TW201237118A - Colored photosensitive resin composition and compound - Google Patents
Colored photosensitive resin composition and compound Download PDFInfo
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- TW201237118A TW201237118A TW101104094A TW101104094A TW201237118A TW 201237118 A TW201237118 A TW 201237118A TW 101104094 A TW101104094 A TW 101104094A TW 101104094 A TW101104094 A TW 101104094A TW 201237118 A TW201237118 A TW 201237118A
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
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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
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
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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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- Polymerisation Methods In General (AREA)
Abstract
Description
201237118 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種著色感光性樹脂組合物及化合物。 【先前技術】 已知液晶顯示元件或固體攝像元件中所使用之彩色慮光 片具有紅色像素,形成該赤色像素之著色感光性樹脂組合 物係使用染料作為著色劑。例如專利文獻1中揭示有一種 含有Orasol Red G作為紅色染料之著色感光性樹脂組合 物。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2009-163226號公報 【發明内容】 [發明所欲解決之問題] 先前已知之上述著色感光性樹脂組合物,就耐溶劑性之 方面而言,有時未必可充分滿足。 [解決問題之技術手段] 本發明係提供以下之[1]〜[1〇]者。 [1 ] 一種著色感光性樹脂組合物,其含有著色劑、樹脂、 光叙合性化合物、光聚合起始劑及溶劑,著色劑為含有式 (1)所示之化合物之著色劑, 161700.doc 201237118201237118 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a colored photosensitive resin composition and a compound. [Prior Art] It is known that a color light-sensitive sheet used in a liquid crystal display element or a solid-state image sensor has a red pixel, and a colored photosensitive resin composition forming the red color pixel uses a dye as a colorant. For example, Patent Document 1 discloses a colored photosensitive resin composition containing Orasol Red G as a red dye. [Prior Art Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2009-163226 [Draft of the Invention] [Problems to be Solved by the Invention] The previously known colored photosensitive resin composition is solvent resistant. In terms of aspects, sometimes it may not be fully satisfied. [Technical means for solving the problem] The present invention provides the following [1] to [1]. [1] A colored photosensitive resin composition comprising a colorant, a resin, a photo-synthesizing compound, a photopolymerization initiator, and a solvent, wherein the colorant is a coloring agent containing a compound represented by the formula (1), 161700. Doc 201237118
[式(1)中’ R〜R相互獨立表示氫原子、鹵素原子、碳數 1〜8之1價之脂肪族烴基、硝基或_s〇2R29, R29表示 _R32、_〇H或·ΝΉΙ130, R30表示氫原子、碳數1〜8之1價之脂肪族烴基、可經碳 數1〜4之烷基取代之環己基、_R31_〇_r32、_r3丨_c〇 〇_ R32、-R31-〇-CO-R32或碳數7〜1〇之芳烷基, R31表示碳數1~8之2價之脂肪族烴基, R32表示碳數1〜8之1價之脂肪族烴基, R19及R20相互獨立表示氫原子、甲基、乙基或胺基, M1表示Cr或Co, R21〜R24相互獨立表示氫原子、碳數1〜8之1價之脂肪族 烴基或碳數6〜10之1價之芳香族烴基,該脂肪族烴基及該 芳香族烴基中所含之氫原子可經羥基、_〇R32、項基、 •S03Na、-S03K或鹵素原子取代, R及R26分別獨立表示氫原子或曱基, R27表示伸乙基、丙·1,3-二基或丙_丨,2-二基, π表示0〜3之整數’於n為2以上之整數之情形時,複數個 R相互相同或不同]。 161700.doc -4 - 201237118 [2] 如[1]之著色感光性樹脂組合物,其中Ri〜Ris相互獨 立為氫原子、硝基或-S02R29, R29為-R32, R32為碳數1〜8之1價之脂肪族烴基, R19及R20相互獨立為曱基, R21〜R24相互獨立為碳數1〜8之1價之脂肪族烴基, R25及R26分別獨立為氫原子, η為〇。 [3] 如[2]之著色感光性樹脂組合物,其中ri〜ru之中, 至少一個為氫原子’至少一個為硝基,且至少一個為 -S02R29。 [4] 如[3]之著色感光性樹脂組合物,其中Ri〜Rl〇相互獨 立為氣原子。 [5] 如[4]之著色感光性樹脂組合物,其中Rn〜Rl8之中, 至少一個為氫原子, R11〜R18之中,至少一個為硝基,且 R11〜R18之中,至少一個為_S〇2R29。 [6] 如Π]之著色感光性樹脂組合物,其中光聚合起始劑係 含有選自由烷基苯酮化合物、三畊化合物、醯基膦氧化物 化合物、肟化合物及聯咪唑化合物所組成之群中之至少— 種的光聚合起始劑。 [7] 如[1]之著色感光性樹脂組合物,其中W為 [8] —種彩色濾光片,其係藉由如π]至[7]中任一項之著 色感光性樹脂組合物而形成。 161700.doc 201237118 m -種顯示裝置,其含有如[8]之彩色濾光片。 [1〇] —種化合物,其係式(1)所示者,[In the formula (1), R to R independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8, a nitro group or _s〇2R29, and R29 represents _R32, _〇H or ΝΉΙ130, R30 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, _R31_〇_r32, _r3丨_c〇〇_R32, -R31-〇-CO-R32 or an aralkyl group having 7 to 1 carbon atoms, R31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. R19 and R20 independently of each other represent a hydrogen atom, a methyl group, an ethyl group or an amine group, M1 represents Cr or Co, and R21 to R24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8 or a carbon number of 6~ The monovalent aromatic hydrocarbon group of 10%, the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a hydroxyl group, _R32, a subgroup, ?S03Na, -S03K or a halogen atom, and R and R26 are each independently Represents a hydrogen atom or a fluorenyl group, R27 represents an ethyl group, a propyl 1,3-diyl group or a propyl group, a 2-diyl group, and π represents an integer of 0 to 3' when n is an integer of 2 or more. Multiple Rs are identical to each other or With]. [2] The colored photosensitive resin composition according to [1], wherein Ri~Ris are each independently a hydrogen atom, a nitro group or -S02R29, R29 is -R32, and R32 is a carbon number of 1 to 8. The monovalent aliphatic hydrocarbon group, R19 and R20 are each independently a fluorenyl group, and R21 to R24 are each independently a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R25 and R26 are each independently a hydrogen atom, and η is hydrazine. [3] The colored photosensitive resin composition according to [2], wherein at least one of ri~ru is a hydrogen atom, at least one of which is a nitro group, and at least one of which is -S02R29. [4] The colored photosensitive resin composition of [3], wherein Ri to R1 are independently a gas atom. [5] The colored photosensitive resin composition according to [4], wherein at least one of Rn to Rl8 is a hydrogen atom, at least one of R11 to R18 is a nitro group, and at least one of R11 to R18 is at least one of _S〇2R29. [6] The color-sensitive photosensitive resin composition of the present invention, wherein the photopolymerization initiator contains a compound selected from the group consisting of an alkylphenone compound, a tri-farming compound, a mercaptophosphine oxide compound, an anthracene compound, and a biimidazole compound. At least one of the group of photopolymerization initiators. [7] The color-sensitive photosensitive resin composition according to [1], wherein W is a color filter of [8], which is a color-sensitive photosensitive resin composition according to any one of π] to [7] And formed. 161700.doc 201237118 m - A display device comprising a color filter as in [8]. [1〇] a compound of the formula (1),
[式(1)中’ R1〜RI8相互獨立表示氫原子、鹵素原子、碳數 1〜8之1價之脂肪族烴基、硝基或·s〇2r29, R29表示-R32、-OH 或-NHR30, R30表示氫原子、碳數1〜8之!價之脂肪族烴基、可經碳 數1〜4之烧基取代之環己基、_r3,_〇_r32、r3i_c〇_〇_ R 、-R31-〇-CO-R32或碳數7〜10之芳烧基, R31表示碳數1〜8之2價之脂肪族烴基, R32表示碳數1〜8之1價之脂肪族烴基, R 9及R2〇相互獨立表示氫原子、曱基、乙基或胺基, M1表示Cr或Co, R21〜R24相互獨立表示氫原子、碳數1〜8之1價之脂肪族 烴基或碳數6〜10之1價之芳香族烴基,該脂肪族烴基及該 芳香族烴基中所含之氫原子可經羥基、_〇R32、確基、 •S03Na、-S03K或鹵素原子取代, R25及R26分別獨立表示氫原子或甲基, 161700.doc 201237118 R27表示伸乙基、丙-1,3-二基或丙-i,2-二基, π表示〇〜3之整數’於η為2以上之整數之情形時,複數個 R27相互相同或不同]。 [發明效果] ’ 根據本發明之著色感光性樹脂組合物,可形成耐溶劑性 較高之著色硬化物(例如塗膜、圖案)。 【實施方式】 本發明之著色感光性樹脂組合物含有著色劑、樹脂 (Β)、光聚合性化合物(C)、光聚合起始劑(D)及溶劑(Ε), 著色劑㈧為含有式⑴所示之化合物(以下有時稱為「化合 物(1)」)之著色劑。 化合物(1)係鉻錯陰離子或鈷錯陰離子與來自二苯并哌 喃(xanthene)化合物之陽離子的鹽。[In the formula (1), R1 to RI8 independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8, a nitro group or a ?s2r29, and R29 represents -R32, -OH or -NHR30. , R30 represents a hydrogen atom, carbon number 1~8! a valence aliphatic hydrocarbon group, a cyclohexyl group which may be substituted with a carbon number of 1 to 4, _r3, _〇_r32, r3i_c〇_〇_R, -R31-〇-CO-R32 or a carbon number of 7 to 10 An aryl group, R31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, R32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R 9 and R 2 are independently represented by a hydrogen atom, a mercapto group or an ethyl group. Or an amine group, M1 represents Cr or Co, and R21 to R24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aliphatic hydrocarbon group and The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a hydroxyl group, 〇R32, an exact group, •S03Na, -S03K or a halogen atom, and R25 and R26 each independently represent a hydrogen atom or a methyl group, 161700.doc 201237118 R27 represents an extension Ethyl, propyl-1,3-diyl or propyl-i,2-diyl, π represents an integer of 〇~3. When η is an integer of 2 or more, a plurality of R27 are the same or different from each other]. [Effect of the Invention] According to the colored photosensitive resin composition of the present invention, a colored cured product (for example, a coating film or a pattern) having high solvent resistance can be formed. [Embodiment] The colored photosensitive resin composition of the present invention contains a colorant, a resin, a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (Ε), and the colorant (VIII) is a content formula. (1) A coloring agent of a compound (hereinafter sometimes referred to as "compound (1)"). The compound (1) is a salt of a chromium cation anion or a cobalt cation anion with a cation derived from a compound of xanthene.
[式⑴中’ R1〜RU相互獨立表[In the formula (1), R1 to RU are independent of each other.
(1) 1 s夕1伸 風原子齒素原子、碳數 η之η貝之脂肪族烴基、確基或_叫r29, 反數 R29表示-R32、-OH或·NHR3。, R表示氫原子、碳數丨〜8之 價之知肪族烴基、可經碳 161700.doc 201237118 數1〜4之烷基取代之環己基、_R31_〇_R32、r31_c〇 〇- R32、-R31-〇-CO-R32或碳數7〜10之芳烷基, R31表示碳數1〜8之2價之脂肪族烴基, R表示碳數1〜8之1價之脂肪族烴基, R19及R20相互獨立表示氫原子、曱基、乙基或胺基, M1表示Cr或Co, R〜R24相互獨立表示氫原子、碳數i〜8之1價之脂肪族 烴基或碳數6〜10之}價之芳香族烴基,該脂肪族烴基及該 芳香族烴基中所含之氫原子可經羥基、_〇R32、項基、 -S03Na、_s〇3K或鹵素原子取代, R及R26分別獨立表示氫原子或曱基, R27表示伸乙基、丙_1,3-二基或丙4,2-二基, η表示〇〜3之整數,於n為2以上之整數之情形時,複數個 R27相互相同或不同]。 作為碳數1〜8之1價之脂肪族烴基,可列舉:甲基、乙 基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正 戊基、正己基、正庚基、正辛基、癸基、卜甲基丁基、 Μ,3,3-四曱基丁基、二曱基己基、16_二甲基庚基、 2-乙基己基及1,1,5,5-四曱基己基等。 作為碳數1〜4之1價之脂肪族烴基,即烷基,可列舉··甲 基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁 基等。 作為碳數1〜8之2價之脂肪族烴基,可列舉:亞甲基、伸 乙基、丙 _1,3-二基、丙 _1,2·二基、丁 _Μ_ 二基、丁 丨 3-二 161700.doc 201237118 基、戊-1,5-二基、 等。 己-1,6_二基、 庚-1,7-二基、 辛-1,8 -二基 作為碳數6〜10之1價之芳香族烴基,可列舉:苯基、甲 :苯基、二曱基苯基、三甲基笨基、乙基笨基、丙基苯 :、丁基苯基、蔡基等芳基;节基、二笨基甲*、苯基乙 基、3-苯基丙基等芳烷基等。 :為可經碳數卜4之烧基取代之環己基,可列舉:2_甲 基裱己基、2-乙基環己基、2•丙基環己基、2異丙基環己 基、丁基環己基、4-甲基環己基' 4_乙基環己基、心丙 基環己基、4-異丙基環己基、4_丁基環己基等。 作為-R31-〇-R32 ’可列舉:甲氧基曱基乙氧基甲基、 丙氧基甲基、甲氧基乙基、乙氧基乙基、丙氧基:基:甲 氧基丙基、乙氧基丙基、丙氧基丙基、2_氧代_4曱氧基丁 基、辛氧基丙基、3-乙氧基丙基、3_(2•乙基己氧基)丙基 等。 作為-R31-CO-〇-R32,可列舉:曱氧基羰基甲基、甲氧基 羰基乙基、乙氧基羰基甲基、乙氧基羰基乙基、丙氧基羰 基甲基、丙氧基羰基乙基、丁氧基羰基曱基、丁氧基羰基 乙基等。 作為-R31-〇-C〇-R32,可列舉:乙醯氧基甲基、乙醯氧基 乙基、乙基羰氧基曱基、乙基羰氧基乙基、丙基羰氧基甲 基、丙基幾氧基乙基、丁基羰氧基甲基、丁基羰氧基乙基 等。 作為-S〇2R29,可列舉:磺基;胺磺醯基; 161700.doc 201237118 N-曱基胺磺醯基、N-乙基胺磺醯基、N-丙基胺磺醯基、 N-異丙基胺磺醯基、N-丁基胺磺醯基、N-異丁基胺磺醯 基、N-第二丁基胺磺醯基、N-第三丁基胺磺醯基、N-戊基 胺磺醯基、N-(l-乙基丙基)胺磺醯基、N-(l,l-二曱基丙基) 胺磺醯基、N-(l,2-二曱基丙基)胺磺醯基、N-(2,2-二曱基 丙基)胺磺醯基、N-(l -曱基丁基)胺磺醯基、N-(2-甲基丁 基)胺磺醯基、Ν·(3-甲基丁基)胺磺醯基、N-環戊基胺磺醯 基、Ν-己基胺續醯基、Ν-( 1,3-二甲基丁基)胺續醯基、Ν-(3,3-二甲基丁基)胺磺醯基、Ν-庚基胺磺醯基、N-(l-甲基 己基)胺磺醯基、N-(l,4-二曱基戊基)胺磺醯基、Ν-辛基胺 磺醯基、Ν-(2-乙基己基)胺磺醯基、N-(l,5-二甲基)己基胺 磺醯基、N-(l,l,2,2-四甲基丁基)胺磺醯基、Ν-烯丙基胺磺 醯基等經脂肪族烴基取代之胺磺醯基; Ν-(2-甲氧基乙基)胺磺醯基、Ν-(2-乙氧基乙基)胺磺醯 基、N-(l-曱氧基丙基)胺磺醯基、Ν-(3-曱氧基丙基)胺磺 酿基、Ν-(3 -乙氧基丙基)胺績酿基、Ν-(3 -丙氧基丙基)胺 磺醯基、Ν-(3-異丙氧基丙基)胺磺醯基、Ν-(3 -己氧基丙 基)胺續醯基、Ν-(2-乙基己氧基丙基)胺罐醯基、ν-(3-第 三丁氧基丙基)胺續醢基、Ν-(4-辛氧基丁基)胺續醢基等 經-R31-0-R32取代之胺磺醯基; N-(曱氧基羰基甲基)胺磺醯基、N-(曱氧基羰基乙基)胺 續醯基、N-(乙氧基幾基曱基)胺磧醢基、N-(乙氧基幾基乙 基)胺磺醯基、N·(丙氧基羰基曱基)胺磺醯基、N-(丙氧基 幾基乙基)胺續醯基、N-(丁氧基幾基曱基)胺續酿基、n_ 161700.doc 10 201237118 (丁氧基羰基乙基)胺磺醯基等經-R31-CO-0-R32取代之胺磺 醯基; N-(乙醯氧基曱基)胺磺醯基、N-(乙醯氧基乙基)胺磺醯 基、N-(乙基羰氧基甲基)胺磺醯基、N-(乙基羰氧基乙基) 胺磺醯基、N-(丙基羰氧基曱基)胺磺醯基、N-(丙基羰氧基 乙基)胺磺醯基、N-(丁基羰氧基曱基)胺磺醯基、N-(丁基 羰氧基乙基)胺磺醯基等經-R3i_〇_C〇_R32取代之胺磺醯 基; N-環己基胺磺醯基、N-(2-甲基環己基)胺磺醯基、N-(3-曱基環己基)胺磺醯基、N-(4-曱基環己基)胺磺醯基、N- (4-丁基環己基)胺磺醯基,等經具有取代基之環己基取代 之胺磺醯基; N-苄基胺磺醯基、N-(l-苯基乙基)胺磺醯基、N-(2-苯基 乙基)胺磺醯基、N-(3-苯基丙基)胺磺醯基、N-(4-苯基丁 基)胺磺醯基、N-[2-(2-萘基)乙基]胺磺醯基、N-[2-(4-曱基 苯基)乙基]胺磺醯基、N-(3-苯基-1-丙基)胺磺醯基、N-(3- 笨基-1-甲基丙基)胺磺醯基等經芳烷基取代之胺磺醯基 等。 -S02R29 為-S〇2R32、_s〇2H 或-so2nhr30。其中,較佳 為-S02R32及-S〇2NHR30。 作為-S〇2NHR3Q之R3G,較佳為氫原子或碳數丨〜8之1價之 脂肪族烴基’更佳為氫原子或2_乙基己基。 於本發明之化合物具有_so2r32之情形時,較佳為 R〜R14之至少一個及Rl5〜R18中之至少一個為_s〇2R32。於 161700.doc • 11 · 201237118 具有複數個-S02R32之情形時,複數個R32相互可相同亦可 不同。 -S〇2R32之R32為碳數1~8之1價之脂肪族烴基,較佳為碳 數1〜4之1價之脂肪族烴基。作為-SOaR32,可列舉:曱基 續酿基、乙基續酿基、丙基續酿基、異丙基續酿基、正丁 基磺醯基、第二丁基磺醯基、第三丁基磺醯基、戊基磺醯 基、己基續醢基、庚基橫酿基、辛基續醢基、1-甲基丁基 磺醯基、1,1,3,3-四甲基丁基磺酿基、1,5-二曱基己基磺醯 基、1,6 - —甲基庚基續酿基、2-乙基己基石黃醯基及ι,ι,5,5_ 四曱基己基磺醯基等。其中,較佳為甲基磺醯基及乙基續 醯基,更佳為曱基磺醯基。 較佳為R1〜R18相互獨立為氫原子、硝基或_3〇汛29。 較佳為R1〜R18之中,至少一個為氫原子。又,更佳為 R1〜R1Q分別獨立為氫原子,R〗g〜ru之中,至少一個為氫原 子。又,進而更佳為Ri〗〜Ri4之至少一個及Ri5〜Ru中之至 少一個為氫原子。 1 ϋ 1 8 & * 〜R 之中,至 一個為硝基。 因存在耐熱性較高之傾向,故而較佳為R 少一個為硝基,更佳為Ru〜Ru之中,至少 又,進而更佳為R"〜之至少—個及r,5〜ri8中之至少 個為硝基。 又,較佳為R1〜R18之至少一個為-S02R29,更佳A 14〜 中,至少一個為-s〇2R29。又,進而更佳為Rll〜 R之至少-個及〜Rl8中之至少一個為·s〇2R29。於具 複數個-so2r 9之情形日寺,複數個r29相互可相同亦可不 161700.doc -12· 201237118 同。 又’進而更佳為“丨。分別獨立為氫原子,Rn〜 少一個及R15~R丨8中之至少一個盔 ^ 個為氫原子,R11〜R14之至少 一個及R15〜RU中之至少一個為 丞 K R之至少一個 及R〜R中之至少一個為_8〇21129。 R19及R20相互獨立為氫《子 風席子甲基'乙基或胺基,較佳 為相互獨立為f基或乙基。 m 因可提高色濃度,故而作為r2〗〜r24,較佳為氫原子或 可具有取代基之碳數1〜8之1價之脂肪族烴基,更佳為以 子或碳數1〜8之1價之脂肪族烴基,進而更佳為乙基等碳數 1 ~4之1價之脂肪族烴基。 二及π分別獨立為氮原子或甲基,較佳為相互獨立為 風原子。 作為R27,較佳為伸乙基 四一基,更佳為伸 基。 η為0〜3之整數,較佳為〇 铉叙& , 又登數,更佳為^若η為該 等數值,則化合物⑴之原料容易獲取。 又’更佳為R丨〜R丨0分別鉬* * & β 獨立為氫原子,R1丨〜R14之黾小 個及R丨5〜R丨《中之至少—钿&^ „RI5 RI8tb至乂個為風原子,W4之至少一個(1) 1 s eve 1 stretching atomic dentate atom, carbon number η η 之 之 之 aliphatic hydrocarbon group, the exact base or _ called r29, the inverse number R29 represents -R32, -OH or · NHR3. , R represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 丨8, a cyclohexyl group which can be substituted with an alkyl group having a carbon number of 161700.doc 201237118, _R31_〇_R32, r31_c〇〇-R32, -R31-〇-CO-R32 or an aralkyl group having a carbon number of 7 to 10, R31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, R19 And R20 independently of each other represents a hydrogen atom, a mercapto group, an ethyl group or an amine group, M1 represents Cr or Co, and R to R24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having a carbon number of i to 8 or a carbon number of 6 to 10. The aromatic hydrocarbon group of the valence, the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a hydroxyl group, 〇R32, a subgroup, -S03Na, _s〇3K or a halogen atom, and R and R26 are each independently Represents a hydrogen atom or a fluorenyl group, R27 represents an extended ethyl group, a propionyl-1,3-diyl group or a C,4,2-diyl group, and η represents an integer of 〇~3. When n is an integer of 2 or more, the plural R27 are the same or different from each other]. Examples of the aliphatic hydrocarbon group having a monovalent number of carbon atoms of 1 to 8 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a t-butyl group, a n-pentyl group, and a hexyl group. Base, n-heptyl, n-octyl, decyl, methyl butyl, anthracene, 3,3-tetradecylbutyl, didecylhexyl, 16-dimethylheptyl, 2-ethylhexyl and 1, 1,5,5-tetradecylhexyl and the like. Examples of the aliphatic hydrocarbon group having a carbon number of 1 to 4, that is, an alkyl group, may be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl or t-butyl. . Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methylene group, an exoethyl group, a propionyl-1,3 diyl group, a propionyl group, a diyl group, a butyl group, a diyl group, and a butyl group.丨3-two 161700.doc 201237118 base, penta-1,5-diyl, and so on. A-1,6-diyl group, a heptane-1,7-diyl group, and an octane-1,8-diyl group are exemplified as a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a methyl group: a phenyl group. , dimethyl phenyl, trimethyl phenyl, ethyl phenyl, propyl benzene, butyl phenyl, aryl, etc.; aryl, benzyl, phenylethyl, 3- An aralkyl group such as phenylpropyl group. : a cyclohexyl group which may be substituted with a carbon group of a carbon number: 2 - methyl hexyl group, 2-ethylcyclohexyl group, 2 - propyl cyclohexyl group, 2 isopropylcyclohexyl group, butyl ring Hexyl, 4-methylcyclohexyl '4-ethylcyclohexyl, propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl, and the like. Illustrative examples of -R31-〇-R32 ': methoxydecylethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxy: methoxy propyl Base, ethoxypropyl, propoxypropyl, 2-oxo-4-cyclomethoxybutyl, octyloxypropyl, 3-ethoxypropyl, 3-(2-ethylhexyloxy) Propyl and the like. Examples of the -R31-CO-oxime-R32 include a methoxycarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, a propoxycarbonylmethyl group, and a propoxy group. Alkylcarbonylethyl, butoxycarbonylindenyl, butoxycarbonylethyl and the like. Examples of -R31-〇-C〇-R32 include etidyloxymethyl, ethoxylated ethyl, ethylcarbonyloxyindenyl, ethylcarbonyloxyethyl, propylcarbonyloxymethyl Base, propyl methoxyethyl, butylcarbonyloxymethyl, butylcarbonyloxyethyl and the like. As -S〇2R29, a sulfo group; an amine sulfonyl group; 161700.doc 201237118 N-mercaptosulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N- Isopropylamine sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-butylbutylsulfonyl, N-t-butylamine sulfonyl, N - amylamine sulfonyl, N-(l-ethylpropyl)amine sulfonyl, N-(l,l-dimercaptopropyl)amine sulfonyl, N-(l,2-di Propyl sulfonyl, N-(2,2-dimercaptopropyl)amine sulfonyl, N-(l-decylbutyl)amine sulfonyl, N-(2-methylbutyl Amine sulfonyl, Ν·(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, fluorenyl-hexylamine hydrazino, Ν-(1,3-dimethyl Butyl)amine hydrazino, Ν-(3,3-dimethylbutyl)amine sulfonyl, hydrazine-heptylamine sulfonyl, N-(l-methylhexyl)amine sulfonyl, N -(l,4-didecylpentyl)amine sulfonyl, fluorenyl-octylamine sulfonyl, fluorenyl-(2-ethylhexyl)amine sulfonyl, N-(l,5-dimethyl ) hexylamine sulfonyl, N-(l,l,2,2-tetramethylbutyl)amine sulfonyl, decyl-allylamine sulfonyl, etc. Hydrocarbyl-substituted aminoxime; Ν-(2-methoxyethyl)amine sulfonyl, fluorenyl-(2-ethoxyethyl)amine sulfonyl, N-(l-methoxypropyl) Aminesulfonyl, Ν-(3-methoxypropyl)amine sulfonyl, Ν-(3-ethoxypropyl)amine, Ν-(3-propoxypropyl)amine Sulfonyl, Ν-(3-isopropoxypropyl)amine sulfonyl, Ν-(3-hexyloxypropyl)amine hydrazino, Ν-(2-ethylhexyloxypropyl) Amine sulfhydryl, ν-(3-t-butoxypropyl)amine hydrazino, fluorenyl-(4-octyloxybutyl)amine hydrazino, etc. substituted with -R31-0-R32 Sulfhydryl; N-(decyloxycarbonylmethyl)amine sulfonyl, N-(decyloxycarbonylethyl)amine hydrazino, N-(ethoxylated fluorenyl)amine fluorenyl, N -(ethoxy ethoxyethyl)amine sulfonyl, N.(propoxycarbonylindenyl)amine sulfonyl, N-(propoxymethylethyl)amine hydrazino, N-(butyl Alkyl sulfhydryl group, N-161700.doc 10 201237118 (butoxycarbonylethyl)amine sulfonyl group, substituted with -R31-CO-0-R32; Ethyloxyindenyl)aminesulfonyl, N-(ethyloxyethyl)amine sulfonate , N-(ethylcarbonyloxymethyl)amine sulfonyl, N-(ethylcarbonyloxyethyl)amine sulfonyl, N-(propylcarbonyloxyindenyl)amine sulfonyl, N-(propylcarbonyloxyethyl)aminesulfonyl, N-(butylcarbonyloxyindenyl)aminesulfonyl, N-(butylcarbonyloxyethyl)aminesulfonyl, etc. R3i_〇_C〇_R32 substituted aminoxime; N-cyclohexylamine sulfonyl, N-(2-methylcyclohexyl)amine sulfonyl, N-(3-indolylcyclohexyl)amine a sulfonyl group, an N-(4-fluorenylcyclohexyl)amine sulfonyl group, an N-(4-butylcyclohexyl)amine sulfonyl group, an aminesulfonyl group substituted with a cyclohexyl group having a substituent; -benzylaminesulfonyl, N-(l-phenylethyl)aminesulfonyl, N-(2-phenylethyl)aminesulfonyl, N-(3-phenylpropyl)aminesulfonate Indenyl, N-(4-phenylbutyl)aminesulfonyl, N-[2-(2-naphthyl)ethyl]aminesulfonyl, N-[2-(4-mercaptophenyl) Ethyl]aminosulfonyl, N-(3-phenyl-1-propyl)aminesulfonyl, N-(3-p-styl-1-methylpropyl)aminesulfonyl, etc. Substituted amine sulfonyl and the like. -S02R29 is -S〇2R32, _s〇2H or -so2nhr30. Among them, -S02R32 and -S〇2NHR30 are preferred. R3G as -S〇2NHR3Q, preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group of carbon number 丨8 is more preferably a hydrogen atom or a 2-ethylhexyl group. In the case where the compound of the present invention has _so2r32, it is preferred that at least one of R to R14 and at least one of Rl5 to R18 are _s〇2R32. 161700.doc • 11 · 201237118 In the case of a plurality of -S02R32, a plurality of R32s may be the same or different from each other. R32 of -S〇2R32 is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms. As the -SOaR32, a mercapto continued base, an ethyl continuation base, a propyl continuation base, an isopropyl continuation base, a n-butyl sulfonyl group, a second butyl sulfonyl group, and a third butyl group are mentioned. Sulfosyl, pentylsulfonyl, hexyl fluorenyl, heptyl aryl, octyl fluorenyl, 1-methylbutylsulfonyl, 1,1,3,3-tetramethyl Base sulfonate, 1,5-didecylhexylsulfonyl, 1,6-methylheptyl aryl, 2-ethylhexyl ruthenium and ι,ι,5,5-tetradecylhexylsulfonate醯基等. Among them, a methylsulfonyl group and an ethyl sulfhydryl group are preferred, and a fluorenylsulfonyl group is more preferred. Preferably, R1 to R18 are each independently a hydrogen atom, a nitro group or _3〇汛29. Preferably, at least one of R1 to R18 is a hydrogen atom. Further, it is more preferable that R1 to R1Q are each independently a hydrogen atom, and at least one of R to g to ru is a hydrogen atom. Further, it is more preferable that at least one of Ri to Ri4 and at least one of Ri5 to Ru are hydrogen atoms. 1 ϋ 1 8 & * ~ R Among them, one to nitro. Since there is a tendency for high heat resistance, it is preferable that one less R is a nitro group, more preferably a Ru~Ru, at least, and more preferably at least one of R"~ and r, 5 to ri8. At least one of them is a nitro group. Further, it is preferable that at least one of R1 to R18 is -S02R29, more preferably A14~, and at least one is -s〇2R29. Further, it is more preferable that at least one of R11 to R and at least one of R15 are ?s2R29. In the case of a plurality of -so2r 9 cases, a plurality of r29 may or may not be the same as 161700.doc -12· 201237118. Further, it is further preferably "丨. Each of them is independently a hydrogen atom, and at least one of Rn~ and one of R15~R丨8 is a hydrogen atom, at least one of R11 to R14 and at least one of R15 to RU. At least one of 丞KR and at least one of R~R is _8〇21129. R19 and R20 are each independently hydrogen "sub-wind mat methyl" ethyl or amine group, preferably independent of each other as f group or B Since m can increase the color density, it is preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8 which may have a substituent, more preferably a sub- or a carbon number of 1 to r2 to r24. The aliphatic hydrocarbon group having a valence of 8 or more is more preferably an aliphatic hydrocarbon group having a carbon number of 1 to 4 such as an ethyl group. The π and π are each independently a nitrogen atom or a methyl group, and preferably each independently is a wind atom. R27 is preferably an ethylidene group, more preferably an extended group. η is an integer of 0 to 3, preferably 〇铉 && , and a number, more preferably ^ if η is such a value , the raw material of the compound (1) is easily obtained. Further, it is more preferably R丨~R丨0, respectively, molybdenum* * & β is independently a hydrogen atom, and R1丨R14 is a small one and R丨5 R | 'or at least in the - Tin & ^ "RI5 RI8tb to Yi in a wind atoms, W4 of at least one
中之至少-個為硝&,R r> 15 n IQ L 八<芏> 一個及 〜中之至少一個為-SOj29, A , p2, D24, ’ R及R20相互獨立為甲 基R〜R相互獨立為碳數 勹丫 , A ,厌數1 4之1價之脂肪族烴基,r25 汉κ分別獨立為1; 巧風席子,η為0,R2、_r32,r32 1〜4之1價之脂肪族烴基。 I61700.doc -13· 201237118 作為化合物(1)之中,成為錯陰離子之配位子之吡唑偶 氮化合物的較佳例,可列舉式(l-al)〜式(l-a64)所示之化合 物等:At least one of them is Nitrate &Rr> 15 n IQ L 八<芏> At least one of - and ~ is -SOj29, A, p2, D24, 'R and R20 are mutually independent methyl R ~R is independent of each other as a carbon number A, A, an aliphatic hydrocarbon group having a valence of 1 4, and r25 Han κ is independently 1; Qiaofeng mat, η is 0, R2, _r32, r32 1~4 A fatty hydrocarbon group of a valence. I61700.doc -13·201237118 A preferred example of the pyrazole azo compound which is a ligand of a wrong anion among the compounds (1) is exemplified by the formula (1-al) to the formula (l-a64). Compounds, etc.:
(1-a1) (1-a3) ho3s ho3s H03S(1-a1) (1-a3) ho3s ho3s H03S
(1-a4) (1-a8) HO(1-a4) (1-a8) HO
(1-a9) H03S ^ OH H〇y(1-a9) H03S ^ OH H〇y
〇H HO 太 N〇2〇H HO too N〇2
H03S ^ OH HO N02H03S ^ OH HO N02
SO3H SO3H •so3h 〇H HOSO3H SO3H •so3h 〇H HO
HO HO3S ^ OHHO HO3S ^ OH
N〇2 N=N. 1 d-a16)N〇2 N=N. 1 d-a16)
OH HOOH HO
SO3H 14- 161700.doc 201237Π8 . N〇2V J 〇H H〇 .CH3SO3H 14- 161700.doc 201237Π8 . N〇2V J 〇H H〇 .CH3
Άη=η- /_Άη=η- /_
H〇# 〇2N'i H〇3SH〇# 〇2N'i H〇3S
〇H H〇〇H H〇
〇H〇H
C\ ,C\ n j4> o-a19)C\ ,C\ n j4> o-a19)
於 (A-a2〇) N、fp、s〇3H 6h ⑻ H2H〇2?(A-a2〇) N, fp, s〇3H 6h (8) H2H〇2?
Qr orQr or
ν=νΛ ^s〇2hh2° OH H〇 〇H H〇 N=^==νΛ ^s〇2hh2° OH H〇 〇H H〇 N=^
H^°2SH^°2S
CrNCrN
NN
N二N-\ 认 (1-a23)N two N-\ recognize (1-a23)
H〇2 〇2NH〇2 〇2N
OH h^n=n_\>s〇2nh2 ^-a24) 〇H H〇OH h^n=n_\>s〇2nh2 ^-a24) 〇H H〇
Qr ch3 (1-a25) HOa OH H〇 H〇 . ch3 nH H〇 S〇2^^ (1-a26) σ (Va27) 0Γ N〇2 n^n=n^^s〇2nh2 〇H H〇 (1-a28) ^1-a3〇)Qr ch3 (1-a25) HOa OH H〇H〇. ch3 nH H〇S〇2^^ (1-a26) σ (Va27) 0Γ N〇2 n^n=n^^s〇2nh2 〇HH〇( 1-a28) ^1-a3〇)
N=H- -s〇^H2N=H- -s〇^H2
H3^ W=H- (Va29) H#〇多H3^ W=H- (Va29) H#〇多
、H〇2H〇2
〇2N〇2N
OH H〇 H〇OH H〇 H〇
Cl PcrCl Pcr
N=NN=N
H〇H〇
n=n-A ^n=n-A ^
N 丄、 (1-a33) 〇H H〇 H2N°^ 〇釕 [ Η2Ν〇2^N 丄, (1-a33) 〇H H〇 H2N°^ 〇钌 [ Η2Ν〇2^
仂V?〇〇.d〇c仂V?〇〇.d〇c
(1 a-32) £r SJ OH HO H〇2 ^m=h^Xs H〇 N〇2 S02HH2 U〇2 , N〇2 nU)— S〇2^H2 H〇 H〇2 (A-a36) SO^iHz OH H〇(1 a-32) £r SJ OH HO H〇2 ^m=h^Xs H〇N〇2 S02HH2 U〇2 , N〇2 nU) — S〇2^H2 H〇H〇2 (A-a36 ) SO^iHz OH H〇
〇H HO hV>w=n^ OH HO〇H HO hV>w=n^ OH HO
,c\,c\
(Va3*H(Va3*H
H〇H〇
(1-a38) • \5- 201237118(1-a38) • \5- 201237118
HN〇asHN〇as
Qr (1-a3S) cQr (1-a3S) c
HOHO
HN〇2s cr“, OH H〇 (1-a4D N〇2HN〇2s cr", OH H〇 (1-a4D N〇2
1J1J
N〇2 U=\ 厂「\ (1-a*»3) ,N >-N=N-N〇2 U=\ factory "\ (1-a*»3) , N > -N=N-
HN〇2SHN〇2S
OH HOOH HO
HN〇2s,HN〇2s,
CrCr
OH HO (1-a45) H〇2 OjOH HO (1-a45) H〇2 Oj
HN〇2sHN〇2s
Η3αΆν=ν~^ OH HO (1-a47) H〇2 0a-49) N〇2Η3αΆν=ν~^ OH HO (1-a47) H〇2 0a-49) N〇2
HN〇2sHN〇2s
HOHO
m〇/^ 0H H〇 ,OH H〇M〇/^ 0H H〇 , OH H〇
(1-a5D (Va5^)(1-a5D (Va5^)
HNO2S ί HN〇2SHNO2S ί HN〇2S
N= OH H〇 (1-a55)N= OH H〇 (1-a55)
OrcrrOrcrr
N — I N H3C02S, 〇H H〇N — I N H3C02S, 〇H H〇
(1-a57)(1-a57)
广N OH HO S〇2CH3 (1-359) ⑹700.doc 201237118Wide N OH HO S〇2CH3 (1-359) (6)700.doc 201237118
作為化合物(1)之中,錯陰離子之較佳例,可列舉式(1-bl)〜式(l-b60)所示之陰離子等:Preferred examples of the wrong anion in the compound (1) include an anion represented by the formula (1-b1) to the formula (1-b60):
161700.doc -17-161700.doc -17-
S 2〇1237ll8S 2〇1237ll8
161700.doc •18 2〇1237ll8161700.doc •18 2〇1237ll8
s 201237118s 201237118
ss
,6,7〇〇.d〇c 22. 201237118,6,7〇〇.d〇c 22. 201237118
作為化合物(1)之中,來自二苯并哌喃化合物之陽離子 之較佳例,可列舉式(l-cl)〜式(1-C36)所示之陽離子等:Among the compounds (1), preferred examples of the cation derived from the dibenzopyran compound include a cation represented by the formula (1-cl) to the formula (1-C36):
161700.doc -23- 201237118161700.doc -23- 201237118
161700.doc ·24· 201237118161700.doc ·24· 201237118
201237118201237118
,化合物(1)可藉由,使用式(ld)所示之化合物(以下有時 稱為化合物(ld)」)與鉻化合物,形成鉻錯鹽,其後使該 鉻錯I與一苯并哌喃化合物進行鹽交換反應,或者使用化 合物(Id)與鈷化合物,形成鈷錯鹽,其後使該 鈷錯鹽與二 苯并哌喃化合物(b)進行鹽交換反應而製造。The compound (1) can be formed by using a compound represented by the formula (ld) (hereinafter sometimes referred to as a compound (ld)") and a chromium compound to form a chromium salt, and then the chromium is I and a benzo The piper compound is subjected to a salt exchange reaction, or a compound (Id) and a cobalt compound are used to form a cobalt salt, and then the cobalt salt is subjected to a salt exchange reaction with the dibenzopyran compound (b).
[式㈣中’ R丨〜R、Rl丨〜Rl4* r19表示與上述相 義]0[In the formula (4), 'R丨~R, Rl丨~Rl4* r19 means the same as above]
價之陰離子]。 作為1價之陰離子,可列舉cl-、Br·、r、Cl〇4.、Anion of the price]. Examples of the monovalent anion include cl-, Br·, r, Cl〇4.
BF4-等。 6 S 一苯并哌喃化合物(b)可藉由使式(bo)所示之化合物與式 161700.doc •26· 201237118 (bl)所示之化合物於有機溶劑中反應而製造。BF4- and so on. The 6 S monobenzopyran compound (b) can be produced by reacting a compound represented by the formula (bo) with a compound represented by the formula 161700.doc •26·201237118 (bl) in an organic solvent.
[式(b0)及式(bl)中,〜r”、η及A-表示與上述相同之意 義]0 於上述反應中,反應溫度較佳為i 5<»c 〜60°c,反應時間 較佳為1小時〜丨2小時。又,就縮短反應時間或提高產率之 面而β較佳為使用酸觸媒及/或脫水劑。 作為酸觸媒’可列舉硫酸、對曱苯磺酸等。 作為脫水劑’可列舉:二環己基碳二醯亞胺、二異丙基 石反一醯亞胺、丨_乙基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽 酸鹽等奴二酿亞胺類;丨_烷基_2_鹵化吡啶鏽鹽類;丨,丨,-羰 基一°米嗤;雙(2-氧代-3-噚唑啶基)次膦醯氣;碳酸二(2-吡 咬)睡繁 # Ay ^ 具中’作為脫水劑,因後處理及純化容易,故 而車乂佳為1·乙基_3_(3_二甲基胺基丙基)碳二醯亞胺鹽酸 L用之有機溶劑,可列舉:二氣甲 曱苯、乙腈等。 作為上述反應中所使用之 烷、氯仿、四氫呋喃、甲苯、 成為化合物(1)之錯陰離子 由染料領域中眾所周知之,.[In the formula (b0) and the formula (bl), 〜r", η and A- represent the same meanings as described above]. 0 In the above reaction, the reaction temperature is preferably i 5 <»c to 60 ° C, reaction time It is preferably from 1 hour to 2 hours. Further, in order to shorten the reaction time or increase the yield, β is preferably an acid catalyst and/or a dehydrating agent. As the acid catalyst, sulfuric acid or p-benzenesulfonate may be mentioned. Acid, etc. As a dehydrating agent, there may be mentioned dicyclohexylcarbodiimide, diisopropyl rock anti-imine, and hydrazine-ethyl-3-(3-dimethylaminopropyl)carbon dioxime. Isoimine hydrochloride, such as imine hydrochloride; 丨-alkyl-2_halogenated pyridine rust; 丨, 丨, -carbonyl, ° 嗤; bis(2-oxo-3-oxazolidine)次phosphine gas; carbonic acid (2-pyrobitate) sleeping complex # Ay ^ with 'in the dehydrating agent, because of post-treatment and purification is easy, so the car 乂 is 1 · ethyl _3_ (3 dimethyl The organic solvent for the aminopropyl)carbodiimide hydrochloride L may, for example, be dimethylbenzene, acetonitrile or the like. The alkane, chloroform, tetrahydrofuran, toluene used in the above reaction may be the compound (1). Wrong anion Materials is well known in the field.
離子之配位子的化合物(1 d),可藉 之’使重氮鹽(diazonium salt)與η比 的方法而製造。例如,可使用將式 161700.doc -27- 201237118 (la)所示之胺(以下有時稱為「胺(la)」)’藉由亞石肖酸、亞 硝酸鹽或亞硝㈣進行錢Μ獲得的式⑽所示之化合 物,作為上述重氮鹽。The compound (1 d) of the ligand of the ion can be produced by a method of making a ratio of diazonium salt to η. For example, an amine represented by the formula 161700.doc -27- 201237118 (la) (hereinafter sometimes referred to as "amine (la)") can be used to carry out money by succinic acid, nitrite or nitrous acid (four). The compound represented by the formula (10) obtained as hydrazine is used as the above diazonium salt.
[式(U)及式(UO中,R"〜Rh表示與上述相同之意義;ν. 表示無機或有機陰離子;I» 作為上述無機陰離子,例如可列舉:氣化物離子、氣化 物離子、漠化物離子、硤化物離子、過氣酸離子、次氣酸 離子等。作為上述有機陰離子,例如可列舉:CH3C〇〇·、 QHsCOO·等。較佳可列舉:氣化物離子、溴化物離子、 CH3CO〇-等。 藉由將式(lb)所示之化合物與式(le)所示之化合物於水 性溶劑中進行重氮偶合,可製造式(ld)所示之化合物(以下 有時稱為「化合物(Id)」)。反應溫度較佳為·rd, 更佳為0°c〜3(TC »反應時間較佳為丨小時〜12小時,更佳為 1小時〜4小時。作為上述水性溶劑,例如可列舉N_甲基吡 咯烷酮等。[In the formula (U) and formula (in UO, R"~Rh represents the same meaning as above; ν. represents an inorganic or organic anion; I» as the above inorganic anion, for example, a vaporized ion, a vaporized ion, and a desert Examples of the organic anion include CH3C〇〇·, QHsCOO·, etc. Preferred examples thereof include a vaporized ion, a bromide ion, and a CH3CO. 〇-, etc. By diazo coupling of a compound represented by the formula (lb) and a compound of the formula (le) in an aqueous solvent, a compound represented by the formula (ld) can be produced (hereinafter sometimes referred to as " The compound (Id)"). The reaction temperature is preferably rd, more preferably 0 ° c to 3 (TC » reaction time is preferably from 丨 to 12 hours, more preferably from 1 hour to 4 hours. For example, N-methylpyrrolidone or the like can be mentioned.
(1C) [式(1C)中,R1〜R5及R19表 化合物(Id)具有-S02R29 示與上述相同之意義]。 ,_S02R29 為-s〇2NHR30 之情形 161700.doc -28- 201237118 時’亦可使用具有·s〇2NHR3Q之胺(la)而製造,但較佳為 使用具有4基之胺(u)進行偶合反錢,料基進行續酿 胺化而製造。例如’可預先合成化合物〇d)中具有續基之 偶氮化合物(以下稱為「化合物(ls)」),藉由亞硫醯函化 合物將績基(別⑻進行姐_化(_s〇2X ; χ㈣素原子) 而獲得磺醯鹵化合物,繼而使磺醯函化合物與胺(r3〇nh2) 進行反應’藉此將磺基進行磺醯胺化,而製造化合物 (Id)。 作為化合物(Is)之具體例,可列舉:式(l ai)、式Ο- β) 、 式(1_a5) 〜 (1_a2〇)所示之化合物 ,較佳可 列舉式(卜 ⑼、(1-a6)、(1_al5)及(1_al6)所示之化合物。作為亞硫醯 齒化合物,可列舉:亞硫醯a、亞硫醯氣、亞硫醯漠、亞 硫醯碘等,較佳可列舉亞硫醯氣、亞硫醯溴等,尤佳可列 舉亞硫醯氯。亞硫醯鹵之使用量,相對於化合物(^口莫 耳,較佳為1〜10莫耳。再者’於反應系中帶入水之情形 時’較佳為過量使用亞硫醯函化合物。 磺醯齒化係於溶劑令進行。作為溶劑,例如可使用: M-二呤烷等醚類(尤佳為環狀醚類);氯仿、二氣甲貌、 四氯化碳、1,2-二氯乙烷、二氯乙烯、三氣乙烯j全氯乙 烯、二氣丙烷、氯戊烷、1,2-二溴乙烷等南化烴類等。溶 敎使用量’相對於化合物(1_量份’例如為墚量: 以上(較佳為5質量份以上)、10質量份以下(較佳為8質量份 以下)》 ” 又,於磺醯幽化中’較佳為併用N,N-二烷基甲醯胺(例 161700.doc •29- 201237118 如’ N,N-二曱基曱醯胺、N,N_:乙基甲醯胺等)。於使用 Ν’Ν-二院基甲醯胺之情形時,其使用量相對於亞硫醢鹵化 合物1莫耳,例如為0.054莫耳。若預先將化合物(ls)與 N,N-二烷基甲醯胺於溶劑中混合後,添加亞硫醯鹵化合 物’則可抑制發熱。 碩醯鹵化之反應溫度,例如為〇它以上、較佳為3〇它以 上,70°C以下、較佳為6〇t以下。反應時間,例如為〇 5 小時以上、較佳為3小時以上,8小時以下、較佳為5小時 以下。 以上述方法製備之磺醯齒化合物,可經單離後與胺 (R3GNH2)反應,亦可不經單離而直接以反應混合物之狀態 與胺(R3GNH2)反應。再者,於單離之情形時,例如,混合 反應混合物與水,過濾獲取析出之結晶即可。取得之磺醯 画化合物之結晶與胺(R^NH2)反應前,視需要可進行水洗 及乾燥。 作為胺(r30nH2),包含正丙胺、正丁胺、正己胺二甲 基己胺(I,5·二甲基己胺等)、四曱基丁胺甲基丁 胺,)、乙基己胺(2-乙基己胺等)、胺基苯基丁院(3_胺基· 1_苯基丁烧等)、異丙氧基丙胺等。胺化3。叫)之使用量, 相對於磺醯函化合物丨莫耳,為2莫耳以上,10莫耳以下、 較佳為7莫耳以下。 相齒化合物與胺(R3〇NH2)之添加順序並無特別限定, 較佳為於磺醯齒化合物中添加(滴加)胺^3%4)。又,磺 酿齒化合物與胺(R3〇NH2)之反應較佳為於溶劑中進行 I61700.doc -30- 201237118 為溶劑,可使用與製備磺醯函化合物時相同之溶劑。 又,磺醯函化合物與胺(R^NH2)之反應,較佳為於鹼性 觸媒之存在下進行。作為驗性觸媒,例如可列舉=級胺 (二乙胺、二乙if·胺專脂肪族三級胺;比咬等芳香族一級 月女)、及·一級胺(一乙胺專脂肪族二級胺;η底咬等環狀月匕肪 族二級胺)等。該等之中,較佳為三級胺,尤佳為三乙胺 等脂肪族三級胺。鹼性觸媒之使用量,相對於胺 (R ΝΗ2) ’為1.1莫耳以上、6莫耳以下,較佳為}」莫耳以 上、5莫耳以下。 於磺酿齒化合物中添加胺(r3〇NH2)與鹼性觸媒之情形 時’鹼性觸媒之添加時序並無特別限定,可於胺(r3QnH2) 添加前及添加後之任一者,亦可以與胺(r3〇NH2)相同之時 序添加。又,可預先與反應性胺混合後進行添加,亦可與 胺(R3GNH2)分開添加。 磺醯鹵化合物與胺(r3〇NH2)之反應溫度,例如為〇β(:以 上、50°C以下’較佳為〇°c以上、30°C以下。又,反應時 間為1〜5小時。 自反應混合物取得作為目標化合物之化合物(ld)的方法 並無特別限定,可採用公知之各種手法。例如,較佳為將 反應混合物與酸(例如乙酸等)及水混合,過濾獲取析出之 結晶。上述酸,較佳為預先製備酸之水溶液後,將反應混 合物添加至上述水溶液中。添加反應混合物時之溫度,較 佳為10°C以上50°c以下,更佳為2〇r以上5〇t以下,進而 更佳為20°C以上30。(:以下。又,較佳為將反應混合物添加 161700.doc •31 · 201237118 至酸之水溶液中後,進而於上述溫度下搜拌〇·5〜2小時左 右。過據獲取之結晶較佳為以水等清洗,繼而㈣。又視 需要,可藉由再結晶等公知之手法進而純化。 於化合物(1)之陰離子部分為鉻錯陰離子(式(1)中之…為 Cr)之情形時,可藉由使化合物〇d)與絡化合物於水性溶劑 中於70〜l〇〇eC下進行反應而製造。較佳為使化合物與 絡化合物以2:1〜4:1之莫耳比進行反應。 作為上述鉻化合物,可列舉:甲酸鉻、乙酸鉻氣化 鉻、氟化鉻等,較佳可列舉:甲酸鉻、乙酸鉻、硫酸鉻 (III)敍十二水酯等。 化合物(1)可藉由使鉻錯鹽與二苯并哌喃化合物(b)於溶 劑中進行鹽交換反應而製造。較佳為使鉻錯鹽與二苯并哌 喃化合物(b)以1:1〜1:4之莫耳比進行反應。 於化合物(1)之陰離子部分為鈷錯陰離子(式(丨)中之河丨為 C〇)之情形時,可藉由使化合物(ld)與鈷化合物於水性溶劑 中於70〜l〇〇°C下進行反應而製造。較佳為使化合物與 始化合物以2:1〜4:1之莫耳比進行反應。 作為上述銘化合物,可列舉:氯化鈷、乙酸鈷、硫酸 姑、乙醯丙酮鈷(III)(tris(2,4-pentanedionato)cobalt(III)) 等,較佳為乙醯丙酮鈷(in)等。 化合物(1)可藉由使鈷錯鹽與二苯并哌喃化合物(b)於溶 劑中進行鹽交換反應而製造。較佳為使鈷錯鹽與二苯并派 喃化合物(b)以1:1〜;L4之莫耳比進行反應。 作為化合物(1) ’具體可列舉式(1-1)〜式(1·26)所示之化 161700.doc •32- 201237118 合物等。(1C) [In the formula (1C), the compound (Id) of R1 to R5 and R19 has -S02R29 which has the same meaning as described above]. When _S02R29 is -s〇2NHR30, 161700.doc -28- 201237118 can also be produced using amine (la) having ·s〇2NHR3Q, but it is preferred to use a 4-group amine (u) for coupling reaction. The money and the base are manufactured by continuous amination. For example, an 'azo compound having a recurring group (hereinafter referred to as "compound (ls)") can be synthesized in the compound 〇d, and the thiol compound can be used as a base (by ss2X). The sulfonium halide compound is obtained, and then the sulfonium halide compound is reacted with the amine (r3〇nh2), whereby the sulfo group is subjected to sulfoximation to produce the compound (Id). Specific examples of the compound include a formula (1 ai), a formula Ο-β), and a compound represented by the formula (1_a5) to (1_a2〇), and preferably a formula (b (9), (1-a6), ( a compound represented by 1_al5) and (1_al6). Examples of the sulphur-based carcass compound include sulfinium a, sulfinium, sulfoxide, sulfoxide, and the like. And sulfinium bromide, etc., particularly preferably sulphur ruthenium chloride. The amount of sulfinium halide used is relative to the compound (mole, preferably 1 to 10 moles. Further in the reaction system) In the case of water, it is preferred to use a sulfite compound in excess. The sulfonate is carried out in a solvent. As a solvent, for example, it can be used. Ethers such as M-dioxane (especially cyclic ethers); chloroform, dioxo, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, triethylene glycol, and perchloroethylene , aeronautical hydrocarbons such as di-propane, chloropentane, 1,2-dibromoethane, etc. The amount of dissolved solute used is relative to the compound (1 _ parts by weight: for example: above (preferably 5 mass) More than or equal to), 10 parts by mass or less (preferably 8 parts by mass or less) ” Further, in the sulfonate cleavage, it is preferred to use N,N-dialkylformamide in combination (Example 161700.doc •29- 201237118 Such as 'N,N-dimercaptoamine, N,N_: ethylformamide, etc.). When using Ν'Ν-二院基甲胺胺, its use is relative to sulfoxide The halogen compound 1 mol is, for example, 0.054 mol. If the compound (ls) and the N,N-dialkylformamide are mixed in a solvent in advance, the addition of the sulfinium halide compound can suppress heat generation. The reaction temperature of the halogenation is, for example, 〇 or more, preferably 3 Å or more, 70 ° C or less, preferably 6 Torr or less. The reaction time is, for example, 5 hours or more, preferably 3 hours or more, 8 The following is preferably 5 hours or less. The sulfonate compound prepared by the above method may be reacted with an amine (R3GNH2) after isolation, or may be directly reacted with an amine (R3GNH2) in a state of a reaction mixture without isolation. Further, in the case of separation, for example, mixing the reaction mixture with water, and filtering to obtain precipitated crystals. The obtained crystals of the sulfonate compound can be washed as needed before reacting with the amine (R^NH2). And drying. As an amine (r30nH2), it contains n-propylamine, n-butylamine, n-hexylamine dimethylhexylamine (I,5·dimethylhexylamine, etc.), tetradecylbutylamine methylbutylamine, A hexylamine (2-ethylhexylamine or the like), an aminophenyl butyl compound (3-amino group, 1-phenylbutyring or the like), isopropoxypropylamine or the like. Amination 3. The amount used is 2 mol or more, 10 mol or less, preferably 7 mol or less, relative to the sulfonium compound. The order of addition of the phase-tooth compound and the amine (R3〇NH2) is not particularly limited, and it is preferred to add (drop) the amine ^3%4) to the sulfonate compound. Further, the reaction of the sulfonate compound with the amine (R3?NH2) is preferably carried out in a solvent. I61700.doc -30-201237118 is a solvent, and the same solvent as that used in the preparation of the sulfonium compound can be used. Further, the reaction of the sulfonium compound with the amine (R^NH2) is preferably carried out in the presence of a basic catalyst. As an organic catalyst, for example, a grade amine (diethylamine, a di-ethylamine, an aliphatic tertiary amine; an aromatic first-degree female such as a bite), and a primary amine (monoethylamine) can be cited. Secondary amine; η bottom bite and other cyclic guanidine aliphatic secondary amines). Among these, a tertiary amine is preferred, and an aliphatic tertiary amine such as triethylamine is preferred. The amount of the basic catalyst used is 1.1 mol or more and 6 mol or less with respect to the amine (R ΝΗ 2) ', preferably 5 Å or more, and 5 mol or less. When the amine (r3〇NH2) and the basic catalyst are added to the saponin compound, the addition timing of the alkaline catalyst is not particularly limited, and may be before or after the addition of the amine (r3QnH2). It can also be added at the same timing as the amine (r3〇NH2). Further, it may be added after mixing with a reactive amine in advance, or may be added separately from the amine (R3GNH2). The reaction temperature of the sulfonium halide compound and the amine (r3〇NH2) is, for example, 〇β (: above, 50 ° C or less, preferably 〇 ° c or more, 30 ° C or less. Further, the reaction time is 1 to 5 hours. The method of obtaining the compound (ld) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferred to mix the reaction mixture with an acid (for example, acetic acid or the like) and water, and to obtain a precipitate by filtration. The above-mentioned acid is preferably prepared by adding an aqueous solution of an acid to the aqueous solution in advance, and the temperature at which the reaction mixture is added is preferably 10 ° C or more and 50 ° C or less, more preferably 2 〇r or more. 5 〇 t or less, and more preferably 20 ° C or more 30. (: The following. Further, it is preferred to add the reaction mixture to 161700.doc • 31 · 201237118 to an aqueous acid solution, and then mix at the above temperature. 5~2 hours or so. The crystal obtained is preferably washed with water or the like, and then (4). Further, if necessary, it can be further purified by a known method such as recrystallization. The anion portion of the compound (1) is chromium. Anion In the case of (1) in the case of Cr), it can be produced by reacting the compound 〇d) with a complex compound in an aqueous solvent at 70 to 1 〇〇e C. Preferably, the compound and the complex compound are The molar ratio of 2:1 to 4:1 is exemplified. Examples of the chromium compound include chromium formate, chromium carbonate vapor, chromium fluoride, and the like. Preferred examples thereof include chromium formate, chromium acetate, and chromium sulfate. III) sulphate or the like. The compound (1) can be produced by subjecting a chromium salt to a salt exchange reaction with a dibenzopyran compound (b) in a solvent. Preferably, the chromium salt is mixed with diphenyl. And the piper compound (b) is reacted at a molar ratio of 1:1 to 1:4. When the anion portion of the compound (1) is a cobalt-substituted anion (the river enthalpy in the formula (丨) is C〇) It can be produced by reacting the compound (ld) with a cobalt compound in an aqueous solvent at 70 to 1 ° C. Preferably, the compound and the starting compound are in a molar ratio of 2:1 to 4:1. The reaction is carried out. As the above-mentioned indicating compound, cobalt chloride, cobalt acetate, sulfuric acid, and cobalt(III) acetate (III) (tris(2,4-pentanedionat) can be cited. o) cobalt (III)), etc., preferably acetonitrile, cobalt (in), etc. The compound (1) can be subjected to a salt exchange reaction with a dibenzopyran compound (b) in a solvent by a cobalt salt. Preferably, the cobalt salt is reacted with the dibenzophenan compound (b) at a molar ratio of 1:1 to L4. Specific examples of the compound (1) ' can be exemplified by the formula (1-1) to (1·26) shown in the 161700.doc •32- 201237118 compound.
(1-1) (1-2)(1-1) (1-2)
161700.doc •33- ,6l?00.d〇c161700.doc •33- ,6l?00.d〇c
(1-6) •34· 201237118(1-6) •34· 201237118
161700.doc -35- l6l7〇〇.d〇c 2〇l237ll8161700.doc -35- l6l7〇〇.d〇c 2〇l237ll8
-36. 201237118 h3co2s-36. 201237118 h3co2s
(1-21) (1-22) so2ch3 Θ σ /卜N=N— 〇〆 o2n(1-21) (1-22) so2ch3 Θ σ /bu N=N— 〇〆 o2n
-Ν=Ν—ι sN-Ν=Ν—ι sN
@、 〇 〜 (1-23)@, 〇 〜 (1-23)
匕 H3C〇2S σ匕 H3C〇2S σ
SOoCHsSOoCHs
o2n H3C02SO2n H3C02S
N=N—f ι N \ J〇 ΘN=N—f ι N \ J〇 Θ
0'^'o^<S (1-24)0'^'o^<S (1-24)
161700.doc •37· 201237118161700.doc •37· 201237118
曾^。°物⑴之含!較佳為於著色劑⑷中為1質量。以上99 /〇以下’更佳為1質量%以上8〇質量%以下進而更佳 為3質量%以上7〇質量%以下。 著色劑(A)可與化合物(1)一同含有與化合物(1)不同之染 料。作為該染料,可列舉:油溶性染料、酸性染料、酸性 染料之胺鹽或酸性染料之磺醯胺衍生物等染料,例如可列 舉:染料索引(The Society of Dyers and Colourists 出版)中 分類為染料之化合物或染料手冊(Dyeing note,色染杜)十 揭示之公知之染料。 具體而言,可列舉:C.I.溶劑黃4(以下,省略C.I.溶劑黃 之記述,僅記述編號)、14、15、23、24、38、62、63、 68 、 82 、 94 、 98 、 99 、 162 ; C.I·溶劑紅45、49、125、130 ; C.I·溶劑橙2、7、11、15、26、56 ;等 C.I.溶劑染料、 C.I.酸性黃 1、3、7、9、11、17、23、25、29、34、 161700.doc •38· 201237118 36、38、40、42、54、65、72、73、76、79、98、99、 111、112、113、114、116、119、123、128、134、135、 138 、 139 、 140 、 144 、 150 、 155 、 157 、 160 、 161 、 163 、 168 、 169 、 172 、 177 、 178 、 179 、 184 、 190 、 193 、 196 、 197 ' 199 、 202 、 203 、 204 、 205 、 207 、 212 、 214 、 220 、 221 、 228 、 230 ' 232 、 235 、 238 、 240 、 242 、 243 、 251 ; C.I.酸性紅 1、4、8、14、17、18、26、27、29、31、 34、35、37、42 ' 44、50、51、52、57、66、73、80、 87、88、91、92、94、97、103、111、114、129、133、 134 、 138 、 143 、 145 ' 150 、 151 、 158 、 176 、 182 、 183 、 198 、 206 、 211 、 215 、 216 、 217 、 227 、 228 、 249 、 252 、 257 ' 258 ' 260 ' 261 ' 266、268、270 ' 274 ' 277 ' 280、 281 、 195 、 308 、 312 、 315 、 316 、 339 、 341 、 345 、 346 、 349 、 382 、 383 、 394 、 401 、 412 、 417 、 418 、 422 ' 426 ; C.I·酸性橙6、7、8、10、12、26、50、51、52、56、 62 、 63 、 64 、 74 、 75 、 94 、 95 、 107 、 108 、 169 、 173 ; C.I.酸性紫6B、7、9、17、19 ;等C.I.酸性染料、 C.I.直接黃 2、33、34、35、38 ' 39、43、47、50、54、 58 、 68 、 69 、 70 、 71 、 86 、 93 、 94 、 95 、 98 、 102 、 108 、 109 ' 129 ' 136 、 138 、 141 ; C.I.直接紅 79、82、83、84、91、92、96、97、98、 99、105、106、107、172、173、176、177 ' 179、181、 182 、 184 ' 204 、 207 、 211 、 213 、 218 、 220 、 221 、 222 ' 232 ' 233、234、241、243、246 ' 250 ; 161700.doc •39- 201237118 C.I.直接橙 34、39、41、46、50、52、56、57、61、 64、 65、 68、 70、 96、 97、 1〇6、 1〇7; C.I·直接紫 47、52、54、59、60、65、66、79、8〇、 81、82、84、89、90、93、95、96、103、104 ;等 CU 直 接染料、 作為C.I·媒染染料之CJ媒染黃5 10、 16、 20、 26、 3〇、31、33、42、43、45、56、61、62、65 19、 39、 86' 23、 <^.1.媒染紅1、2、3、4、9、11、12、14、17、18 22、23、24、25、26、30、32、33、36、37、38 41、43、45、46、48、53、56、63、71、74、85 88 、 90 、 94 、 95 ; C.I.媒染燈3、4、5、8、12、U、14、20、21 24 28 、 29 、 32 、 34 、 35 、 36 、 37 、 42 、 43 、 47 、 48 ; C.I·媒染紫 1、2、4、5、7、14、22、24、3〇、3ι、&、 37、40、41、44、45、47'48、53 58;等^媒染染料 等0 著色劑(A)可進而與化合物(丨)一同含有顏料。 作為顏料,可列舉有機顏料,例如,C.I.顏料紫1、19、 23 ' 29、32、36、38等紫色顏料;^丄顏料黃丨、3、12、 13、14、15、16、17、20、24、31、53、83、86、93 ' 94、109、11〇、ι17、125、128、137、138、139、147、 148 ' 150 ' 153 ' 154 ' 166、173、194、214等黃色顏料; 〇.1.顏料燈13、31、36、38、40、42、43、51、55、59、 61、64、65、71、73等橙色顏料; 161700.doc • 40· 201237118 C.I.顏料紅 9、97、105、122、123、144、149、16ό、 168 、 176 、 177 、 180 、 192 、 209 、 215 、 216 、 224 、 242 、 254、255、264、265等紅色顏料等。其中,較佳為含有選 自 C.I·顏料黃 138、139、15〇,〇 工顏料紅 177、242、254 中 之至;一種。藉由含有上述顏料,可使透射光譜之最適化 變得容易’耐化學品性變得良好。 該等顏料可單獨亦可混合兩種以上使用。 有機顏料視需要可實施松香處理、使用導入有酸性基或 鹼性基之顏料衍生物等之表面處理、藉由高分子化合物等 之對顏料表面之接枝處理、藉由硫酸微粒化法等之微粒化 處理、或用以除去雜質之藉由有機溶劑或水等之清洗處 理離子性雜質之藉由離子交換法等之除去處理等。 有機顏料較佳為粒徑均勻。藉由含有顏料分散劑而進行 分散處理’可獲得顏料於溶液中均勻分散狀態的顏料分散 液。 作為上述顏料分散劑,例如可列舉:陽離子系、陰離子 系、非離子系、兩性、聚酯系、聚胺系、丙烯酸系等之界 面活性劑等。該等顏料分散劑可單獨亦可組合兩種以上使 用。作為顏料分散劑,可列舉:商品名為κρ(信越化學工 業(股)製造)、Flowlen(共榮社化學(股)製造)、 (Zeneca(股)製造)、EFKA(CIBA公司製造)、Ajispe《味之 素精細化學(Ajinomoto Fine-Techn〇 c〇 Inc )(股)製造)' Disperbyk(BYK-Chemie公司製造)等。 於使用顏料分散劑之情形時,苴使用 ,、使用重相對於顏料 161700.doc • 41 · 201237118 (A2),較佳為1 〇〇質量%,更佳為5質量%以上、5〇質量%以 下。若顏料分散劑之使用量為上述範圍,則存在可獲得均 勻之分散狀態之顏料分散液的傾向。 於著色劑(A)中含有顏料之情形時,該顏料之含量較佳 為1〜99質量%,更佳為10〜97質量%。 化合物(1)與顏料之含量比率(質量比)較佳為1:99〜99:ι, 更佳為3:97〜90:10。藉由設為此種比率,可使透射光譜之 最適化變得容易,獲得高對比度、高亮度,故而較佳。進 而,耐熱性、耐化學品性變得良好。 尤佳為化合物(1)與選自由〇 顏料黃138、c丨顏料黃 139、C.I·顏料黃150、CI顏料紅177、ci顏料紅242及 C.I.顏料紅254所組成之群中之至少一種的質量比為 3.97〜90:10’ 更佳為 3:97〜7〇:3〇。 著色劑(A)之含量,相對於著色感光性樹脂組合物中之 固形物成分,較佳為5〜6〇質量%,更佳為8〜55質量%,進 而更佳為10〜50質量%β此處,所謂固形物成分係指著 色感光性樹脂組合物中之,除去溶劑之成分的合計。若著 色劑(Α)之含量為上述範圍,則作為彩色濾光片時之色濃 度充分’且可於組合物中含有必需量之黏合劑聚合物,故 而可形成機械強度充分之圖案。 本發明之著色感t性樹脂組合物含有樹脂⑻。作為樹 月曰⑻’並無特別限定,較佳為驗可溶性樹脂。 作為接Ha(B) ’例如可列舉以下之樹脂[κι]〜[κ4]等。 [Κ1]具有碳數2〜4之環狀醚結構與乙烯性不飽和鍵之單 161700.doc -42- 201237118 體(a)(以下有時稱為「⑷」)與選自由不飽和缓酸及不飽和 叛酸野所組成之群中之至少一種⑻(以下有時稱為「㈨」) 的共聚物。 [K2]⑷與⑻與可與⑷共聚合之單體⑷(其中,與⑷及 (b)不同)(以下有時稱為「⑷」)的共聚物 [K3](b)與(c)之共聚物 [K4]使(b)與(e)之共聚物與⑷反應而獲得之樹脂。 藉由使樹脂(B)含有來自(a)之結構單元,可進一步提高 所得著色圖案之耐熱性、耐化學品性等可靠性。 (a)係例如具有碳數2〜4之環狀醚結構(例如,選自由環氧 乙烧環、氧雜環丁燒環及四氫。夫嗔環(氧雜環戊炫環)所組 成之群中之至少一種)與乙烯性不飽和鍵的聚合性化合 物。(a)較佳為具有碳數2〜4之環狀醚與(甲基)丙烯醯氧基 之單體。 再者,於本說明書中’所謂「(甲基)丙烯酸」,係表示 選自由丙烯酸及甲基丙烯酸所組成之群中之至少一種。 「(甲基)丙稀醯基」及「(曱基)丙烯酸醋」等表述亦具有 相同意義。 作為⑷’例如可列舉:具有環氧乙絲與乙稀性不餘和 鍵之單體⑷)(以下有時稱為「(al)」)、具有氧雜環丁院基 與乙烯性不飽和鍵之單體(a2)(以下有時稱為「(&2)」)、具 有四氫呋喃基與乙烯性不飽和鍵之單體(a3)(以下有時稱為 「⑷)」)等。 (al)例如可列舉:具有將鏈式烯烴進行環氧化之結構之 161700.doc -43- 201237118 °°體(al 1)(以下有時稱為「(al l)」)、具有將環式稀煙進 行環氧化之結構之單體(al_2)(以下有時稱為「(Μ)」 作為⑷·1) ’可列舉:(甲基)丙烯酸縮水甘油醋、(甲基) =歸酸β-曱基縮水甘油醋、(甲基)丙稀酸ρ·乙基縮水甘油 酯、縮水甘油基乙烯基醚、鄰乙烯基苄基縮水甘油醚、間 乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、&甲. 基鄰乙烯基?基縮水甘㈣U基.間乙稀基f基縮水 ' 甘油醚、α-甲基-對乙烯基苄基縮水甘油醚、2,3•雙(縮水 甘油氧基甲基)苯乙烯、2,4_雙(縮水甘油氧基甲基)苯乙 烯、2,5-雙(縮水甘油氧基曱基)苯乙烯、2,6_雙(縮水甘油 氧基甲基)苯乙烯、2,3,4-三(縮水甘油氧基甲基)苯乙烯、 2.3.5- 三(縮水甘油氧基甲基)苯乙烯、2,3,6_三(縮水甘油氧 基甲基)苯乙烯、3,4,5-三(縮水甘油氧基曱基)苯乙烯、 2.4.6- 三(縮水甘油氧基曱基)苯乙烯等。 作為(al-2),可列舉:一氧化乙烯基環己烯、12環氧_ 4-乙烯基環己烷(例如,Ceii〇xide 2000 ; Daicel化學工業 (股)製造)、3,4-環氧環己基曱基(曱基)丙烯酸g旨(例如, Cyclomer A400 ; Daicel化學工業(股)製造)、3,4-環氧環己 基曱基(曱基)丙烯酸酯(例如,Cyclomer M100 ; Daicel化 學工業(股)製造)、式(I)所示之化合物及式(Η)所示之化合 物等。Once ^. °The content of (1)! It is preferably 1 mass in the colorant (4). The above 99 / 〇 or less is more preferably 1% by mass or more and 8 % by mass or less, more preferably 3% by mass or more and 7 % by mass or less. The coloring agent (A) may contain a dye different from the compound (1) together with the compound (1). Examples of the dye include dyes such as an oil-soluble dye, an acid dye, an amine salt of an acid dye, or a sulfonamide derivative of an acid dye, and examples thereof include a dye index (published as a dye in The Society of Dyers and Colourists). A well-known dye disclosed in the Dyeing note. Specific examples include CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162 ; CI · Solvent Red 45, 49, 125, 130; CI · Solvent Orange 2, 7, 11, 15, 26, 56; CI solvent dye, CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 161700.doc • 38· 201237118 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119 , 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197 '199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230' 232, 235, 238, 240, 242, 243, 251; CI acid red 1, 4, 8, 14 17, 18, 26, 27, 29, 31, 34, 35, 37, 42 '44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145 '150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257 '258 ' 260 ' 261 ' 266, 268, 270 ' 274 ' 277 ' 280, 281 , 195 , 308 , 312 , 315 , 316 , 339 , 341 , 345 , 346 , 349 , 382 , 383 , 394 , 401 , 412 , 417 , 418 , 422 ' 426 ; CI · Acidic Oranges 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; etc. CI acid dye, CI direct yellow 2, 33, 34, 35, 38 '39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94 , 95 , 98 , 102 , 108 , 109 ' 129 ' 136 , 138 , 141 ; CI Direct Red 79 , 82 , 83 , 84 , 91 , 92 , 96 , 97 , 98 , 99 , 105 , 106 , 107 , 172 , 173, 176, 177 '179, 181, 182, 184 '204, 207, 211, 213, 218, 220, 221, 222 '232' 233, 234, 241, 243, 246 '250; 161700.d Oc •39- 201237118 CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 1〇6, 1〇7; CI·Direct Purple 47, 52, 54, 59, 60, 65, 66, 79, 8〇, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CU direct dye, as CI mordant dye CJ mediated yellow 5 10, 16, 20, 26, 3 〇, 31, 33, 42, 43, 45, 56, 61, 62, 65 19, 39, 86' 23, <^.1. mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85 88, 90, 94, 95; CI mordant lamps 3, 4, 5, 8, 12, U, 14, 20, 21 24 28, 29, 32, 34, 35, 36, 37, 42 , 43 , 47 , 48 ; CI · mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 3〇, 3ι, &, 37, 40, 41, 44, 45, 47' 48, 53 58; etc. The mordant dye (0) may further contain a pigment together with the compound (丨). Examples of the pigment include organic pigments such as violet pigments such as CI Pigment Violet 1, 19, 23 '29, 32, 36, and 38; and 丄 pigment jaundice, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93 '94, 109, 11 〇, ι 17, 125, 128, 137, 138, 139, 147, 148 ' 150 ' 153 ' 154 ' 166, 173, 194, 214 Etc. yellow pigment; 〇.1. Pigment lamps 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; 161700.doc • 40· 201237118 Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 16 ό, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. . Among them, it is preferred to contain one selected from the group consisting of C.I. Pigment Yellow 138, 139, 15 〇, and 〇 颜料 Pigment Red 177, 242, 254; By containing the above pigment, it is possible to optimize the transmission spectrum. The chemical resistance is improved. These pigments may be used alone or in combination of two or more. The organic pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment on a pigment surface by a polymer compound or the like, a sulfuric acid micronization method, or the like, as needed. The micronization treatment or the removal treatment of the ionic impurities by washing with an organic solvent or water to remove impurities, etc., by an ion exchange method or the like. The organic pigment preferably has a uniform particle size. The dispersion treatment is carried out by containing a pigment dispersant, and a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include κρ (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), (made by Zeneca), EFKA (manufactured by CIBA), and Ajispe. "Ajinomoto Fine-Techn〇c〇 Inc.") manufactured by Disperbyk (manufactured by BYK-Chemie Co., Ltd.). In the case of using a pigment dispersant, it is used in a weight ratio of 161700.doc • 41 · 201237118 (A2), preferably 1% by mass, more preferably 5% by mass or more, and 5% by mass. the following. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained. In the case where the colorant (A) contains a pigment, the content of the pigment is preferably from 1 to 99% by mass, more preferably from 10 to 97% by mass. The content ratio (mass ratio) of the compound (1) to the pigment is preferably from 1:99 to 99:m, more preferably from 3:97 to 90:10. By setting such a ratio, it is preferable to optimize the transmission spectrum and obtain high contrast and high luminance. Further, heat resistance and chemical resistance become good. More preferably, the compound (1) and at least one selected from the group consisting of ruthenium pigment yellow 138, c 丨 pigment yellow 139, CI·pigment yellow 150, CI pigment red 177, ci pigment red 242, and CI pigment red 254. The mass ratio is 3.97~90:10', preferably 3:97~7〇: 3〇. The content of the coloring agent (A) is preferably 5 to 6 % by mass, more preferably 8 to 55% by mass, still more preferably 10 to 50% by mass, based on the solid content of the colored photosensitive resin composition. β Here, the solid content component refers to the total of the components of the coloring photosensitive resin composition excluding the solvent. When the content of the coloring agent (ytterbium) is in the above range, the color density when the color filter is used is sufficient, and a necessary amount of the binder polymer can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed. The color-sensitive t-resin composition of the present invention contains a resin (8). The tree 曰 (8)' is not particularly limited, and is preferably a soluble resin. Examples of the contact Ha(B)' include the following resins [κι] to [κ4]. [Κ1] A cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond. 161700.doc -42 - 201237118 The body (a) (hereinafter sometimes referred to as "(4)")) is selected from the group consisting of unsaturated acid And a copolymer of at least one of (8) (hereinafter sometimes referred to as "(9)")). [K2] (4) and (8) and copolymers [K3] (b) and (c) which are copolymerizable with (4) monomer (4) (which is different from (4) and (b)) (hereinafter sometimes referred to as "(4)"). The copolymer [K4] is a resin obtained by reacting the copolymer of (b) and (e) with (4). By including the structural unit derived from (a) in the resin (B), the reliability of heat resistance and chemical resistance of the obtained colored pattern can be further improved. (a) is, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, selected from the group consisting of an ethylene epoxide ring, an oxetan ring, and a tetrahydro fluorene ring (oxocyclohexyl ring)). At least one of the group) is a polymerizable compound having an ethylenically unsaturated bond. (a) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group. In the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acrylonitrile" and "(mercapto) acrylate vinegar have the same meaning. Examples of (4)' include a monomer (4) having an epoxy group and an ethylene bond and a bond (hereinafter sometimes referred to as "(al)"), and having an oxetane group and an ethylenic unsaturated group. The monomer (a2) of the bond (hereinafter sometimes referred to as "(&2)"), the monomer (a3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(4))")). (al), for example, 161700.doc -43 - 201237118 °° body (al 1) (hereinafter sometimes referred to as "(al l)") having a structure in which a chain olefin is epoxidized, and has a ring type A monomer (al_2) having a structure in which epoxidized epoxidation is carried out (hereinafter sometimes referred to as "(Μ)") (4)·1) ', exemplified by: (meth)acrylic acid glycerin vinegar, (meth) = acidated β - mercapto-glycidyl vinegar, (meth)acrylic acid ρ·ethyl glycidyl ester, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, vinyl Benzyl glycidyl ether, & methyl-based vinyl? Dimethyl sulphate (iv) U-based. Inter-ethylene di-f-hydrating glycerol ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3 bis (glycidoxymethyl) styrene, 2, 4 _bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxycarbonyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4 - tris(glycidoxymethyl)styrene, 2.3.5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4 , 5-tris(glycidyloxyindenyl)styrene, 2.4.6-tris(glycidoxyfluorenyl)styrene, and the like. Examples of (al-2) include vinylcyclohexene oxide, 12 epoxy-4-vinylcyclohexane (for example, Ceii〇xide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), and 3,4- Epoxycyclohexylfluorenyl (fluorenyl) acrylate g (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyldecyl (fluorenyl) acrylate (for example, Cyclomer M100; A compound represented by the formula (I), a compound represented by the formula (I), and the like are produced by Daicel Chemical Industry Co., Ltd.
161700.doc 201237118 [式⑴及式(II)中,Ra及Rb相互獨立表示氫原子或碳數 1 ~4之烧基’該烧基中所含之氫原子可經經基取代; X1及X2相互獨立表示單鍵、_RC *-Rc-NH-; *-Rc-0- *-Rc-S_、 1^表示碳數1〜6之烷二基; *表示與〇之鍵結鍵] 作為碳數1〜4之烷基,可列舉:甲基、乙基、正丙基、 異丙基、正丁基、第二丁基、第三丁基等。 作為氫原子經羥基取代之烷基,可列舉:羥基甲基、1 _ 羥基乙基、2-羥基乙基' 1_羥基丙基、2羥基丙基、3羥 基丙基、1-羥基-1-甲基乙基、2·羥基_丨_曱基乙基、〖羥基 丁基、2-羥基丁基、3_羥基丁基、4_羥基丁基等。 作為Ra&Rb,較佳可列舉氫原子、甲基、羥基曱基、卜 羥基乙基、2-羥基乙基,更佳可列舉氫原子、曱基。 作為烷二基,可列舉:亞曱基、伸乙基、丙·U2二基、 丙1,3-一基、丁·14_二基、戊_15二基、己·16二基等。 作為X1及X2,較佳可列舉單鍵、亞甲基、伸乙基、 表示與〇之鍵結鍵)基、*-CH2CH2-〇-基,更佳 可列舉單鍵、*-CH2CH2_0·基。 2為式(I)所示之化合物,可列舉式(1_1}〜式(115)所示之 化合物等。較佳可列舉式㈣、式(1_3)、式(15)、式⑴ )式(1-9)、式(1-11)~式(1-15) »更佳可列舉式…丨)、式 + 7卜式(1-9)、式(1_15)。 " 161700.doc -45- i?201237118 Η2〇=ΟΗ—c~o161700.doc 201237118 [In the formulae (1) and (II), Ra and Rb independently of each other represent a hydrogen atom or a carbon group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a base; X1 and X2 Independent of each other means a single bond, _RC *-Rc-NH-; *-Rc-0- *-Rc-S_, 1^ represents an alkyldiyl group having a carbon number of 1 to 6; * represents a bond with hydrazine] as carbon The alkyl group of 1 to 4 may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group or a t-butyl group. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl '1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy-1 group. -methylethyl, 2, hydroxy-hydrazine-hydrazinoethyl, hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like. The Ra & Rb is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a fluorenyl group. Examples of the alkanediyl group include an anthracene group, an exoethyl group, a propionium U2 diyl group, a propane 1,3-methyl group, a 1,4-14-diyl group, a pentyl-15-diyl group, and a hexa-diyl group. X1 and X2 are preferably a single bond, a methylene group, an ethylidene group, a bond group with a fluorene bond, a *-CH2CH2-fluorenyl group, and more preferably a single bond or a *-CH2CH2_0. group. . 2 is a compound represented by the formula (I), and examples thereof include a compound represented by the formula (1_1} to the formula (115), and preferably a formula (4), a formula (1_3), a formula (15), and a formula (1)) 1-9), Formula (1-11)~Formula (1-15) »More preferably can be enumerated...丨), Formula + 7 (1-9), Formula (1_15). " 161700.doc -45- i?201237118 Η2〇=ΟΗ—c~o
h2c=ch-c—o—ch2H2c=ch-c—o—ch2
H2C=CH ~C —O CjH,H2C=CH ~C —O CjH,
CH30 u 0 I 11 H2C=C—C-〇-C2h4 ) Ο (1-1) C—0—C2H4· -0 〇 (1-3) HjCsCH—C—Ο*C2H4 CH30 Hi C2H5O H2C=C—c—oCH30 u 0 I 11 H2C=C—C-〇-C2h4 ) Ο (1-1) C—0—C2H4· -0 〇(1-3) HjCsCH—C—Ο*C2H4 CH30 Hi C2H5O H2C=C—c —o
-C—〇—C2 H4 —s CH30 H2C=C—C-0-C2H4-N-C—〇—C2 H4 —s CH30 H2C=C—C-0-C2H4-N
作為式(II)所示一 ,,丁, 、~〜叭、1卜 i 5)戶/ 不之化合物等°較佳可列舉式式(Π-3)'式(„_5)、 弋(7)式(11_9)、式(Π-11)~式(11-丨5)。更佳可列舉式 (11)1(11-7)4(19)1(11-15)0 之化合物’可列舉:式(IM)〜式(II15)所As shown in the formula (II), D, ~, 〜 叭, 1 卜 i 5) household / no compound, etc. ° can be exemplified by the formula (Π-3) 'form („_5), 弋 (7 Formula (11_9), formula (Π-11)~Formula (11-丨5). More preferably, the compound of the formula (11) 1(11-7)4(19)1(11-15)0 can be used. List: Formula (IM) ~ (II15)
HjCjCH—C-—Ο一C2H4—S 0 || μ H2C:CH—C一0—C2H4—N ch3〇 / II HjC=0 —-0 一 〇_C2H4—SHjCjCH—C——Ο一C2H4—S 0 || μ H2C:CH—C—0—C2H4—N ch3〇 / II HjC=0 —-0 一 〇_C2H4—S
161700.doc 201237118161700.doc 201237118
h2c:ch - L 0〜C2H4-0H2c:ch - L 0~C2H4-0
H2c=c 11H2c=c 11
Ul H2C=i '' 〇 h2c=c—M ^Ul H2C=i '' 〇 h2c=c-M ^
ch3〇 I II H H2C=C—C_O一C2H4—N η2ο=Π-ο ch2oh o I II h2c=c-c—oCh3〇 I II H H2C=C—C_O—C2H4—N η2ο=Π-ο ch2oh o I II h2c=c-c—o
CH3 o H2C=d〇—C2H4.CH3 o H2C=d〇—C2H4.
c2h4oh o h2c=c-c—oC2h4oh o h2c=c-c-o
式(I)所不之化合物及式(II)所示之化合物可分別單獨使 又,該等可以任意之比率混合。於混合之情形時其 展α比率以莫耳比計,較佳為式(I):式(II)為5:95〜95:5, 更佳為1〇:9()〜90:10 ’尤佳為20:80〜80:20。 作為具有氧雜環丁院基與乙稀性不飽和鍵之單體(a2), 更佳為具有氧雜環丁烧基與(甲基)丙烯醢氧基之單體。作 為(a2)’可列舉:3甲基·3•曱基丙烯酿氧基甲基氧雜環丁 烷、3-曱基_3_丙烯醯氧基甲基氧雜環丁烷、 Π:基氧雜環丁…—氧基甲I: ’ ’元 m甲基丙烯輯基乙基氧 =^=_基乙基氧雜環丁烧、3.乙基_基丙稀 丁燒乙基_3_丙稀醯氧基乙基氧雜環 佳有,°夫°南基與乙烯性不飽和鍵之單體(a3),更 佳為具有四虱°夫°南基與(甲基)丙烯酿氧基之單體。 I6I700.doc •47· 201237118 作為(a3),具體可列舉:丙烯酸四氫糠酯(例如,visc〇at V#150,大阪有機化學工業(股)製造)、f基丙烯酸四氫糠 酯等。 作為(a),就可進一步提高所得著色圖案之耐熱性、耐化 學品性等可靠性之方面而言,較佳為⑷)。進而就著色感 光性樹脂組合物之保存穩定性優異之方面而言,更佳為 (al-2)。 作為(b),具體而言,例如可列舉:丙烯酸、甲基丙烯 酸、丁烯酸、鄰乙烯基苯甲酸、間乙烯基苯甲酸、對乙烯 基本甲酸等不飽和一元幾酸類; 順丁烯二酸、反丁烯二酸、甲基順丁烯二酸、甲基反丁 烯二酸、衣康酸、3-乙烯基鄰苯二甲酸、4_乙烯基鄰苯二 曱酸、3,4,5,6-四氫鄰苯二甲酸、四氫鄰苯二曱 酸、二甲基四氫鄰苯二曱酸、1>4•環己烯二甲酸等不飽和 二元羧酸類; 甲基-5-降莅烯-2’3-二甲酸、5_羧基雙環[221]庚_2_烯、 5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1] 庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲 基雙環[2.2.1]庚-2-稀、5-敌基_6-乙基雙環[2.2.1]庚-2-稀等 含有羧基之雙環不飽和化合物類; 順丁烯二酸酐、甲基順丁烯二酸酐、衣康酸酐、3 •乙烯 基鄰本一甲酸針、4-乙烯基鄰苯二甲酸酐' 3,4,5,6-四氩鄰 苯二曱酸酐、1,2,3,6-四氫鄰笨二甲酸酐、二曱基四氣鄰 本一曱酸酐、5,6-二叛基雙環[2.2.1]庚-2-烯酐(雙環庚烯二 161700.doc •48· 201237118 甲酸酐)等不飽和二元羧酸類酐; 卓[2-(甲基)丙稀酿氧基乙基]醋、鄰苯二曱酸單 [2-(曱基)丙烯醯氧基乙基]酯等2元以上之多元羧酸之不飽 和單[(甲基)丙烯醯氧基烷基]酯類; 如α-(經基曱基)丙烯酸之,同一分子辛含有經基及叛基 之不飽和丙稀酸酯類等。 该等之中,就共聚合反應性之方面或對鹼性水溶液之溶 解性之方面而言,較佳為丙烯酸、甲基丙烯酸、無水順丁 烯二酸等。 作為(c),例如可列舉:(曱基)丙烯酸曱酯、(甲基)丙烯 酸乙酯、(甲基)丙烯酸正丁酯、(曱基)丙烯酸第二丁酯、 (甲基)丙烯酸第三丁酯、(曱基)丙烯酸2_乙基己酯、(曱基) 丙烯酸十二烷基酯、(甲基)丙烯酸月桂基酯、(甲基)丙烯 酸硬脂基醋、(曱基)丙烯酸環戊酯、(甲基)丙烯酸環己 醋、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環 [5.2.1.〇2’6]癸-8-基酯(於該技術領域中,作為慣用名,稱為 (甲基)丙稀酸二環戊酯)、(甲基)丙烯酸二環戊氧基乙酯、 (曱基)丙烯酸異葙基酯、(曱基)丙烯酸金剛烷基酯、(曱基) 丙烯酸烯丙酯、(曱基)丙烯酸炔丙酯、(甲基)丙烯酸苯 醋、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(曱基)丙烯酸 酯類; (甲基)丙烯酸2-羥基乙酯、(曱基)丙烯酸2_羥基丙酯等含 有羥基之(甲基)丙烯酸酯類; 順丁烯二酸二乙酯、反丁烯二酸二乙酯、衣康酸二乙酯 161700.doc -49- 201237118 等二羧酸二酯; 雙環[2.2.1]庚-2-烯、5-曱基雙環[2.2.1]庚-2-烯、5-乙基 雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥基甲 基雙環[2.2.1]庚-2-烯、5-(2··羥基乙基)雙環[2.2.1]庚-2-烯、%甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2_烯、5,6-二羥基雙環[2.2.1]庚_2·烯、5,6-二(羥基甲基)雙 環[2.2.1]庚-2-烯、5,6-二(2·-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2_1]庚-2-烯、5,6-二乙氧基雙環 [2.2.1] 庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥 基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-曱基雙環 [2.2.1] 庚-2-烯、5-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環 [2.2.1] 庚-2-烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]庚-2- 烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽 和化合物類; N-笨基順丁烯二醯亞胺、N_環己基順丁烯二醯亞胺、N_ 苄基順丁烯二醯亞胺、N- 丁二醯亞胺基-3-順丁烯二醯亞 胺苯曱酸酯、N- 丁二醯亞胺基-4-順丁烯二醯亞胺丁酸 酯、N-丁二醯亞胺基_6_順丁烯二醯亞胺己酸酯、N_丁二 醯亞胺基-3-順丁烯二醯亞胺丙酸酯、ν·(9-吖啶基)順丁歸 二醯亞胺等二羰基醯亞胺衍生物類; 苯乙烯、α_甲基苯乙烯、間甲基苯乙烯、對甲基笨乙 稀、乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、曱基丙歸 腈、氣乙烯、偏二氣乙烯、丙烯醯胺、甲基丙烯酿胺、乙 161700.doc -50- 201237118 酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-丨’弘丁二 烯等。 該等之中’就共聚合反應性及耐熱性之方面而言,較佳 為苯乙烯、N-苯基順丁烯二醯亞胺、N•環己基順丁烯二醯 亞胺、N_苄基順丁烯二醯亞胺、雙環[2 2丨]庚_2_烯等。 於樹脂[K1]中,分別來自(a)及(b)之結構單元的比率, 較佳為於構成樹脂[K1]之總結構單元中,處於以下之範 圍。 來自(a)之結構單元:6〇〜98莫耳%(更佳為65〜95莫耳%) 來自(b)之結構單元:2〜4〇莫耳%(更佳為5〜35莫耳0/〇) 右樹脂[K1]之結構單元之比率為上述範圍,則存在保存 穩定性、顯影性、硬化圖案之耐溶劑性變得良好之傾向。 樹脂[K1]例如可以文獻「高分子合成之實驗法」(大津 隆行著發行所(股)化學同人第i版第i次印刷MU年3月 1曰發行)中揭示之方法及該文獻中揭示之引用文獻為參考 而製造。 具體而言,可例示將特定量之(a)及(b)、聚合起始劑及 溶劑等投人反應容器中’於藉由以氮置換氧而脫氧之情形 下加以擾拌、加熱、保溫的方法。再者,此處所使用之 =合起始劑及溶料並無特職定,可使用於該領域中通 ㊉所使用者中之任—者。例如,作為聚合起始劑,可列 舉:偶氮化合物(2,2,_偶氮二異丁腈、2,2,-偶氮雙(2,4_二甲 土戊腈)等)或有機過氧化物(過氡化苯甲酿等),作為溶 劑’若為可溶解各單體者即可,可使用作為感光性樹脂組 161700.doc 201237118 合物之溶劑而後述之溶劑等。 再者,所得共聚物可直接使用反應後之溶液,亦可使用 濃縮或稀釋之溶液,亦可使用藉由再沈澱等方法作為固體 (粉體)而提取者。尤其,該聚合時,藉由使用後述溶劑(D) 作為溶劑,可直接使用反應後之溶液,可使製造步驟簡略 化。 於樹脂[K2]中,分別來自(a)、(b)及⑷之結構單元的比 率,較佳為於構成樹脂[K2]之總結構單元中,處於以下之 範圍。 來自(a)之結構單元:2〜95莫耳%(更佳為5〜8〇莫耳 來自(b)之結構單元:2〜4〇莫耳%(更佳為5〜35莫耳%) 來自(c)之結構單元:丨〜65莫耳%(更佳為卜6〇莫耳 右樹脂[K2]之結構單元之比率為上述範圍則存在保存 穩定性、顯影性、硬化圖案之雜劑性、財熱性及機械強 度變得良好之傾向。 樹脂[K2]例如可藉由與作為樹脂[κι]之製造方法而揭示 之方法相同之方式進行製造。 具體而言’可列舉將特^量之⑷、(b)及⑷,聚合起始 劑及溶劑投人反應容器中,於藉由以氮置換氧⑽氧之情 形下加以攪拌、加熱、保溫的方法。所得共聚物可直接 使用反應後之溶液,亦可使用濃縮或稀釋之溶液,亦可使 用藉由再沈澱等方法而作為固體(粉體)提取者。 於樹脂[K3]中’分別來自⑻及⑷之結構單元的比率, 較佳為於構成樹脂[K3]之總結構單元中處於以下之範 161700.doc -52- 201237118 圍0 (b)2〜40莫耳%,更佳為5〜35莫耳% (060〜98莫耳%,更佳為“〜^莫耳% 樹脂[K3]例如可進行製造。 樹MK4J可藉由獲得⑻與⑷之共聚物於⑷所具有之 碳數2 4之環狀㈣上加成⑷所具有之叛基而獲得。 首先藉由與作為樹脂[K1]之製造方法而揭示之方法相 同之方式而製造⑻與⑷之共聚物。於該情形時,分別來 自(b)及(c)之結構單元的比率,較佳為於構成⑻與⑷之共 聚物之總結構單元中,處於以下之範圍。 (b)5〜50莫耳°/°,更佳為10〜45莫耳% (c)50〜95莫耳%,更佳為55〜9〇莫耳% 其次’使上述共聚物中之來自⑷之結構單元中所含的敌 基及/或叛酸if之-部分,與⑷所具有之碳數2〜4之環狀喊 進行反應。 製造⑻與(c)之共聚物之後,將燒瓶内環境自氣置換為 空氣,將(a)、羧基與環狀醚之反應觸媒(例如三(二甲基胺 基甲基)苯酚等)以相對於(a)〜(c)i總量為〇 〇〇丨〜5質量%之 量、及聚合抑制劑(例如對苯二酚等)等以相對於h卜(c)之 總量為0.001〜5質量%之量投入燒^,例如於H耽 下,反應1〜10小時,藉此可獲得樹脂[K4]。投入方法 應溫度及時間等反應條件,可考慮製造設備或聚合所引2 之發熱量等而進行適宜調整。再者,與聚合條件相同α 考慮製造設備或聚合所引起之發熱量等, 而適宜調整投入 I6l700.doc •53· 201237118 方法或反應溫度。 該情形時之⑷之使用量,較佳為相對於(b)為5〜8〇莫耳 %,更佳為10〜75莫耳%,更佳為15〜7〇莫耳藉由設為 該範圍,存在保存穩定性、顯影性、耐溶劑性、二熱 機械強度及感光度之平衡變得良好之傾向。 作為樹脂(B),具體可列舉:(甲基)丙烯酸3,心環氧環己 基曱酯/(甲基)丙烯酸共聚物、丙烯酸3,4_環氧三<環 [5.2.1.02,6]癸醋/(甲基)丙烯酸共聚物等樹脂[κι];(曱基) 丙烯酸縮水甘油酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚 物、(甲基)丙烯酸縮水甘油酯/苯乙烯/(曱基)丙烯酸共聚 物、丙烯酸3,4-環氧三環[5·2丄〇2,6]癸醋/(曱基)丙烯酸/Ν_ 環己基順丁烯二醯亞胺共聚物、3·曱基_3·(曱基)丙烯醯氧 基甲基氧雜環丁烷/(曱基)丙烯酸/苯乙烯共聚物等樹脂 [Κ2];(曱基)丙烯酸苄酯/(曱基)丙烯酸共聚物、苯乙婦/ (甲基)丙烯酸共聚物等樹脂[Κ3];(甲基)丙烯酸苄酯/(甲 基)丙稀酸共聚物上加成有(曱基)丙烯酸縮水甘油酯的樹 脂、(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物上 加成有(甲基)丙烯酸縮水甘油酯的樹脂、(甲基)丙稀酸三 環癸酯/(曱基)丙烯酸苄酯/(甲基)丙烯酸共聚物上加成有 (甲基)丙烯酸縮水甘油酯的樹脂等樹脂[Κ4]等。其中,較 佳為樹脂[Κ1 ]及樹脂[Κ2],更佳為樹脂[Κ1 ],進而更佳為 丙烯酸3,4-環氧三環[5.2.1.〇2,6]癸酯/(曱基)丙烯酸共聚 物0 樹脂(Β)之聚苯乙烯換算之重量平均分子量,較佳為 161700.doc -54 - 201237118 3,000〜100,_ ’ t佳為5 〇〇〇〜5〇 〇〇〇,進而更佳為5,_〜 3 5,000,尤佳為6 〇〇〇〜3〇,_,特佳為?,〇〇〇〜⑽〇。若分 子量為上述範圍,則存在塗膜硬度提高,殘膜率亦較高, 且未曝光部對顯影液之溶解性良好,解像度提高之傾向。 樹脂(B)之分子量分佈[重量平均分子量(Mw)/數平均分 子量(Mn)],較佳為1·1〜6,更佳為1.2〜4。 樹月曰(Β)之酸值較佳為5〇〜15〇,更佳為6〇〜135,進而更 佳為70〜135。此處,酸值係作為中和i g之樹脂(β)所必需 之氫氧化鉀之量(mg)而測定之值,例如可藉由使用氫氧化 鉀水溶液進行滴定而求得。 樹月曰(B)之a 1,相對於著色感光性樹脂組合物之固形 物成分,較佳為7〜65質量%,更佳為13〜6〇質量%,進而更 佳為17〜55質量%。若樹脂⑺)之含量為上述範圍,則可形 成圖案,又,存在解像度及殘膜率提高之傾向。 本發明之著色感光性樹脂組合物含有光聚合性化合物 (C)光聚合性化合物(C)係可藉由藉由光照射而自光聚合 起始劑(D)產生之活性自 由基及酸等而聚合的化合物,例 如可列舉具有聚合性之乙烯性不飽和鍵之化合物等,較佳 可列舉(甲基)丙烯酸酯化合物。 其中,作為光聚合性化合物(c),較佳為具有3個以上之 乙烯〖生不飽和鍵之光聚合性化合物。作為此種光聚合性化 合物’例如可列舉:季戊四醇四丙烯酸醋、季戊四醇四曱 土丙稀酸g日—季戊四醇五丙稀酸自旨、二季戊四醇五甲基 丙稀酸S日、一季戊四醇六丙烯酸酯 二季戊四醇六甲基丙 161700.doc •55· 201237118 烯酸酯等。 以上使用。 光聚合性化合物(c)可單獨使 用亦可組合兩種 光聚合性化合物(C)之含量’相對於著色感光性樹脂組 合物之固形物成分’較佳為7〜65f量%,更佳為13〜60質 量。/。,進而更佳為⑽質量%。若上述光聚合性化合物 ⑹之含量為上述範圍,則存在硬化充分進行,顯影前後 之膜厚比率提高’冑案難以產生底切(under⑽),密著性 變得良好之傾向,故而較佳。 本發明之著色感光性樹脂組合物含有光聚合起始劑 (D)。 作為上述光聚合起始劑(D),若為藉由光之作用而產生 活性自由基、酸等從而使聚合開始的化合物,則並無特別 限疋,可使用公知之聚合起始劑。光聚合起始劑(D)可與 藉由光之作用而產生活性自由基、酸等之化合物一同含有 光聚合起始助劑(D1)。光聚合起始助劑(D1)係用以促進藉 由光聚合起始劑而開始聚合之光聚合性化合物之聚合的化 σ物’或敏化劑(sensitizer)。 作為光聚合起始劑(D),較佳為藉由光之作用而產生活 性自由基之化合物’更佳為含有選自由烷基苯酮化合物、 二_化合物、醯基膦氧化物化合物、肟化合物及聯咪唑化 合物所組成之群中之至少一種的光聚合起始劑,進而更佳 為含有肪化合物之光聚合起始劑。 作為烷基苯酮化合物,可列舉:二乙氧基苯乙酮、2-甲 基-2-咪啉基4-(4-甲基硫烷基苯基)丙-卜酮、2-二甲基胺 161700.doc -56· 201237118 基-1-(4-咪琳基苯基)_2_苄基丁 _ι_酮、2_二甲基胺基_ι_(4_ 味琳基苯基)-2-(4-甲基苯基甲基)丁-卜酮、2_羥基_2_甲基_ 1- 苯基丙-1-酮、苯偶醯二曱基縮酮(benzildimethy][keta丨)、 2- 羥基-2-曱基-l_[4-(2-羥基乙氧基)苯基]丙_丨_酮、卜羥基 環己基苯基酮、2-羥基-2-甲基-1-[4-(1_曱基乙烯基)苯基] 丙-1-酮之券聚物等,較佳為2-甲基_2_咪啉基_i-(4-甲基硫 烧基苯基)丙-1-酮、2-二甲基胺基咮啉基苯基)_2_苄 基丁 -1-酮等。可使用 lrgacure 369、9〇7(以上,ciba Japan 公司製造)等市售品。 作為三。井化合物,可列舉:2,4-雙(三氯甲基)-6_(4_甲氧 基苯基)-1,3,5-三啡、2,4-雙(三氣曱基)_6·(4-甲氧基萘基)-1,3,5-二畊、2,4-雙(三氣甲基)-6-向日葵基_1,3,5-三畊、 2.4- 雙(三氯甲基曱氧基苯乙烯基)_丨,3,5_三畊、2,4· 雙(三氣曱基)·6-[2-(5-甲基呋喃-2-基)乙烯基]三畊、 2.4- 雙(二乳曱基)_6-[2-(吱喃_2-基)乙烯基]_1,3,5-三'?井、 2.4- 雙(三氣曱基)_6·[2_(4_二乙基胺基_2曱基苯基)乙烯 基]-1,3,5-三畊、2,4-雙(三氣甲基)-6_[2-(3,4-二甲氧基苯 基)乙烯基]-1,3,5-三畊等。 作為醯基膦氧化物系起始劑,可列舉:2,4,6-三曱基苯 甲醯基二苯基氧化膦等。可使用Irgacure 819(Ciba 了邛抓公 司製造)等市售品。 作為肟化合物’可列舉:N-笨曱醯氧基_丨_(4·苯基硫烷 基苯基)丁-1-酮-2-亞胺、N-苯甲醯氧基-ΐ·(4-苯基硫烷基 苯基)辛-1-酮-2-亞胺、Ν_乙醯氧基_ι_[9_乙基_6_(2_甲基苯 161700.doc -57- 201237118 曱醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-i-[9-乙 基-6-{2-曱基-4-(3,3-二甲基-2,4-二哼環戊基甲基氧基)苯曱 醯基}-9H-咔唑-3-基]乙烷-1-亞胺等。可使用Irgacure OXE-01、〇XE-02(以上 ’ Ciba Japan 公司製造),N-1919 (ADEKA公司製造)等市售品。 作為聯咪唑化合物,可列舉:2,2'-雙(2. 4,4’,5,5’-四苯基聯咪唑、2,2,-雙(2,3-二氣苯基)-4,4·,5,5'-四 苯基聯咪唾(例如,參照日本專利特開平6 — 75372號公報、 曰本專利特開平6-75373號公報等)、2,2,-雙(2-氯苯基) 4,4’,5,5'-四苯基聯咪唑、2,2,·雙(2_氣苯基)_4,4,,5,5,_四(頰 氧基苯基)聯咪唑、2,2,-雙(2-氣苯基)-4,4,,5,5·_四(二烷萆 基苯基)聯咪唑、2,2,·雙(2_氣苯基)·4,4,,5,5·-四(三烷氧遵 苯基)聯咪唑(例如,參照日本專利特公昭48_384〇3號么 報、日本專利特開昭62_1742〇4號公報等)、4,4,5,5,_位之澤 基經烷氧羰基取代之咪唑化合物(例如,參照日本專利稍 開平7-10913號公報等)等。較佳可列舉:2,2,_雙(2·氣萍 基KW四苯基聯。米唾、2,2,·雙(2,3·二氯苯基) 4,4,,5,5.·四苯基聯㈣、2,2,_雙(2,4•二氯苯基)_4,4,,5,5,_ 四 本基聯味β坐。 進而作為光聚合起始劑⑼’可列舉:安息香、安魚 甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚等: :化合物;二苯甲_、鄰苯甲醯基笨甲酸甲醋、4·苯其 苯甲酮、4-苯曱醯基_4、甲基二笨硫醚、π,,四(: 化第三丁基裁基)二笨甲酮、2,4,6-三甲基二苯甲酮等二 161700.doc • 58 - 201237118 甲酮化合物;9,1〇-菲醌、2-乙基蒽醌、樟腦醌等醌化合 物;10-丁基-2-氯吖啶酮、二苯乙二_、苯基乙醛酸甲 酯、二茂鈦(titan〇cene)化合物等。該等較佳為與後述之光 聚合起始助劑(D1)(尤其胺類)組合使用。 作為藉由光而產生酸之酸產生劑,例如可列舉:4_經基 苯基二甲基銕鑌對甲苯磺酸鹽、4_羥基苯基二甲基鎳鑌六 敦録酸鹽、4-乙醯氧基苯基二甲基錡鏽對甲苯磺酸鹽、4_ 乙醯氧基苯基•甲基•苄基锍鏽六氟銻酸鹽、三苯基疏鏽 對曱本續酸鹽、二苯基疏鎘六氣錄酸鹽、二苯基錤鑌對曱 苯磺酸鹽、二苯基錤鏽六氟銻酸鹽等鏽鹽類,或确基节基 甲苯磺酸酯類,安息香甲苯磺酸酯類等。 光聚合起始劑(D)例如亦可為如三p井化合物之,藉由光 而同時產生活性自由基與酸的化合物。 作為光聚合起始助劑(D1)’可列舉:胺化合物、烧氧基 蒽化合物、硫雜蒽酮(thioxanthone)化合物、缓酸化合物 等。 作為胺系化合物,可列舉:三乙醇胺、甲基二乙醇胺、 二異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二曱基胺基苯 甲酸乙酯、4-二曱基胺基苯曱酸異戊酯、苯曱酸2_二曱基 胺基乙酯、4-二曱基胺基苯曱酸2-乙基己酯、Ν,Ν-二甲基 對曱苯胺、4,4’-雙(二甲基胺基)二苯曱酮(俗稱米其勒 酮)、4,4’-雙(二乙基胺基)二苯曱酮、4,4,_雙(乙基甲基胺 基)二苯曱酮等’其中較佳為4,4,-雙(二乙基胺基)二苯曱 酮。可使用EAB-F(保土谷化學工業(股)製造)等市售品。 161700.doc •59- 201237118 光聚合起始劑(D)之含量,相對於樹脂(B)及光聚合性化 合物(C)之總量1〇〇質量份,較佳為0.^30質量份,更佳為 1〜20質量份。若光聚合起始劑之含量為上述範圍,則高感 光度化而縮短曝光時間提高生產性。 於本發明之著色感光性樹脂組合物中可進而含有光聚合 起始助劑(D1)。光聚合起始助劑(D1)通常係與光聚合起始 劑(D)組合使用’係用以促進藉由光聚合起始劑而開始聚 合之光聚合性化合物之聚合的化合物,或敏化劑。 作為光聚合起始助劑(D1),可列舉:胺化合物、烷氧基 蒽化合物、硫雜蒽酮化合物、羧酸化合物等。 作為胺化合物,可列舉:三乙醇胺、曱基二乙醇胺、三 異丙醇胺、4-二甲基胺基苯曱酸曱酯、4-二曱基胺基苯甲 酸乙酯、4-二甲基胺基苯曱酸異戊酯、苯甲酸2_二甲基胺 基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、n,N-二甲基對 曱苯胺、4,4’·雙(二甲基胺基)二苯曱酮(俗稱米其勒酮)、 4,4·-雙(二乙基胺基)二苯甲酮、4,4,_雙(乙基甲基胺基)二 苯甲酮等’其中較佳為4,4'-雙(二乙基胺基)二苯甲酮。可 使用EAB-F(保土谷化學工業(股)製造)等市售品。 作為烧氧基蒽化合物,可列舉:9,1 〇-二甲氧基蒽、2-乙 基-9,1〇-二甲氧基蒽、91〇_二乙氧基蒽、2_乙基_91〇_二乙 氧基蒽、9,10-二丁氧基蒽、2_乙基·9,10_二丁氧基蒽等β 作為硫雜蒽酮化合物,可列舉:2-異丙基硫雜蒽酮、4-異丙基硫雜蒽酮、2,4-二乙基硫雜蒽酮、2,4-二氣硫雜蒽 酮、1-氣-4-丙氧基硫雜蒽酮等。 161700.doc •60· 201237118 作為羧酸化合物,可列舉:苯基硫烷基乙酸、甲基苯基 硫烷基乙酸、乙基苯基硫烷基乙酸、甲基乙基苯基硫烷基 乙酸、二曱基苯基硫烷基乙酸、甲氧基苯基硫烷基乙酸、 二曱氧基苯基硫烷基乙酸、氯苯基硫烷基乙酸、二氯苯基 硫烷基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘硫乙酸、N_ 萘基甘胺酸、萘氧基乙酸等。 光聚合起始助劑(D1)可單獨使用亦可組合兩種以上使 於使用該等光聚合起始助劑(D1)之情形時,其使用量相 對於樹脂(B)及聚合性化合物之總量1〇〇質量份,較佳為 0.01 50質量A,更佳為〇卜扣質量份。又相對於光聚合 起始劑(D)l莫耳,較佳為〇〇1〜1〇莫耳,更佳為〇〇ι〜5莫 耳。若聚合起始助劑(D1)之量為該範圍,則存在可以進一 步之尚感光度形成圖案,提高圖案之生產性之傾向。 本發明之著色感光性樹脂組合物含有溶劑(E)。 /谷齊1 (E)並無特別限定,可使用該領域中通常所使用之 溶劑。例如可自酯溶劑(含有_c〇〇·之溶劑)、酯溶劑以外 之醚浴劑(含有_〇_之溶劑)、醚酯溶劑(含有_c〇〇_與_〇-之 溶劑)、酯溶劑以外之酮溶劑(含有·c〇_之溶劑)、醇溶劑、 芳香族烴溶劑、醯胺溶劑、二甲基亞砜等中選擇使用。 作為酯溶劑,可列舉:乳酸曱酯、乳醆乙酯、乳酸丁 酯、2-羥基異丁酸曱酯、乙酸乙酯、乙酸正丁酯、乙酸異 丁画曰甲心戊酯、乙酸異戊酯、丙酸丁酯' 丁酸異丙酯、 丁馱乙Sa、丁酸丁酯、丙酮酸曱酯、丙酮酸乙酯、丙酮酸 161700.doc •61- 201237118 乙酿乙酸乙酿 丙醋、乙酿乙酸甲昏旨 丁内酯等。 環己醇乙酸酯、γ- 作為蝴,合劑,可列舉 r -好平甲醚、乙二醇單乙醚、 乙一醇单丙醚、乙二 _ mu 早』—乙—醇單曱醚、二乙二 醇單乙 _1、- 7 —L·_醇單丁謎、丙二酿留 .. 醇卓甲醚、丙二醇單乙 醚、丙二醇單而_ _ ^ μλ3 Λ 、3mn :氧基-3·甲基丁醇、四氫㈣、四氩n an 一乙一醇二曱醚、二乙__薛__ , 0—鉍一乙醚、二乙二醇曱基乙基 趟 一乙一醇二丙喊、臨_Taji ;^ 一 〇 一醇—丁醚、苯曱醚、笨乙 醚、曱基苯甲醚等。 作為醚酯溶劑,可列舉:甲氧基乙酸甲酯、甲氧基乙酸 乙酯、曱氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙 酯、3-甲氧基丙酸甲酯、3_甲氧基丙酸乙酯、弘乙氧基丙 酸曱酯、3-乙氧基丙酸乙酯、2-曱氧基丙酸甲酯、2_甲氧 基丙酸乙酯、2-曱氧基丙酸丙酯、2-乙氧基丙酸甲酯、2 乙氧基丙酸乙醋、2 -甲氧基-2-甲基丙酸甲g旨、2 -乙氧基 甲基丙酸乙酯、3-曱氧基乙酸丁酯、3-甲基_3_甲氧基乙酸 丁酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酿、丙二 醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單乙峻乙 酸酯、二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酉旨 等。 作為酮溶劑,可列舉:4-經基-4-曱基-2-戊酮、丙_、 丁酮、2-庚酮、3-庚_、4-庚酮、4-甲基-2 -戊酮、環戊 酮、環己酮、異佛酮等。 161700.doc -62- 201237118 作為醇溶劑,可列舉:甲醇、乙醇、丙醇、丁醇、已 醇、環己醇、乙-醢工 Q —.、丙二醇、丙三醇等。 作為芳香族經溶劑,可列舉:苯、甲苯、 甲苯等》 T个 J — 乍為酿*劑’可列舉:Ν,Ν·二甲基甲酿胺、N,N_二甲 基乙醯胺、N-甲基吡咯烷酮等。 該等溶劑可單獨使用亦可組合兩種以上使用。 上述溶劑中’就塗佈性、乾燥性之方面而言,較佳以 m下^弗點為12〇t以上、18代以下之有機溶劑。其 中’較佳為丙二醇單曱趟乙酸醋、乳酸乙醋、丙二醇單甲 醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、二乙二醇單甲 醚、二乙二醇單乙醚、4_羥基_4_甲基_2_戊嗣、N,N_二甲 基甲酿胺、N_甲基吼°各燒酮等,更佳為丙二醇單曱_、丙 一醇早甲驗乙酸醋、乳酸乙醋、3乙氧基丙酸乙醋等。若 含有该等溶劑,則塗佈時之平坦性優異。 著色感光性樹脂組合物中之溶劑(E)之含量,相對於著 色感光性樹脂組合物,較佳為7〇〜95質量%,更佳為75〜% 質1 換。之,著色感光性樹脂組合物之固形物成分, 較佳為質量%,更佳為8〜25f量%。若溶劑⑻之含量 為上述範圍,則存在塗佈時之平坦性變得良好,又,形成 慮光片時不會出現色濃度不A ’故而顯示特性 好之傾向。 於本發明之著色感光性樹脂組合物令可進而含有界面舌 性劑⑺。作為界面活性劑(F),可列舉:石夕氧,系界面活性 161700.doc -63- 201237118 劑、氟系界面活性劑及具有氟原子之矽氧系界面活性劑 等。該等可於側鏈具有聚合性基。 作為矽氧系界面活性劑,可列舉具有矽氧烷鍵之界面活 性劑等。具體而言,可列舉:Toray Silicone DC3PA、 Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、聚醚改質石夕油 SH8400 (商品名,Toray Dow Corning(股)製造),KP321、KP322、 KP323、KP324、KP326、KP340、KP341(信越化學工業 (股)製造),TSF400、TSF401、TSF410、TSF4300、 TSF4440、TSF4445、TSF-4446、TSF4452、TSF4460(邁圖 高新材料日本有限公司(Momentive Performance Materials Japan)製造)等。 作為上述氟系界面活性劑,可列舉具有氟碳鏈之界面活 性劑等。具體可列舉:Fluorad(商品名)FC430、Fluorad FC431(Sumitomo 3M(股)製造),Megafac(商品名)F142D、 Megafac F171、Megafac F172、Megafac F173、Megafac F177、Megafac F183、Megafac R30、Megafac RS-718-K(DIC(股)製造),Eftop(商品名)EF301、Eftop EF303、 Eftop EF351、Eftop EF352(三菱綜合材料電子化成 (Mitsubishi Materials Electronic Chemicals)(股)製造), Surflon(商品名)S381、Surflon S382、Surflon SC101、 81^1〇1130:105(旭硝子(股)製造),£5844((股)大金精密化學 研究所製)等。 161700.doc -64- 201237118 作為上述具有IL原子之石夕氧系界面活性劑,可列舉且有 矽氧烷鍵及氟碳鏈之界面活性劑等。具體可列舉:The compound of the formula (I) and the compound of the formula (II) may be separately and in combination, and these may be mixed in any ratio. In the case of mixing, the ratio of α is expressed in molar ratio, preferably Formula (I): Formula (II) is 5:95 to 95:5, more preferably 1:9 () to 90:10 ' Yu Jia is 20:80~80:20. The monomer (a2) having an oxetane group and an ethylenically unsaturated bond is more preferably a monomer having an oxetan group and a (meth) acryloxy group. Examples of (a2)' include: 3-methyl·3·mercaptopropene oxymethyloxetane, 3-mercapto-3-propenyloxymethyloxetane, and fluorenyl group. Oxetane...-oxyl I: ''m-m-methylpropenyl-ethyloxy=^=_ylethyloxetane, 3.ethyl-propylpropanyl-ethylate_3 _ propylene oxiranyloxy oxirane is preferred, the monomer of the south and the ethylenically unsaturated bond (a3), more preferably has a 虱 虱 ° ° South base and (meth) propylene brewing A monomer of an oxy group. I6I700.doc •47·201237118 Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, visc〇at V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and f-based tetrahydrofurfuryl acrylate. (a) is preferably (4)) in terms of further improving the reliability of heat resistance and chemical resistance of the obtained colored pattern. Further, it is more preferably (al-2) from the viewpoint of excellent storage stability of the colored photosensitive resin composition. Specific examples of (b) include unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; Acid, fumaric acid, methyl maleic acid, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3, 4 , 5,6-tetrahydrophthalic acid, tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1>4•cyclohexene dicarboxylic acid, unsaturated dicarboxylic acids; methyl -5-norkenylene-2'3-dicarboxylic acid, 5-carboxybicyclo[221]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5 -Methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]g a bicyclic unsaturated compound containing a carboxyl group such as -2-thin, 5-enyl- 6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, clothing Tonic anhydride, 3 • vinyl phthalate, 4-vinyl phthalic anhydride ' 3,4,5,6-tetra-argon phthalic anhydride, 1,2,3,6-four O-diacetic acid anhydride, dimercapto tetra-tetra- ortho-phthalic anhydride, 5,6-di-resylbicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene II 161700.doc •48· 201237118 And other unsaturated dicarboxylic acid anhydride; benzo [2-(methyl) propylene oxyethyl] vinegar, phthalic acid mono [2-(indenyl) propylene oxyethyl] ester, etc. Unsaturated mono[(meth)acryloxyalkyl]esters of polyvalent carboxylic acids of 2 or more; such as α-(p-fluorenyl)acrylic acid, the same molecule contains osmotic and thiol-saturated Acrylates, etc. Among these, acrylic acid, methacrylic acid, anhydrous cis-butenedioic acid, and the like are preferable in terms of the aspect of the copolymerization reactivity or the solubility to the alkaline aqueous solution. Examples of (c) include (mercapto) decyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and (meth) acrylate. Tributyl ester, (2-mercapto)acrylic acid 2-ethylhexyl ester, (decyl) decyl acrylate, lauryl (meth) acrylate, stearyl methacrylate, (fluorenyl) Cyclopentyl acrylate, cyclohexanic acid (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.〇2'6]癸-8-yl ester (In the technical field, as a conventional name, it is called (meth)acrylic acid dicyclopentanyl ester), (meth)acrylic acid dicyclopentyloxyethyl ester, (decyl)isodecyl acrylate, ( Adamantyl adamantyl acrylate, (mercapto) allyl acrylate, propargyl (meth) acrylate, phenyl methacrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate Ethyl (meth) acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. (Meth) acrylates; diethyl maleate, diethyl fumarate, diethyl itaconate 161700.doc -49- 201237118 and other dicarboxylic acid diester; double ring [2.2. 1]hept-2-ene, 5-mercaptobicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]g 2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2.hydroxyethyl)bicyclo[2.2.1]hept-2-ene, % methoxybicyclo[ 2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di (hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2.-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclo[2.2_1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene , 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-fluorenylbicyclo[2.2.1]hept-2-ene, 5-t-butoxy Carbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5, a bicyclic unsaturated compound such as 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl succinimide, N-cyclohexyl succinimide Amine, N-benzyl maleimide, N-butylenedimino-3-methyleneimine benzoate, N-butylenediamine-4-pentene Diterpenoid butyl sulphate, N-butyl succinimide -6-m-butylene imidate hexanoate, N-butyl quinone imino-3-butyl succinimide propionic acid Dicarbonyl quinone imine derivatives such as ester, ν·(9-acridinyl)-cis-diimide, styrene, α-methylstyrene, m-methylstyrene, p-methylethene , vinyl toluene, p-methoxystyrene, acrylonitrile, mercaptopropyl nitrile, ethylene, ethylene, propylene, methacrylic acid, ethylene 161700.doc -50- 201237118 , 1,3-butadiene, isoprene, 2,3-dimethyl-anthracene, etc. Among these, 'styrene, N-phenyl maleimide, N•cyclohexyl maleimide, N_ are preferable in terms of copolymerization reactivity and heat resistance. Benzylmethyleneimine, bicyclo[2 2丨]hept-2-ene, and the like. In the resin [K1], the ratio of the structural units derived from (a) and (b), respectively, is preferably in the following range from the total structural unit constituting the resin [K1]. The structural unit from (a): 6〇~98mol% (more preferably 65~95mol%) The structural unit from (b): 2~4〇% by mole (more preferably 5~35 moles) 0/〇) When the ratio of the structural unit of the right resin [K1] is in the above range, the storage stability, the developability, and the solvent resistance of the cured pattern tend to be good. The resin [K1] can be disclosed, for example, in the literature "Experimental method for polymer synthesis" (published by Otsuka Ryokan, Ltd., i.S., ed., ith, MU, March 1). The citations are made by reference. Specifically, it can be exemplified that a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are injected into a reaction vessel to be scrambled, heated, and kept warmed by deoxidizing oxygen by replacing nitrogen with nitrogen. Methods. Furthermore, the initiators and solutions used herein are not specifically defined and can be used in any of the ten users in the field. For example, examples of the polymerization initiator include an azo compound (2,2,-azobisisobutyronitrile, 2,2,-azobis(2,4-dimethylcarbonitrile), etc.) or organic A peroxide (such as a ruthenium benzoate) may be used as a solvent, and a solvent which is a solvent of the photosensitive resin group 161700.doc 201237118 and a solvent to be described later may be used. Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution obtained by concentration or dilution, or a solid (powder) by a method such as reprecipitation. In particular, in the polymerization, by using the solvent (D) described later as a solvent, the solution after the reaction can be used as it is, and the production steps can be simplified. In the resin [K2], the ratio of the structural units derived from (a), (b) and (4), respectively, is preferably in the range of the total structural unit constituting the resin [K2]. The structural unit from (a): 2 to 95 mol% (more preferably 5 to 8 m Mo from the structural unit of (b): 2 to 4 〇 mol% (more preferably 5 to 35 mol%) The structural unit derived from (c): 丨~65 mol% (more preferably, the ratio of the structural unit of the 〇6〇莫耳右树脂 [K2] is the above range, and there are impurities for storage stability, developability, hardening pattern The resin, the heat, and the mechanical strength tend to be good. The resin [K2] can be produced, for example, in the same manner as the method disclosed as a method for producing a resin [κι]. (4), (b) and (4), a polymerization initiator and a solvent are introduced into a reaction vessel, and the mixture is stirred, heated, and kept warm by replacing oxygen (10) with nitrogen. The obtained copolymer can be directly used after the reaction. The solution may also be a concentrated or diluted solution, or may be used as a solid (powder) extractor by reprecipitation or the like. The ratio of structural units derived from (8) and (4) in the resin [K3], respectively. It is in the total structural unit constituting the resin [K3] which is in the following 161700.doc -5 2- 201237118 0 (b) 2 to 40 mol%, more preferably 5 to 35 mol% (060 to 98 mol%, more preferably "~^ mol % resin [K3] can be manufactured, for example. The tree MK4J can be obtained by obtaining the reductive group of the copolymer of (8) and (4) in the cyclic (4) addition (4) having a carbon number of 4 (4). First, by the method of producing the resin [K1] The copolymers of (8) and (4) are produced in the same manner as disclosed. In this case, the ratio of the structural units derived from (b) and (c), respectively, is preferably the total structural unit of the copolymer constituting (8) and (4). Medium, in the following range: (b) 5 to 50 mol ° / °, more preferably 10 to 45 mol % (c) 50 to 95 mol %, more preferably 55 to 9 m Mo % % The ester group and/or the taurine-if portion contained in the structural unit derived from (4) in the copolymer is reacted with the ring-shaped ring having the carbon number of 2 to 4 in (4). (8) and (c) After the copolymer, the environment in the flask is replaced by air from air, and the reaction catalyst of (a), a carboxyl group and a cyclic ether (for example, tris(dimethylaminomethyl)phenol, etc.) is relative to (a) The total amount of (c)i is 〇〇〇丨5 to 5% by mass, and the polymerization inhibitor (for example, hydroquinone or the like) is 0.001 to 5% by mass based on the total amount of h (c). The amount of the raw material is calcined, for example, under H耽, and the reaction is carried out for 1 to 10 hours, whereby the resin [K4] can be obtained. The input method is based on reaction conditions such as temperature and time, and the heat generation amount of the manufacturing equipment or the polymerization can be considered. Appropriate adjustment is carried out. In addition, the polymerization conditions are the same as α, considering the heat generated by the manufacturing equipment or polymerization, etc., and it is appropriate to adjust the input method or the reaction temperature. In this case, the usage amount of (4) is Preferably, it is 5 to 8 mol%, more preferably 10 to 75 mol%, more preferably 15 to 7 mol%, and is set to be in this range, and has storage stability and developability. The balance between solvent resistance, thermomechanical strength, and sensitivity tends to be good. Specific examples of the resin (B) include (meth)acrylic acid 3, a core epoxycyclohexyl decyl ester/(meth)acrylic acid copolymer, and an acrylic 3,4_epoxy triple <ring [5.2.1.02,6). ] resin such as vinegar/(meth)acrylic copolymer [κι]; (fluorenyl) glycidyl acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer, glycidyl (meth) acrylate /styrene/(indenyl)acrylic acid copolymer, 3,4-epoxytricyclo[5.2丄〇2,6]anthracene vinegar/(mercapto)acrylic acid/Ν_cyclohexylmethyleneimine Copolymer, 3·mercapto-3((fluorenyl) propylene methoxymethyl oxetane / (mercapto) acrylic acid / styrene copolymer resin [Κ 2]; (mercapto) benzyl acrylate / (Mercapto) acrylic copolymer, styrene/(meth)acrylic copolymer, etc. [Κ3]; (meth)acrylic acid benzyl ester / (meth)acrylic acid copolymer addition (fluorenyl) a resin of glycidyl acrylate, a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer, a resin obtained by adding glycidyl (meth)acrylate, and (meth)acrylic acidDecyl acrylate / (Yue-yl) benzyl acrylate / (meth) acrylic acid adduct has a (meth) acrylate resin resin [Κ4] and the like. Among them, preferred are resin [Κ1] and resin [Κ2], more preferably resin [Κ1], and more preferably 3,4-epoxytricyclo[5.2.1.〇2,6]decyl acrylate/( The polystyrene-equivalent weight average molecular weight of the fluorenyl acrylate copolymer 0 resin (Β) is preferably 161700.doc -54 - 201237118 3,000~100, _ 't preferably 5 〇〇〇~5〇〇〇〇 , and more preferably 5, _~ 3 5,000, especially good for 6 〇〇〇~3〇, _, especially good? , 〇〇〇 ~ (10) 〇. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, and the solubility of the unexposed portion to the developer is good, and the resolution tends to be improved. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4. The acid value of the tree 曰 (曰) is preferably from 5 〇 to 15 〇, more preferably from 6 〇 to 135, and still more preferably from 70 to 135. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing the resin (β) of i g , and can be obtained, for example, by titration with an aqueous solution of potassium hydroxide. A1 of the sapphire (B) is preferably 7 to 65 mass%, more preferably 13 to 6 mass%, and still more preferably 17 to 55 mass, based on the solid content of the colored photosensitive resin composition. %. When the content of the resin (7)) is in the above range, a pattern can be formed, and the resolution and the residual film ratio tend to be improved. The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C), and the photopolymerizable compound (C) is an active radical and an acid which can be produced from a photopolymerization initiator (D) by light irradiation. The compound to be polymerized is, for example, a compound having a polymerizable ethylenically unsaturated bond, and the like, and a (meth) acrylate compound is preferred. In particular, the photopolymerizable compound (c) is preferably a photopolymerizable compound having three or more ethylene-unsaturated bonds. Examples of such a photopolymerizable compound include, for example, pentaerythritol tetraacrylate vinegar, pentaerythritol tetraammine acrylate, g-pentaerythritol penta-propionic acid, dipentaerythritol pentamethyl acrylate S, and pentaerythritol hexaacrylate. Ester dipentaerythritol hexamethyl propyl 161700.doc • 55· 201237118 enoate. Used above. The photopolymerizable compound (c) may be used alone or in combination of the two photopolymerizable compounds (C), and the solid content of the colored photosensitive resin composition is preferably from 7 to 65 % by volume, more preferably 13~60 quality. /. More preferably, it is (10)% by mass. When the content of the photopolymerizable compound (6) is in the above range, the curing is sufficiently performed, and the film thickness ratio before and after the development is increased. The undercut (under (10)) is less likely to occur, and the adhesion tends to be good, which is preferable. The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). The photopolymerization initiator (D) is not particularly limited as long as it is a compound which generates an active radical, an acid or the like by the action of light to initiate polymerization, and a known polymerization initiator can be used. The photopolymerization initiator (D) may contain a photopolymerization initiation aid (D1) together with a compound which generates an active radical, an acid or the like by the action of light. The photopolymerization initiation aid (D1) is a sensitizer or a sensitizer for promoting polymerization of a photopolymerizable compound which starts polymerization by a photopolymerization initiator. The photopolymerization initiator (D) is preferably a compound which generates an active radical by the action of light. More preferably, it contains a compound selected from the group consisting of an alkylphenone compound, a di-compound, a mercaptophosphine oxide compound, and an anthracene. The photopolymerization initiator of at least one of the compound and the biimidazole compound is more preferably a photopolymerization initiator containing a fat compound. Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-tomolinyl 4-(4-methylsulfanylphenyl)propanone, and 2-dimethyl Alkylamine 161700.doc -56· 201237118 -1-(4-imidylphenyl)_2-benzylbutanyl- ketone, 2-dimethylamino _ι_(4_ 琳 phenyl) 2-(4-methylphenylmethyl)butan-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzilidine ketal (benzildimethy)[keta丨), 2-hydroxy-2-indolyl-l-[4-(2-hydroxyethoxy)phenyl]propanone-one, hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 a [00-(4- mercaptovinyl)phenyl]propan-1-one valence polymer or the like, preferably 2-methyl-2-phenylolino-i-(4-methylthioalkyl) Phenyl)propan-1-one, 2-dimethylaminoporphyrinylphenyl)_2-benzylbutan-1-one, and the like. Commercial products such as lrgacure 369 and 9〇7 (above, manufactured by Ciba Japan Co., Ltd.) can be used. As three. Well compounds, may be exemplified by 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-trimorphine, 2,4-bis(tris). · (4-methoxynaphthyl)-1,3,5-two tillage, 2,4-bis(trimethylmethyl)-6-sunflower base_1,3,5-three tillage, 2.4-double ( Trichloromethyl methoxy styrene) 丨, 3, 5 _ three tillage, 2, 4 · bis (trimethyl fluorenyl) · 6-[2-(5-methylfuran-2-yl) ethylene Base] three tillage, 2.4-bis (di-mercapto)_6-[2-(pyrano-2-yl)vinyl]_1,3,5-three'? well, 2.4-bis (three gas sulfhydryl) _6·[2_(4_Diethylamino-2-mercaptophenyl)vinyl]-1,3,5-three tillage, 2,4-bis(trismethyl)-6_[2-(3 , 4-dimethoxyphenyl)vinyl]-1,3,5-three tillage, and the like. Examples of the mercaptophosphine oxide-based initiator include 2,4,6-trimercaptobenzoyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by Ciba) can be used. The hydrazine compound 'is exemplified by N-indoleoxy_丨_(4·phenylsulfanylphenyl)butan-1-one-2-imine, N-benzylformyloxy-oxime ( 4-phenylsulfanylphenyl)oct-1-one-2-imine, Ν_乙醯oxy_ι_[9_ethyl_6_(2_methylbenzene 161700.doc -57- 201237118 曱Mercapto)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-i-[9-ethyl-6-{2-mercapto-4-(3,3 -Dimethyl-2,4-diindenylpentylmethyloxy)phenylhydrazinyl}-9H-indazol-3-yl]ethane-1-imine and the like. Commercial products such as Irgacure OXE-01, 〇XE-02 (manufactured by the above-mentioned 'Ciba Japan Co., Ltd.), and N-1919 (manufactured by ADEKA Co., Ltd.) can be used. As the biimidazole compound, 2,2'-bis(2.4,4',5,5'-tetraphenylbiimidazole, 2,2,-bis(2,3-diphenyl)- 4,4·,5,5'-tetraphenyl pyridine (for example, refer to Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2, 2, -double ( 2-chlorophenyl) 4,4',5,5'-tetraphenylbiimidazole, 2,2,bis(2-hydrophenyl)_4,4,5,5,_tetra(p-oxyl Phenyl)biimidazole, 2,2,-bis(2-phenylphenyl)-4,4,5,5·-tetrakis(dialkylnonylphenyl)biimidazole, 2,2,·bis (2) _ gas phenyl)·4,4,,5,5·-tetrakis(lutaneoxyphenyl)biimidazole (for example, refer to Japanese Patent Special Publication No. 48_384〇3, Japanese Patent Laid-Open No. 62_1742〇4 The imidazole compound which is substituted with an alkoxycarbonyl group in the 4th, 4th, 5th, 5th, and 5th positions (for example, refer to Japanese Patent Laid-Open No. Hei 7-10913, etc.), etc. Preferably, 2, 2, _ double (2· gasping base KW tetraphenyl linkage. rice saliva, 2, 2, · bis (2,3 · dichlorophenyl) 4,4,,5,5.·tetraphenyl linkage (four) , 2,2,_bis(2,4•dichlorophenyl)_4,4,,5,5,_ four The basal flavor β is sitting. Further, as the photopolymerization initiator (9), exemplified by benzoin, amphibious methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.: : compound; benzophenone _, o-benzonitrile醯 笨 笨 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲2,4,6-trimethylbenzophenone and other two 161700.doc • 58 - 201237118 ketone compound; 9,1 〇-phenanthrenequinone, 2-ethyl hydrazine, camphorquinone and other hydrazine compounds; 10-butyl a chloro-2-hydrazinone, a diphenylethylene di-, a phenylglyoxylate methyl ester, a titanocene compound, etc. These are preferably the photopolymerization start aids (D1 described later). (In particular, amines) are used in combination. Examples of the acid generator which generates an acid by light include, for example, 4-phenylphenyldimethylphosphonium p-toluenesulfonate and 4-hydroxyphenyldimethylene. Nickel hexamidine, 4-ethyl methoxy phenyl dimethyl ruthenium p-toluene sulfonate, 4 ethoxylated phenyl • methyl • benzyl rust hexafluoroantimonate, triphenyl Base rusting bismuth sulfonate, diphenyl Cadmium hexahydrate acid salt, diphenyl sulfonium terephthalate, diphenyl sulfonium hexafluoroantimonate and other rust salts, or basal toluene sulfonate, benzoin toluene The photopolymerization initiator (D) may be, for example, a compound such as a tri-p well compound which simultaneously generates an active radical and an acid by light. As a photopolymerization initiation aid (D1)' An amine compound, an alkoxy quinone compound, a thioxanthone compound, a slow acid compound, or the like. Examples of the amine compound include triethanolamine, methyldiethanolamine, diisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-didecylaminobenzoate, and 4-diindole. Isoamyl phenyl benzoate, 2-didecylaminoethyl benzoate, 2-ethylhexyl 4-didecylaminobenzoate, hydrazine, hydrazine-dimethyl-p-anilide , 4,4'-bis(dimethylamino)dibenzophenone (commonly known as mickleone), 4,4'-bis(diethylamino)benzophenone, 4,4, _ double (Ethylmethylamino)diphenyl fluorenone or the like ' Among them, 4,4,-bis(diethylamino)dibenzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used. 161700.doc • 59- 201237118 The content of the photopolymerization initiator (D) is preferably 0.1 part by mass based on the total amount of the resin (B) and the photopolymerizable compound (C). More preferably, it is 1 to 20 parts by mass. When the content of the photopolymerization initiator is in the above range, high sensitivity is obtained, and the exposure time is shortened to improve productivity. Further, the coloring photosensitive resin composition of the present invention may further contain a photopolymerization initiation aid (D1). The photopolymerization initiation aid (D1) is usually used in combination with a photopolymerization initiator (D) to promote the polymerization of a photopolymerizable compound which starts polymerization by a photopolymerization initiator, or sensitization. Agent. The photopolymerization initiation aid (D1) may, for example, be an amine compound, an alkoxy fluorene compound, a thioxanthone compound or a carboxylic acid compound. Examples of the amine compound include triethanolamine, decyldiethanolamine, triisopropanolamine, decyl 4-dimethylaminobenzoate, ethyl 4-didecylaminobenzoate, and 4-dimethyl Isoamyl phenyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, n,N-dimethyl-p-anilide, 4 , 4'·bis(dimethylamino)dibenzophenone (commonly known as mickleone), 4,4·-bis(diethylamino)benzophenone, 4,4,_double (B The methylamino) benzophenone or the like is preferably 4,4'-bis(diethylamino)benzophenone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used. Examples of the alkoxy hydrazine compound include 9,1 fluorene dimethoxy hydrazine, 2-ethyl-9, 1 fluorene dimethoxy fluorene, 91 〇 diethoxy fluorene, and 2-ethyl group. _91〇_Diethoxy hydrazine, 9,10-dibutoxy fluorene, 2_ethyl·9,10-dibutoxy fluorene, etc. β As the thioxanthone compound, 2-isopropyl Isothioxanthone, 4-isopropylthioxanthone, 2,4-diethylthiaxanone, 2,4-dioxathioxanthone, 1-gas-4-propoxythiazepine Anthrone and the like. 161700.doc •60· 201237118 As the carboxylic acid compound, phenylthioalkylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid Di-nonylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylthioalkylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like. The photopolymerization initiation aid (D1) may be used alone or in combination of two or more. When the photopolymerization initiation aid (D1) is used, it is used in an amount relative to the resin (B) and the polymerizable compound. The total amount is 1 part by mass, preferably 0.01 50 mass A, more preferably the mass part by weight. Further, with respect to the photopolymerization initiator (D), it is preferably 〇〇1 to 1 Torr, more preferably 〇〇ι 5 摩尔. When the amount of the polymerization starting aid (D1) is in this range, there is a tendency that the sensitivity can be further formed into a pattern to improve the productivity of the pattern. The colored photosensitive resin composition of the present invention contains a solvent (E). / Gu Qi 1 (E) is not particularly limited, and a solvent generally used in the field can be used. For example, it may be an ester solvent (a solvent containing _c〇〇·), an ether bath other than an ester solvent (a solvent containing _〇_), an ether ester solvent (a solvent containing _c〇〇_ and 〇〇-), A ketone solvent (solvent containing ·c〇_) other than the ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl sulfoxide, or the like is optionally used. Examples of the ester solvent include decyl lactate, decyl ethyl acrylate, butyl lactate, decyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, and amyl acetate. Amyl pentoxide, butyl propionate isopropyl butyrate, butyl sulfonium Sa, butyl butyrate, decyl pyruvate, ethyl pyruvate, pyruvic acid 161700.doc • 61- 201237118 B, acetic acid, glycerin, butyrolactone and the like. Cyclohexanol acetate, γ- as a butterfly, a mixture, may be exemplified by r-homomethyl ether, ethylene glycol monoethyl ether, ethyl alcohol monopropyl ether, ethylene _ mu early 』-ethyl alcohol monoterpene ether, two Ethylene glycol monoethyl _1, - 7 - L _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ^ μλ3 Λ , 3mn : oxy-3 · Methyl butanol, tetrahydro (tetra), tetra-argon n an- ethoxylated dioxime ether, di- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Pro_Taji; ^ monoterpene alcohol - butyl ether, benzoin ether, stupid ether, mercapto anisole and the like. Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl oxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, decyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl ethoxyacetate, 2-methoxy-2-methylpropionic acid, 2-B Ethyl oxymethylpropionate, butyl 3-methoxyoxyacetate, butyl 3-methyl-3-methoxyacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like. The ketone solvent may, for example, be 4-transyl-4-mercapto-2-pentanone, propyl-, butanone, 2-heptanone, 3-gly-, 4-heptanone or 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone, and the like. 161700.doc -62- 201237118 The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexane, cyclohexanol, ethyl bromide, propylene glycol or glycerin. Examples of the aromatic solvent include benzene, toluene, toluene, and the like. T J — 乍 is a brewing agent. Examples thereof include hydrazine, hydrazine dimethyl carbamide, and N,N dimethyl acetamide. , N-methylpyrrolidone and the like. These solvents may be used singly or in combination of two or more. In the above-mentioned solvent, in terms of coatability and drying property, an organic solvent having a height of 12 〇t or more and 18 or less generations is preferable. Wherein 'preferably propylene glycol monoterpene acetate vinegar, lactic acid ethyl vinegar, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, 4-hydroxyl_4-methyl-2-indene, N,N-dimethylamine, N-methylhydrazine, etc., more preferably propylene glycol monoterpene _, propanol Early test of acetic acid vinegar, lactic acid ethyl acetate, 3 ethoxy propionate ethyl vinegar and so on. When these solvents are contained, the flatness at the time of coating is excellent. The content of the solvent (E) in the colored photosensitive resin composition is preferably from 7 to 95% by mass, more preferably from 7 to 95% by mass based on the photosensitive photosensitive resin composition. The solid content of the colored photosensitive resin composition is preferably % by mass, more preferably 8 to 25 % by volume. When the content of the solvent (8) is in the above range, the flatness at the time of coating becomes good, and when the light-sensitive sheet is formed, the color density is not A', and the display property tends to be good. The colored photosensitive resin composition of the present invention may further contain an interface lingual agent (7). The surfactant (F) may, for example, be an oxygenated surfactant, a surfactant of 161700.doc-63 to 201237118, a fluorine-based surfactant, and a fluorene-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain. Examples of the rhodium-based surfactant include an interface active agent having a decane bond. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Shishing Oil SH8400 (trade name, Toray Dow Corning) (manufacturing), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 Illustrated by Momentive Performance Materials Japan, etc. The fluorine-based surfactant may, for example, be an interface active agent having a fluorocarbon chain. Specific examples include Fluorad (trade name) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), Megafac (trade name) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30, Megafac RS- 718-K (manufactured by DIC), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (trade name) S381 , Surflon S382, Surflon SC101, 81^1〇1130:105 (made by Asahi Glass Co., Ltd.), £5844 (made by Daikin Institute of Precision Chemistry). 161700.doc -64-201237118 The above-mentioned azeoxy-based surfactant having an IL atom may, for example, be a surfactant having a siloxane chain or a fluorocarbon chain. Specific examples are:
Megafac(註冊商標)R〇8、Megafac BL2〇、Megafac F475、 Megafac F477、Megafac F443(DIC(股)製造)等。 該等界面活性劑可單獨使用亦可組合兩種以上使用。 界面活性劑(F)之含量,相對於著色感光性樹脂組合 物,較佳為0.001質量%以上、〇 2質量%以下較佳為 0.002質量%以上、〇]質量%以下,更佳為q別質量%以 上、〇·〇5質量%以下。若界面活性劑(F)之含量為上述範 圍’則可使塗媒之平坦性變得良好。 右本發明之著色感光性樹脂組合物係含有著色劑(A)、 驗可溶性樹脂(B)、光聚合性化合物⑹、光聚合起㈣ (D) ’合劑(E)及界面活性劑(F)之組合物,則塗佈性優異, 可獲得耐溶劑性及分光優異之著色圖案。 較佳為於本發明之著色感光性樹脂組合物中,著色劑 (A)之含4為〇·5〜10質量%,樹脂(B)之含量為U質量%, 光聚合性广合物(〇之含量為1〜15質量。/。,光聚合起始劑 〇(D)之含置為〇,5〜1〇質量%,溶劑(幻之含量為Μ—"質量 曰又’更佳為著色劑⑷之含量為Η質量%,樹脂⑻之 3 !為3〜1〇質量% ’光聚合性化合物(C)之含量為3〜12質量 %,光聚合起始劑⑼之含量為卜5質量%,溶劑⑻之含量 :92質置/〇。進而,更佳為著色劑(Α)之含量為2〜5質量 :樹月曰⑻之含置為4〜8質量%,丨聚合性化合物(。)之含 里為5〜1〇質置% ’光聚合起始劑(D)之含量為2〜4質量。/。, I61700.doc •65- 201237118 溶劑(E)之含量為73〜87質量%。 於本發明之著色感光性樹脂組合物巾使用光聚合起始助 劑(D1)之情形時’相對於著色感光性樹脂組合物中之固形 物成刀1〇〇重量份,光聚合起始助劑之含量較佳為0.1〜10 質量份’更佳為0.5〜5質量份,進而更佳為卜3質量份。 於本發月之著色感光性樹脂組合物中使用界面活性劑 (F)之If形時,相對於著色感光性樹脂組合物中之固形物 成分100重量份,界面活性劑(F)之含量較佳為〇.〇〇!〜〗質量 份’更佳狀G1〜G.5f量份,進而更佳為Q心丨質量份。 本發月之著色感光性樹脂組合物,視需要可含有填充 劑、其他高分子化合物、密著促進劑、抗氧化劑、紫外線 吸收劑、光穩定劑、鏈轉移劑等各種添加劑。 作為使用本發之著色感光性樹脂組合物形成著色圖案 之方法’例如可列舉:將本發明之著色感光性樹脂組合物 塗佈於基板或其他樹脂層(例如,於基板上事先形成之其 他著色感光性樹餘合物層等)上,除去/乾燥溶劑等揮發 成分,形成著色層’經由光罩對該著色層進行曝光,顯影 的方法,以及使用不需要光微影法之喷墨機器的方法等。 該情形之塗膜之膜厚並無特別限定, 料、用途荨而適宜調整’例如為〇. 1〜3 〇 μηι ’更佳為1〜6 μηι。 可根據所使用之材 μηι,較佳為U0 著色感光性樹脂組合物之塗佈方法’例如可列舉··擠出 塗佈法、直接凹版印刷塗佈法、反向凹版印刷塗佈法、 CAP塗佈法(CAP coating)、模塗法等。又亦可使用浸塗 161700.doc • 66 - 201237118 機、棒式塗佈機'旋轉塗佈機、狹縫&旋轉塗佈機、狹縫 式塗佈機(有時亦稱為狹縫擠壓式塗佈機(die coater)、幕式 淋塗機(curtain flow coater)、非旋轉塗佈機(spinless coater))等塗佈機進行塗佈。 溶劑之除去/乾燥’例如可列舉:自然乾燥、通風乾 燥、減壓乾燥、加熱乾燥等。具體之乾燥溫度較佳為 10〜120°C,更佳為25〜100°C。乾燥時間較佳為10秒鐘〜6〇 分鐘,更佳為30秒鐘〜30分鐘。減壓乾燥較佳為於5〇〜15〇 Pa之壓力下,於2〇〜25。(:之範圍内進行。 乾燥後之塗膜經由用以形成目標圖案之光罩而曝光。此 時之光罩上之圖案形狀並無特別限定,可使用對應於目標 用途之圖案形狀。 作為曝光所使用之光源,較佳為產生25〇〜45〇 nm波長之 光之光源^具體可列舉:水銀燈、發光二極體、金屬齒化 物燈、函素燈等’可使用截斷特定波段之遽光器進行截 斷,或使用提取特定波段之帶通濾波器進行選擇性提取而 曝光。 因可對曝光面整體均勾照射平行I線,或可進行光罩盘 基材之正確的位置對準,故而較佳為❹光㈣ 機、步進式曝光機等裝置。 曝光後,與顯影液接觸,使特定部分例如未曝光部溶 解,顯影,藉此可獲得圖案。作為顯影液,可列舉:驗性 ^合^氫氧化_、碳_、氫氧細甲基料)之水溶液 專。違顯影液可含有界面活性劑。 161700.doc -67· 201237118 顯影方法可為覆液法(puddle)、浸潰法、噴霧法等任一 種。進而顯影時可使基板於任意角度傾斜。較佳為顯影後 進行水洗。 進而視需要,可進行後烘烤。後烘烤例如較佳為150〜 23〇C ’ 10〜240分鐘之範圍。 本發明之著色感光性樹脂組合物,可獲得色濃度、亮 ^對比度、感光度、解像度、耐熱性等良好之塗膜或圖 案’該等可用作彩色濾光片。又,可以公知之態樣,用於 所有具備該等彩色濾光片作為其構成零件之—部分的顯示 裝置,例如公知之液晶顯示裝置、有機EL裝置、固體攝像 元件等各種與著色圖像相關之機器中。 [實施例] 以下,藉由實施例進一步詳細說明本發明之著色感光性 樹脂組合物。例中之「%」及「份」,若無特別表述,則 表示質量%及質量份。 合成例1 將玫瑰紅B(東京化成工業(股)製造)3〇份溶解於氯仿288 伤中,添加N,N-二甲基-4-胺基吡啶2.3份、1〇_樟腦磺酸 1.75份、去水甘油16.24份,於20°C以下攪拌1小時。一邊 攪拌一邊滴加於氣仿72份中溶解之1-乙基_3_(3·二甲基胺 基丙基)碳二醯亞胺鹽酸鹽(東京化成工業(股)製造)17.41 份。反應結束後’於該反應液中添加1 N鹽酸水溶液進行 分液’獲取有機層。對該有機層進而重複兩次該操作。其 次,於該有機層中添加10%食鹽水進行分液,獲取有機 16I700.doc • 68 · 201237118 層。對該有機層進而重複兩次該操作。於所得有機層中添 加硫酸鎂進行脫水後’過濾而獲取濾液。藉由蒸發器自該 濾液除去溶劑,將所得紅色固體於減壓6〇。〇下加以乾燥, 藉此獲得式(d-Ι)所示之化合物30份(產率89.5%)。 式(d-Ι)所示之化合物的鑑定 (質量分析)離子化模式=ESI+: m/z=499.3[M-Cl_] +Megafac (registered trademark) R〇8, Megafac BL2〇, Megafac F475, Megafac F477, Megafac F443 (manufactured by DIC), and the like. These surfactants may be used singly or in combination of two or more. The content of the surfactant (F) is preferably 0.001% by mass or more, 〇2% by mass or less, preferably 0.002% by mass or more, and 〇% by mass or less, more preferably less than the coloring photosensitive resin composition. The mass% or more and the 〇·〇5 mass% or less. When the content of the surfactant (F) is in the above range, the flatness of the coating medium can be improved. The colored photosensitive resin composition of the present invention contains a coloring agent (A), a soluble resin (B), a photopolymerizable compound (6), photopolymerization (4) (D) 'mixture (E), and a surfactant (F). In the composition, the coating property is excellent, and a coloring pattern excellent in solvent resistance and spectral separation can be obtained. In the colored photosensitive resin composition of the present invention, the colorant (A) is preferably contained in an amount of 5 to 10% by mass, and the content of the resin (B) is 0% by mass, and the photopolymerizable compound ( The content of bismuth is 1 to 15 mass%, the photopolymerization initiator 〇(D) is set to 〇, 5 to 1% by mass, and the solvent (the content of phantom is Μ-" The content of the coloring agent (4) is Η% by mass, and the resin (8) is 3 to 1% by mass. The content of the photopolymerizable compound (C) is 3 to 12% by mass, and the content of the photopolymerization initiator (9) is 5 mass%, the content of the solvent (8): 92 texture / 〇. Further, the content of the coloring agent (Α) is 2 to 5 mass: the content of the tree 曰 (8) is set to 4 to 8 mass%, 丨 polymerizability The content of the compound (.) is 5 to 1%. The content of the photopolymerization initiator (D) is 2 to 4 mass. /, I61700.doc • 65- 201237118 The content of the solvent (E) is 73. In the case of using the photopolymerization initiation aid (D1), the coloring photosensitive resin composition towel of the present invention is formed in a weight ratio of 1 part by weight relative to the solid content in the colored photosensitive resin composition. The content of the photopolymerization initiation aid is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, still more preferably 3 parts by mass. Interfacial activity is used in the colored photosensitive resin composition of the present month. In the case of the If of the agent (F), the content of the surfactant (F) is preferably 〇.〇〇!~〗 by mass of the content of the solid content of the coloring photosensitive resin composition in 100 parts by weight. G1 to G.5f parts, and more preferably Q core parts by mass. The colored photosensitive resin composition of the present month may contain a filler, other polymer compound, adhesion promoter, antioxidant, ultraviolet rays, if necessary. Various additives such as an absorbent, a light stabilizer, and a chain transfer agent. The method of forming a colored pattern by using the colored photosensitive resin composition of the present invention, for example, is to apply the colored photosensitive resin composition of the present invention to a substrate or The other resin layer (for example, another colored photosensitive tree residue layer formed on the substrate, etc.) is removed, and the volatile component such as a solvent is removed/dried to form a colored layer. The colored layer is exposed through a photomask, and the developed layer is formed. And a method of using an inkjet apparatus that does not require a photolithography method, etc. The film thickness of the coating film in this case is not particularly limited, and it is suitable for adjustment of materials and uses, for example, 〇. 1~3 〇μηι 'better It is 1 to 6 μηι. The coating method of the coloring photosensitive resin composition of U0 can be used according to the material used, for example, extrusion coating method, direct gravure coating method, reverse gravure Printing coating method, CAP coating method, die coating method, etc. Dip coating 161700.doc • 66 - 201237118 machine, bar coater 'rotary coater, slit & rotation A coater or a slit coater (also sometimes referred to as a die coater, a curtain flow coater, or a spinless coater) The coating machine is applied. The solvent removal/drying's may, for example, be naturally dried, ventilated, dried under reduced pressure, dried by heating, or the like. The specific drying temperature is preferably from 10 to 120 ° C, more preferably from 25 to 100 ° C. The drying time is preferably from 10 seconds to 6 minutes, more preferably from 30 seconds to 30 minutes. The drying under reduced pressure is preferably at a pressure of 5 Torr to 15 Torr Pa at 2 Torr to 25 °. The coating film after drying is exposed through a mask for forming a target pattern. The pattern shape on the mask is not particularly limited, and a pattern shape corresponding to the intended use can be used. The light source used is preferably a light source that generates light having a wavelength of 25 〇 to 45 〇 nm. Specifically, a mercury lamp, a light emitting diode, a metal toothed lamp, a light element lamp, etc. can be used to cut off a specific band of light. The device is cut off or exposed by selective extraction using a band pass filter for extracting a specific band. Since the entire exposed surface can be illuminated with parallel I lines, or the correct alignment of the mask substrate can be performed, Preferably, it is a device such as a calender (four) machine, a stepper, etc. After exposure, a specific portion such as an unexposed portion is dissolved and developed by contact with a developing solution, whereby a pattern can be obtained. An aqueous solution of ^ Hydroxide _, carbon _, hydrogen oxy fine methyl material). The developer may contain a surfactant. 161700.doc -67· 201237118 The development method may be any one of a puddle method, a dipping method, and a spray method. Further, the substrate can be tilted at any angle during development. It is preferred to carry out water washing after development. Further, post-baking can be performed as needed. The post-baking is, for example, preferably in the range of 150 to 23 〇C '10 to 240 minutes. In the colored photosensitive resin composition of the present invention, a coating film or pattern which is excellent in color density, brightness, contrast, sensitivity, resolution, heat resistance, etc. can be used as the color filter. Further, it is known that all of the display devices having such color filters as their constituent parts, such as known liquid crystal display devices, organic EL devices, solid-state imaging devices, and the like, are associated with colored images. In the machine. [Examples] Hereinafter, the colored photosensitive resin composition of the present invention will be described in further detail by way of examples. In the examples, "%" and "parts", unless otherwise stated, mean % by mass and parts by mass. Synthesis Example 1 3 parts of Rose Bengal B (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in chloroform 288 wound, and 2.3 parts of N,N-dimethyl-4-aminopyridine and 1〇_camphorsulfonic acid 1.75 were added. A portion of dehydroglycerin (16.24 parts) was stirred at 20 ° C for 1 hour. While stirring, 17.41 parts of 1-ethyl_3_(3·dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 72 parts of the sample was added dropwise. After the completion of the reaction, the organic layer was obtained by adding a 1 N aqueous hydrochloric acid solution to the reaction mixture to carry out liquid separation. This operation was repeated twice more on the organic layer. Next, 10% saline solution was added to the organic layer to carry out liquid separation to obtain an organic 16I700.doc • 68 · 201237118 layer. This operation was repeated twice more on the organic layer. After adding magnesium sulfate to the obtained organic layer for dehydration, the mixture was filtered to obtain a filtrate. The solvent was removed from the filtrate by means of an evaporator, and the obtained red solid was evaporated under reduced pressure. The mixture was dried under a crucible to obtain 30 parts of the compound of the formula (d-?) (yield: 89.5%). Identification of the compound represented by formula (d-Ι) (mass analysis) ionization mode = ESI+: m/z = 499.3 [M-Cl_] +
Exact Mass(精確質量):534.2Exact Mass: 534.2
實施例1 於2-胺基-4-曱基續醯基-6-石肖基苯齡(CAS No.101861-04-5)7·5份中添加水65份後,添加氫氧化鈉1.3份,使之溶 解。於冰浴冷卻下,添加35%亞硝酸鈉(和光純藥工業(股) 製造)水溶液6.1份,繼而一點一點地添加35%鹽酸19.4份使 之溶解並授拌2小時,獲得含有重氮鹽之懸浮液。繼而緩 慢添加將胺基磺酸(和光純藥工業(股)製造)5.6份溶解於水 26份中的水溶液,將過剩之亞硝酸鈉淬滅。 繼而’使3·曱基-1-苯基-5-η比唾琳顚)(和光純藥工業(股) 製造)5.6份懸浮於水70份中,使用氫氧化鈉將pH值調整至 8.0。於其中一邊以15分鐘滴加上述含有重氦^鹽之懸浮 液,一邊適宜追加1Ό%氫氧化納溶液而使pH值存在於7至 7.5之範圍内。滴加結束後,進而擾拌3 0分鐘,藉此獲得 161700.doc -69- 201237118 黃色之懸浮液。攪拌1小時。將過濾獲得之黃色固體於減 壓60°C下加以乾燥,獲得式(p_2)所示之化合物11.7份(產率 87%) 〇Example 1 After adding 65 parts of water to 7 parts of 2-amino-4-indolyl fluorenyl-6-succinyl benzene (CAS No. 101861-04-5), 1.3 parts of sodium hydroxide was added. Dissolve it. After cooling in an ice bath, 6.1 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added little by little to dissolve and mix for 2 hours to obtain a heavy weight. A suspension of nitrogen salts. Then, an aqueous solution in which 5.6 parts of an aminosulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water was slowly added, and excess sodium nitrite was quenched. Then, 5.6 parts of '33-yl-1-phenyl-5-η than 唾 顚 顚) (made by Wako Pure Chemical Industries Co., Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. . One of the above suspensions containing the heavy sulfonium salt was added dropwise thereto over 15 minutes, and a 1% by weight sodium hydroxide solution was added thereto to have a pH of 7 to 7.5. After the completion of the dropwise addition, the mixture was further disturbed for 30 minutes to obtain a yellow suspension of 161700.doc -69 - 201237118. Stir for 1 hour. The yellow solid obtained by filtration was dried at a reduced pressure of 60 ° C to obtain 11.7 parts of a compound of the formula (p_2) (yield: 87%).
將式(p-2)之化合物1〇份添加至二曱基甲醯胺(東京化成工 業(股)製造)100份中使之溶解,添加硫酸鉻(III)銨十二水 酯(和光純藥工業(股)製造)3.1份、乙酸鈉(和光純藥工業 (股)製造)1 · 1份後,加熱回流4小時半。冷卻至室溫後,將 反應溶液注入20%食鹽水1500份中,將過濾後獲得之橙紅 色固體於60°C下加以乾燥,獲得式(z-2)所示之化合物13.6 份(產率63%)。Add 1 part of the compound of the formula (p-2) to 100 parts of dimercaptocarboxamide (manufactured by Tokyo Chemical Industry Co., Ltd.) to dissolve it, and add chromium (III) ammonium sulfate decahydrate (and pure light) Manufactured by the pharmaceutical industry (stock), 3.1 parts, sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 1 part, and heated under reflux for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline solution, and the orange-red solid obtained after filtration was dried at 60 ° C to obtain 13.6 parts of the compound of the formula (z-2). 63%).
© Na (z-2) 式(z-2)所示之化合物之鑑定 (質量分析)離子化模式=ESI-: m/z=882.1 [M-Na+]·© Na (z-2) Identification of the compound of formula (z-2) (mass analysis) Ionization mode = ESI-: m/z = 882.1 [M-Na+]·
Exact Mass : 905.1 將式(z-2)所示之化合物5份溶解於义甲基_2_吡咯烷酮75 份中》於該溶液中添加將式(d-Ι)所示之化合物2 63份溶解 161700.doc ·70· 201237118 於N-曱基-2-吡咯烷酮35份中的溶液,攪拌2小時。反應結 束後,將其滴加至水300份中,過濾獲取析出之紅色固 體’於減壓6(TC下加以乾燥,藉此獲得式(卜27)所示之化 合物6.4份(產率86.8%)。 式(1_2 7)所示之化合物之鑑定 (質量分析)離子化模式=ESI+: m/z=1382.4[M-Cn +Exact Mass : 905.1 Dissolve 5 parts of the compound of the formula (z-2) in 75 parts of the meaning of methyl 2-pyrrolidinone. Adding 63 parts of the compound represented by the formula (d-Ι) to the solution is dissolved. 161700.doc ·70· 201237118 A solution of 35 parts of N-mercapto-2-pyrrolidone was stirred for 2 hours. After completion of the reaction, it was added dropwise to 300 parts of water, and the precipitated red solid was collected by filtration to dryness under reduced pressure 6 (TC), whereby 6.4 parts of the compound of formula (b) was obtained (yield 86.8%). Identification of the compound represented by formula (1_2 7) (mass analysis) ionization mode = ESI+: m/z = 1382.4 [M-Cn +
Exact Mass : 138 1.3Exact Mass : 138 1.3
合成例2 <樹脂B 1溶液之合成〉 於具備攪拌機、溫度計、回流冷卻器及滴液漏斗之燒瓶 内以0.02 L/分流入氮,成為氮環境,裝入乳酸乙酯3〇5質 量份,一邊攪拌一邊加熱至70°C。繼而,將甲基丙烯酸6〇 質量份、丙烯酸3,4-環氧三環[sj.i.o2,6]癸醋(將下述式(ι· 1)所示之化合物及式(ΙΜ)所示之化合物以莫耳比5〇:5〇混 合)240質量份溶解於乳酸乙自旨14Qf量份巾製備溶液,使 用滴液漏斗以4小時將該;容解液滴加至保溫在7〇e>c之燒瓶 内。另-方面’使用其他滴液漏斗以4小時滴加將 始劑2,2,·偶氮雙(2,4-二甲基戊腈㈣量份溶解於乳酸乙 醋225質量份中的溶液至燒瓶内。聚合起始劑之溶液滴加 I61700.doc 71 201237118 結束後,保持在70°C下4小時,其後冷卻至室溫,獲得重 量平均分子量Mw為1·3χ1〇4,固形物成分為33質量。/。,溶 液酸值為34 mg-KOH/g之樹脂Β1溶液。自上述固形物成分 與溶液酸值計算出樹脂B1之固形物成分酸值為1〇〇 mg-KOH/g。Synthesis Example 2 <Synthesis of Resin B 1 Solution> In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was introduced at 0.02 L/min to form a nitrogen atmosphere, and 5 parts by mass of ethyl lactate was charged. Heat to 70 ° C while stirring. Then, 6 parts by mass of methacrylic acid, 3,4-epoxytricyclo[sj.i.o2,6] vinegar of acrylic acid (the compound represented by the following formula (1) and the formula (ΙΜ)) The compound shown is dissolved in a molar ratio of 5 〇:5 )) in an amount of 240 parts by mass to a solution prepared from the 14Qf portion of the lactic acid, and is used in a dropping funnel for 4 hours; the solution is added to the heat retention at 7 〇e>c in the flask. On the other hand, using a different dropping funnel, a solution of the starting agent 2,2,· azobis(2,4-dimethylvaleronitrile (tetra) in 225 parts by mass of lactic acid was added dropwise over 4 hours. In the flask, the solution of the polymerization initiator was added dropwise to I61700.doc 71 201237118, and kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.3·1χ4, solid content. It is a mass of 33% by weight of a resin Β1 solution having a solution acid value of 34 mg-KOH/g. The acid value of the solid content of the resin B1 is calculated from the above solid content and the acid value of the solution to be 1 〇〇 mg-KOH/g. .
合成例3 <樹脂B2溶液之合成> 於具備攪拌機、溫度計、回流冷卻管、滴液漏斗及氣體 導入管之燒瓶内導入丙二醇單曱醚乙酸酯333 g。其後, 通過氣體導入管將氮氣導入燒瓶内,將燒瓶内環境置換為 氣氣。其後,將燒瓶内之溶液升溫至1〇〇。(:後,使用滴液 漏斗以2小時將含有N-苄基順丁烯二醯亞胺18.7 g、曱基丙 烯酸苄酯70.5 g、曱基丙烯酸5 17 g、甲基丙烯酸甲酯9〇.〇 g、偶氮二異丁腈5.2 g及丙二醇單曱醚乙酸酯182 g之混合 物滴加至燒瓶内,滴加完成後進而於l〇〇°c下持續攪拌5小 時。 攪拌結束後’通過氣體導入管將空氣導入燒瓶内,將燒 瓶内環境置換為空氣後’將甲基丙烯酸縮水甘油酯28.5 g、二(二甲基胺基曱基)苯酚13 g及對苯二酚0.165 g投入 燒瓶内’反應於11(TC下持續6小時,獲得重量平均分子量 161700.doc •72· 201237118Synthesis Example 3 <Synthesis of Resin B2 Solution> 333 g of propylene glycol monoterpene ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere inside the flask was replaced with an air gas. Thereafter, the solution in the flask was heated to 1 Torr. (: After that, using a dropping funnel to contain N-benzyl maleimide imine 18.7 g, benzyl methacrylate 70.5 g, methacrylic acid 5 17 g, methyl methacrylate 9 以. A mixture of 〇g, 5.2 g of azobisisobutyronitrile and 182 g of propylene glycol monoterpene ether acetate was added dropwise to the flask, and after the completion of the dropwise addition, stirring was continued for 5 hours at 10 ° C. The air was introduced into the flask through a gas introduction tube, and the environment inside the flask was replaced with air, and then 28.5 g of glycidyl methacrylate, 13 g of bis(dimethylaminomercapto)phenol, and 0.165 g of hydroquinone were put. The reaction in the flask was carried out at 11 (TC for 6 hours to obtain a weight average molecular weight of 161700.doc • 72· 201237118
Mw為16xl03,固形物成分為31%,酸值為80 mg-KOH/g (固形物成分換算)之樹脂B2溶液。 上述樹脂之聚苯乙烯換算重量平均分子量之測定,係使 用GPC法,以下述條件進行。 裝置 管柱 管柱溫度 溶劑 流速 被檢液固形物成分濃度 注入量 檢測器 校正用標準物質 :HLC-8120GPC(Tosoh(股)製 造)The resin B2 solution having a Mw of 16×10 3 and a solid content of 31% and an acid value of 80 mg-KOH/g (solid content conversion). The measurement of the polystyrene-equivalent weight average molecular weight of the above resin was carried out under the following conditions using a GPC method. Device String Column Temperature Solvent Flow Rate Concentration of Solid Content of Inspected Liquid Injection Injector Detector Standard Material for Calibration : HLC-8120GPC (Manufactured by Tosoh)
:TSK-GELG2000HXL :40°C :THF:TSK-GELG2000HXL :40°C :THF
:1.0 mL/min :0.001 〜0·01〇/〇 :50 μί :RI:1.0 mL/min :0.001 ~0·01〇/〇 :50 μί :RI
:TSK STANDARD POLYSTYRENE F-40 、 F-4 、 F-288 、 A-2500 、A-500(Tosoh(股)製造) 實施例2 [著色感光性樹脂組合物之製備] 混合 (A) 化合物(1):式(1-27)所示之化合物 30份 (B) 樹脂:樹脂B1(固形物成分換算) 40份 (C) 光聚合性化合物:二李戊四醇五丙烯酸酯與二季戊四 161700.doc -73-:TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh) Example 2 [Preparation of colored photosensitive resin composition] Mixed (A) compound (1) ): 30 parts of the compound represented by the formula (1-27) (B) Resin: Resin B1 (in terms of solid content) 40 parts (C) Photopolymerizable compound: dipentaerythritol pentaacrylate and dipenta tetra 161700 .doc -73-
S 201237118 醇六丙烯酸酯之混合物(KAYARAD DPHA ;日本化藥(股) 製造) 60份 (D)光聚合起始劑:N-苯曱醯氧基-1-(4-苯基硫烷基苯基) 辛-1-酮-2-亞胺(Irgacure OXE 01 ; BASF日本公司製造) 12份 (D)光聚合起始劑:2-苄基-2-二甲基胺基-1-(4-咮啉基苯 基)丁-1-酮(Irgacure 369 ; BASF日本公司製造) 6份 (D1)光聚合起始助劑:4,4·-雙(二乙基胺基)二苯曱酮(EAB-F ;保土谷化學(股)製造) 2份 (E)溶劑:丙二醇單甲醚 597份 (E) 溶劑:乳酸乙酯 43份 (F) 界面活性劑:聚醚改質矽油(Toray Silicone SH8400;S 201237118 Mixture of alcohol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 60 parts (D) Photopolymerization initiator: N-benzoquinone-1-(4-phenylsulfanylbenzene) Base) oct-1-one-2-imine (Irgacure OXE 01; manufactured by BASF Japan) 12 parts (D) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4) -Phenolinylphenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan) 6 parts (D1) photopolymerization starter: 4,4·-bis(diethylamino)benzophenone (EAB-F; manufactured by Baotu Valley Chemical Co., Ltd.) 2 parts (E) Solvent: propylene glycol monomethyl ether 597 parts (E) Solvent: ethyl lactate 43 parts (F) Surfactant: polyether modified eucalyptus oil (Toray Silicone SH8400;
Toray Dow Corning(股)製造) 0.09份 ,獲得著色感光性樹脂組合物。 [圖案之形成] 於2英吋見方之玻璃基板(Eagle2000 ;康寧公司製造) 上’以旋塗法塗佈著色感光性樹脂組合物後,於1 下 進行3分鐘預烘烤。冷卻後,將該塗佈有著色感光性樹脂 組合物之基板與石英玻璃製光罩之間隔設為1〇〇 μπι,使用 曝光機(TME-150RSK ; TOPCON(股)製造),於大氣環境 下,以100 mJ/cm2之曝光量(365 nm基準)進行光照射。再 者,作為光罩’使用可形成100 μηι之線與間隙圖案者。光 照射後,將該基板於23Ό下浸潰於含有非離子系界面活性 劑0.12%與氫氧化鉀0.04%之水溶液中8〇秒鐘進行顯影,水 161700.doc • 74- 201237118 洗後’於洪箱中,於230。(:下進行30分鐘後烘烤。放置冷 卻後’使用媒厚測定裝置(DEKTAK3 ;曰本真空技術(股) 製造))測定所得圖案之膜厚,結果為 2.0 μιη 〇 [色性能評價] 對於所得圖案,使用測色機(OSP-SP-200 ; Olympus(股) 製造)測定分光,使用C光源之配色函數測定CIE之XYZ表 色系中之浸漬前後之xy色度座標(X、y)(即色度)及亮度Y。 結果示於表1。 [耐溶劑性評價] 於上述圖案形成中,除不使用光罩而曝光以外,進行相 同操作’製作塗膜。將所得塗膜浸潰於23〇c之N•曱基_2· °比洛院酮中30分鐘,使用測色機(〇sp_sp_2〇〇 ; 〇lyjnpus (股)製造)測定分光’使用C光源之配色函數測定CIE之 XYZ表色系中之浸潰前後之xy色度座標(Rx、Ry)(即色度) 及亮度RY ’計算浸潰前後之色差△ Eab*。色差△ Eab*越 小則耐溶劑性越良好。色差△ Eab*之結果示於表1。 又’於浸潰後之塗膜上,使用切機及supei· cutter guide(太佑機材(taiyukizai)公司製造)以1 mm間隔切入切 口 ’製作100個1 mmxl mm之網格。於該網格上黏貼Toray Dow Corning (manufactured by Toray Dow Corning Co., Ltd.) was 0.09 parts to obtain a colored photosensitive resin composition. [Formation of Pattern] The colored photosensitive resin composition was applied by a spin coating method on a glass substrate (Eagle 2000; manufactured by Corning Incorporated) of 2 inches square, and then prebaked for 3 minutes in 1 time. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the mask made of quartz glass was set to 1 μm, and the exposure machine (TME-150RSK; TOPCON) was used in an atmosphere. Light irradiation was performed at an exposure amount of 100 mJ/cm 2 (365 nm reference). Further, as the photomask, a line which can form a line of 100 μm and a gap pattern can be used. After the light irradiation, the substrate was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 8 seconds to develop, and the water was 161700.doc • 74-201237118 after washing In the flood box, at 230. (: After baking for 30 minutes, the film thickness of the obtained pattern was measured by using a medium thickness measuring device (DEKTAK3; manufactured by Sakamoto Vacuum Technology Co., Ltd.)), and the result was 2.0 μm 〇 [color performance evaluation] The obtained pattern was measured for spectroscopicity using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (X, y) before and after immersion in the XYZ color system of CIE were measured using the color matching function of the C light source. (ie chromaticity) and brightness Y. The results are shown in Table 1. [Evaluation of Solvent Resistance] In the above pattern formation, a coating film was produced by performing the same operation except that the mask was not exposed. The obtained coating film was immersed in 23 〇c of N•曱基_2·° piroxone for 30 minutes, and a color measuring machine (〇sp_sp_2〇〇; 〇lyjnpus (manufactured by 〇)) was used to measure the spectroscopic use of the C light source. The color matching function determines the xy chromaticity coordinates (Rx, Ry) (ie, chromaticity) and the brightness RY ' before and after the immersion in the XYZ color system of CIE to calculate the color difference Δ Eab* before and after the immersion. The smaller the color difference Δ Eab*, the better the solvent resistance. The results of the color difference Δ Eab* are shown in Table 1. Further, on the coating film after the immersion, a slit and a supei· cutter guide (manufactured by Taiyukizai Co., Ltd.) were used to cut the slits at intervals of 1 mm to make 100 grids of 1 mm x 1 mm. Paste on the grid
Sellotape(註冊商標)24 mm宽(Nichiban(股)公司製造),自Sellotape (registered trademark) 24 mm wide (manufactured by Nichiban Co., Ltd.), from
Sellotape( §主冊商標)之上以橡皮摩擦使|§eii〇tape(註冊商標) 附著於硬化塗臈上,2分鐘後拿住Sellotape(註冊商標)之邊 端’ 一邊與塗膜面保持直角’一邊一口氣剝離。其後,目 視計數塗膜未剝離而於基板上殘留之網格之數目。將該網 161700.doc .75- 201237118 格數作為密著性,示於表1。 比較例1 混合 (A) 著色劑:Orasol Red G(Ciba Japan(股)製造) 47.5# (B) 樹脂:樹脂B2溶液 16份 (C) 光聚合性化合物:二季戊四醇五丙烯酸酯與二季戊四 醇六丙烯酸酯之混合物(KAYARAD DPHA ;日本化藥(股) 製造) 23.9份 (D) 光聚合起始劑:2-甲基-2-咮啉基-1-(4-甲基硫烷基苯 基)丙-1-酮(Irgacure 907 ; BASF曰本(股)製造) 3.6份 (D) 光聚合起始劑:2,4-雙(三氯甲基)-6-向曰葵基-1,3,5-三 畊(TAZ-PP ; Nihon SiberHegner(股)製造) 2.8份 (D1)光聚合起始助劑:4,4·-雙(二乙基胺基)二苯曱酮(EAB-F ;保土谷化學(股)製造) 1.2份 (E) 溶劑:丙二醇單甲醚 267份 (E) 溶劑:丙二醇單甲醚乙酸酯 138份 (F) 界面活性劑:Megafac F475(DIC(股)製造) 0.1份 獲得著色感光性樹脂組合物。對著色感光性樹脂組合物, 以實施例1相同之方式進行評價。結果示於表1。 161700.doc -76- 201237118 [表1]On the Sellotape (the main book mark), rubber friction is used to attach the §eii〇tape (registered trademark) to the hardened enamel. After 2 minutes, hold the side of the Sellotape (registered trademark) and keep it at right angles to the coated surface. 'One side stripped. Thereafter, the number of the grids remaining on the substrate without peeling off the coating film was visually counted. The grid number 161700.doc .75 - 201237118 is shown as the adhesion, as shown in Table 1. Comparative Example 1 Mixing (A) Colorant: Orasol Red G (manufactured by Ciba Japan Co., Ltd.) 47.5# (B) Resin: Resin B2 solution 16 parts (C) Photopolymerizable compound: dipentaerythritol pentaacrylate and dipentaerythritol Acrylate mixture (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 23.9 parts (D) Photopolymerization initiator: 2-methyl-2-indolyl-1-(4-methylsulfanylphenyl) Propan-1-one (Irgacure 907; manufactured by BASF Co., Ltd.) 3.6 parts (D) Photopolymerization initiator: 2,4-bis(trichloromethyl)-6-to geranyl-1, 3,5-three tillage (TAZ-PP; manufactured by Nihon Siber Hegner) 2.8 parts (D1) photopolymerization starter: 4,4·-bis(diethylamino)benzophenone (EAB- F; manufactured by Baotu Valley Chemical Co., Ltd.) 1.2 parts (E) Solvent: 267 parts of propylene glycol monomethyl ether (E) Solvent: 138 parts of propylene glycol monomethyl ether acetate (F) Surfactant: Megafac F475 (DIC) )) 0.1 part of the obtained photosensitive resin composition was obtained. The colored photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1. 161700.doc -76- 201237118 [Table 1]
耐溶劑性 _^AEab* o.iSolvent resistance _^AEab* o.i
-—---_Ijoo ^~~ ' ”於N -甲其0 ~~ί …咯烷酮浸潰中著色塗膜自剝離基板剝離 故而…、法測定色差△ Eab*及密著性。 使用本發明之著色感光性樹脂組合物而形成之塗膜確 認具了良好之耐溶劑性。因此可知,根據本發明之著色感 光性樹脂組合物,可獲得輕劑性優異之塗膜、圖案及高 品質之彩色濾光片。 [產業上之可利用性] 根據本發明之著色感光性樹脂組合物,可獲得耐溶劑性 良好之塗膜、圖案及高品質之彩色濾光片。 161700.doc 77·-—---_Ijoo ^~~ ' ” In the N-A, 0~~ί... sulphide immersion, the colored coating film is peeled off from the peeling substrate, and the color difference Δ Eab* and the adhesion are measured. The coating film formed by the coloring photosensitive resin composition of the invention has a good solvent resistance. Therefore, according to the colored photosensitive resin composition of the present invention, it is possible to obtain a coating film, a pattern, and a high quality which are excellent in lightness. [Colorful filter] [Industrial Applicability] According to the colored photosensitive resin composition of the present invention, a coating film, a pattern, and a high-quality color filter excellent in solvent resistance can be obtained. 161700.doc 77·
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TW201035677A (en) * | 2008-12-09 | 2010-10-01 | Sumitomo Chemical Co | Colored photosensitive resin composition |
JP5760584B2 (en) * | 2011-03-29 | 2015-08-12 | 住友化学株式会社 | Colored curable resin composition |
JP5993626B2 (en) * | 2011-06-24 | 2016-09-14 | 住友化学株式会社 | Salt and colored curable composition |
-
2012
- 2012-01-31 JP JP2012017676A patent/JP5807568B2/en active Active
- 2012-02-08 TW TW101104094A patent/TWI515268B/en active
- 2012-02-13 KR KR1020120014289A patent/KR101766745B1/en active IP Right Grant
- 2012-02-13 CN CN201210038468.0A patent/CN102636957B/en active Active
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JP5807568B2 (en) | 2015-11-10 |
KR20120093096A (en) | 2012-08-22 |
JP2012185483A (en) | 2012-09-27 |
KR101766745B1 (en) | 2017-08-09 |
TWI515268B (en) | 2016-01-01 |
CN102636957B (en) | 2016-06-22 |
CN102636957A (en) | 2012-08-15 |
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