylate 65 201243499 (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) Polymerization initiator (D): (Dl) ; N -benzoic acid-1-(4-phenylthiophenyl)octyl- ketone-2-imine (IRGACURE (registered trademark) 〇χΕ 01; manufactured by BASF Corporation) Polymerization initiator (D): (D- 2) 2-methyl-2-morpholino-1-(4-mercaptothiophenyl)propan-1-one (IRGACURE 907; manufactured by BASF Corporation) Polymerization initiation aid (D1) : 2, 4 -Diethylthioxanthone (KAYACURE DETX-S; manufactured by Nippon Chemical Co., Ltd.) Solvent (E): (E-1); Propylene glycol monoformate acetate solvent (E): (E-2) Propylene glycol monomethyl ether solvent (E): (E-3); ethyl lactate surfactant (F): (F-1); polyether modified eucalyptus oil (TORAY SILICON SH8400, manufactured by Toray Dow Corning) <Solubility evaluation> A glass substrate having an angle of 2 inches (Eagle 2®; After being washed with a neutral detergent, water and ethanol, it is dried, and then the colored green resin composition is applied onto the glass substrate by spin coating, and then placed in a clean oven. In the middle, the pre-co-baked treatment was carried out for 3 minutes at 100 t. Next, the developer was immersed in a liquid temperature of 25 ° C (in terms of mass fraction, it contained respectively 5% by weight of hydrazine and butyl naphthyl acid) The development is carried out in a sodium G 2% aqueous solution) and the dissolution is completed from the center of the substrate. The end time of the off portion is taken as the dissolution time. If the dissolution time is 2 (sec) or less, the solubility is good. In the case where the coloring photosensitive resin composition has a short development time of 66 201243499, it is possible to suppress a development failure such as a residue and to produce a colored pattern, so that the yield is extremely high. The results are shown in Table 2. <Production of Coloring Pattern> On a glass substrate (Eagle 2000; manufactured by Corning Co., Ltd.) having a 5 cm angle, 'the coloring photosensitive resin composition was applied by spin coating method' at 10 ° C 3 minutes pre-baking treatment, and After drying, the film is formed. After cooling, the substrate having the dried coating film is placed at a distance of 80 μm from the quartz glass mask, and an exposure machine (TME-150RSK; Topcon) is used in the atmosphere. The lower portion was irradiated with light at an exposure amount of 6 〇mJ/cm 2 (365 nm reference). In the case of a reticle, a line of 1 ine and space which can form 丨〇〇|Jin is used. After the light irradiation, the coating film was immersed in a developing solution at 25 C (in terms of mass fraction, an aqueous solution containing 0.05% of potassium hydroxide and 2% of butylnaphthalene, respectively). After performing development "washing, and then performing 23 〇ΐ '3 〇 minutes of post-baking treatment" in an oven, a colored pattern can be obtained. <Measurement of film thickness> The thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2. <Evaluation of the coloring pattern shape> The scanning coloring electron microscope (S 4000, manufactured by Hitachi High Technology Co., Ltd.) was used to observe the shape shown by the following (Pi). Straight taper shape) Hit 67 201243499 〇, play X 0, the right shape shown as (P2) is △, if it is the shape shown by Ar u 勹 〖p3) ^ ^ B 阄The pits in which the inorganic film is deposited are not easily cracked and peeled on the inorganic film. π away. The results are shown in Table 2.
(Ρ2) (ρ3) <色度評價> 針對所得到的著色圖形,使用測色機(0SP-SP一200.(Ρ2) (ρ3) <Chroma evaluation> For the obtained coloring pattern, a color measuring machine (0SP-SP-200.
Olympus(股份有限)製)來測定分光,並使用C光源的㈣ 函數來測的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。 [表2]Olympus (limited stock system) is used to measure the astigmatism, and the xy chromaticity coordinates (x, y) and the tristimulus value Y in the XYZ color system are measured using the (four) function of the C light source. If the value of Y is larger, it means that the brightness is higher. The results are shown in Table 2. [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’其餘步驟皆與實施你"〜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。 由上述的結果可確知’本發明的著色感光性樹脂組合 物-方面具有優異的色性能及圖形形狀’另一方面在著色 201243499 圖形形成之際,對於顧旦彡.泣μ〜, 一 了 π顯衫液的溶解性也非常高。因此可4 藉由本發明的著色感光 _ , w伽.'丑σ物,即可以高產 造出彩色濾光片。 & [產業上可利用性] 藉由本發明的著色感光性樹胳έΒ人 t 舛如組合物,就可在著色圖 形形成之際,令未曝光部對於部县彡、六θ丄 .身影液具有高溶解性。 【圖式簡單說明】 無。 【主要元件符號說明】 <»»、 69Except that the dye A1 was changed to the compound represented by the formula (1_31), the remaining steps were the same as those of the implementation of "3", and a coloring photosensitive resin composition was obtained. The same operation as described above was carried out, and it was confirmed that the solubility was excellent. Further, a colored pattern excellent in both brightness and shape is obtained. From the above results, it is confirmed that the color-developing photosensitive resin composition of the present invention has excellent color properties and pattern shape. On the other hand, when the coloring 201243499 pattern is formed, for Gu Danyu, weep μ~, a π The solubility of the shirting liquid is also very high. Therefore, the color filter can be produced with high color by the coloring _, w gamma, ugly sigma of the present invention. & [Industrial Applicability] By the coloring photosensitive tree of the present invention, for example, a composition can be formed on the coloring pattern, and the unexposed portion can be used for the part of the county, the six θ 丄. Has high solubility. [Simple description of the diagram] None. [Main component symbol description] <»», 69
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