TW201219977A - capable of forming a colored hardened film with excellent long-term stability in liquid state, wide development latitude, no odor problem and excellent solvent resistance - Google Patents
capable of forming a colored hardened film with excellent long-term stability in liquid state, wide development latitude, no odor problem and excellent solvent resistance Download PDFInfo
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- TW201219977A TW201219977A TW100130885A TW100130885A TW201219977A TW 201219977 A TW201219977 A TW 201219977A TW 100130885 A TW100130885 A TW 100130885A TW 100130885 A TW100130885 A TW 100130885A TW 201219977 A TW201219977 A TW 201219977A
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- Prior art keywords
- acid
- pigment
- compound
- photosensitive composition
- colored
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Liquid Crystal (AREA)
Abstract
Description
201219977 六、發明說明: 【發明所屬之技術領域1 本發明係有關著色4忠R 4丄 级先性組成物、使用該著 性組成物之彩色濾光片之制 顯示裝置。 …法、彩色遽光片 【先前技術】 型咴4 里彆哏 線良杯 之咴晶 晶_系 裝薏的 以往 純度 的 的 以往’行動電話、轉维剂乱 一 、▼型遊戲機、PDA等小 顯示裝置中由於需使用二, -人電池或乾電池等電容 的背光源,故此等顯示萝荖故冰ro .^ „ L 裝置所使用之彩色濾光片 係有利地使用呈高透明性,廿π & A ^ ^ ^ 月性,亚可使背光源之放射 地穿透而進行色彩顯示的色材。 近年來,液晶顯示梦罢沾功丨 展置的大型化因個人電腦 ;示榮幕、液晶電視等用途而持續進展,此等液 ::中亚無背光源的電源之限制’且重視顯示 RGB色再現性。因此, 心色濾光片的色材除要求 透明性之外,還要求含 更间的晝貝,亦即對比及色 提升。 針對上述要求,已開發 小化之顏料級成物中,進一 性化合物、光聚合起始劑及 ,使用該著色性組成物並透 明基板上形成紅色、綠色、 ’且其已實用化。 有一種在顏料之粒徑更為微 步以鹼可溶性樹脂、光聚合 其他成分作為著色性組成物 過光微影法等,於玻璃等透 藍色三色圖案的彩色濾光片 ^由色調及堅固性觀點而言,其中綠色著色圖案一般 係使用乳化銅醜菁素顏料(C.I.顏料、綠7)、氯化漠化銅酞 菁素顏料(C.1.顏料綠36)等綠色顏料。 201219977 就綠色顏料 月洛嘈♦、* 5近年來以提高顏料之彩度(色純度 鋅、錫、錯等 業已對中心金屬為銘、鈦、始、錄、 利文獻υ進行研巧 化金屬酉大菁素顏料(例如參照專201219977 VI. Description of the Invention: [Technical Field 1 of the Invention] The present invention relates to a display device for coloring a 4 loyal R 4 丄 precursor composition and a color filter using the same. ... method, color twilight film [prior art] type 咴 4 哏 哏 哏 良 良 良 _ _ _ 以往 以往 以往 以往 以往 以往 以往 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' In a small display device, since a backlight of a capacitor such as a human battery or a dry battery is required, the color filter used in the device is advantageously used for high transparency.廿π & A ^ ^ ^ Month, the color material that allows the backlight to radiate through and display the color. In recent years, the liquid crystal display has been greatly expanded due to the personal computer; The use of curtains, LCD TVs, etc. continues to progress, such liquids:: Central Asia without backlight power supply restrictions 'and pay attention to display RGB color reproducibility. Therefore, in addition to the transparency required for the color filter of the heart color filter, It is also required to contain more mussels, that is, contrast and color enhancement. In response to the above requirements, a pigmented product has been developed, a further compound, a photopolymerization initiator, and the use of the coloring composition and transparency. Red, green, Moreover, it has been put into practical use. There is a color filter in which the particle diameter of the pigment is more microstep, the alkali-soluble resin, the photopolymerization other component is used as a coloring composition, and the chromatic lithography method is used, and the blue color pattern of the glass is transparent. In terms of color tone and robustness, the green coloring pattern generally uses an emulsified copper phthalocyanine pigment (CI pigment, green 7), a chlorinated desertified copper phthalocyanine pigment (C.1. Pigment Green 36) ) Green pigments. 201219977 In the past, green pigments 洛 嘈 ♦, * 5 in recent years to improve the color of pigments (color purity zinc, tin, wrong, etc. have been the center metal for the Ming, Titanium, Shi, recorded, Lee literature Research and development of metal ruthenium pigments (for example, reference
Pt # (C I 4. °、,特別是針對彩度高的鹵化鋅酞菁素 顏科(C.I.顏料綠5 ^ 0 ^ )徒出各式各樣的顏料(例如參照專利 文獻2〜4)。例如p _ .、 進仃Br、Cl之取代度、採用甜菜鹼 (betame)型界面活性 , W之顏枓處理法、各種結晶形等的 詳細研究,並報導於y 、X線%射光譜中,在相對Cu-Κα線 的布拉格角(2θ±〇 2。、盔κ 1。 .)為26.4 、25.5。具有最大繞射峰的 鹵化銅酞菁素係5古〜& ,+ 保王问衫度(色純度及色濃度),且經時穩 定性優良而有用(例如灸n7) # 、』如參妝專利文獻5)。又提出使用此等 顏料可製!透明度高且色純度高的彩色濾光片。 准同月度内衫度、高對比之齒化金屬酞菁素顏 料其粒子尺寸小,且比起以往顯影寬容度較窄,又有時 會發生作為著色感光性組成物保存之際經時性能不穩定 的問題。為提高此經時穩定性而提出使用具支鏈構造的 硫醇化合物(例如參照專利文獻6),惟進—步係要求高經 時穩定性與針對臭氣等之作業環境的改善、硬化膜之耐 溶劑性。 、 [先前技術文獻] [專利文獻] [專利文獻曰本特開2003-1 6 1 823號公報 [專利文獻2]日本特開2〇〇7_284592號公報 [專利文獻3]日本特開2004-70342號公報 [專利文獻4]日本特開2〇〇8_24743號公報 201219977 [專利文獻5]日本特開2009-223288號公報 [專利文獻6]日本特開2〇〇4_264435號公報 【發明内容】 [發明所欲解決之課題] 本發明係鑑於上述問題而開發,本發明之課題在於 提供一種可形成液體狀態下的經時穩定性優良.、顯影寬 容度廣、無臭氣問題且财溶劑性良好之著色硬化膜的著 色感光性組成物。又,本發明之進一步課題在於提供一 種使用前述本發明著色感光性組成物而成之色純度高、 對比高之色特性良好的彩色濾光片、彩色濾光片之製造 方法及具備該彩色濾光片之液晶顯示裝置。 [解決課題之手段] 本發明人等為解決上述課題而戮力進行研討的結果 發現,藉由以下手段便可達成本發明之課題,而完成本 發明。 <1> 一種著色感光性組成物,其含有(A)鹵化辞酞菁素 顏料、(B)具有酸基之聚合性單體、(c)黏著劑樹脂、(D) 光聚合起始劑、(E)選自二級或三級脂肪族硫醇化合物之 鏈轉移劑及(F)溶劑。 <2> 如<1>之著色感光性組成物,其中前述二級或三級 脂肪族硫醇化合物為單官能或二官能脂肪族硫醇化合物。 <3> 如<1>或<2>之著色感光性組成物,其中前述(D)光 聚合起始劑為六芳基雙咪唑化合物。 <4>如<1>至<3>中任一項之著色感光性組成物,其中 前述(C)黏著劑樹脂為具有酸基之樹脂。 201219977 <5> 如<1>至中任一項之著色感光性組成物,其進 一步含有(G)光敏化劑。 <6> —種圖案形成方法,其包含將如< 1 >至<5>中任一 項之者色感光性組成物提供至基板上而形成著色層的著 色層形成步驟;對所形成之著色層進行圖樣的曝光以使 曝光區域硬化的曝光步驟;及使曝光後之著色層中的未 曝光部分顯影並予以去除而形成圖案的顯影步驟。 <7> —種彩色濾光片,其係採用如<6>之製造方法所製 造。 <8> 一種液晶顯示裝置,其係具備<7>之彩色濾光片而 成。 [發明之效果] 根據本發明,可提供一種可形成液體狀態下的經時 %定性優良 '顯影寬容度廣、無臭氣問題且耐溶劑性良 #之著色硬化膜的著色感光性組成物。又可提供一種使 田 -.V- ’述本發明著色感光性組成物而成之色純度高、對比 两之色特性良好的彩色濾光片、彩色濾光片之製造方法 及具' 備該彩色濾光片之液晶顯示裝置。 【實施方式】 以下’對本發明著色感光性組成物、使用該著色感 光性組成物之彩色濾光片及使用該彩色濾光片之液晶顯 示裝置詳細進行說明。 <著色感光性組成物> 本發明著色感光性組成物之特徵為含有(A)鹵化鋅 酉太菁素顏料、(B)具有酸基之聚合性單體、(C)黏著劑樹 201219977 脂、(D)光聚合起始劑、(E)選自二級或三級脂肪族硫醇 化合物之鏈轉移劑及(F)溶劑。 —1^· 對構成.本發明著色感光性組成物的各成分谁 行欽述。 <(A)鹵化鋅酞菁素顏料> 本發明著色感光性組成物所使用之顏料為i化辞软 菁素。 最夕1 6/固溴原子及/或氯原子來取代此等氫原子。 此等齒素原子可完全相同,亦可各自相異。 、齒素原子的取代數較佳為8以上16以下,更佳^ 1 〇以上1 6以下之範圍。 ’、、 或漠Γ:取係各自單獨為氫原子、氣原ϊ 4至v _者較佳為氯原子或溴原子。 呈:鋅酞菁素顏料透過卩8個以上漠原子予 便呈現帶有黃色之明度 片的綠色畫素部圖案。 .彔色,而適用於彩色^ 特別是溴原子的取代 高而適用於本發明。 為〜16個者因明度更為* 本發明t所使用之鹵化錄 酸法、_化觖映土 ,辛敢月素顏料可由例如氣巧 。“醜腈法、溶融法等各種週知製造方法她 報所揭露之_化鋅酞 言較佳。 曰本特開2004-70342號公 的製造方法以成本觀點而 201219977 在穩定性方面,其 古彳而S ^ ± ^、'、因其他添加劑、後步驟 方式而異,惟較佳為曰 /π 之婉姓曰棘拖Μ + 特開2008-1 9383號公報 之、…曰轉換的齒化鋅酞菁素顏料。 特別是在提升分散性 0. ν . 注方面,日本特開2007- 波公報所揭露之樹脂被覆 化 设之_化辞酞菁素顏料為 態。 本發明鹵化辞酞菁素顏料的平均一次粒徑 1〇nm〜100nm之範圍,更佳為i〇nm〜4〇nm之範圍 使用此範圍之平均一次粒徑的酿菁素系顏料 製得分散穩定性、t色力優良,且輝度高、對比 色濾光片用著色感光性組成物。 此外,本發明中的平均—次粒徑係指,以穿 子顯微鏡對視野内的粒子進行拍攝,並針對二維 之構成凝聚體的駄菁素顏料的一次粒子丨〇 〇個, 出其較長之直徑(長徑)與較短之直徑(短徑)的平友 將其平均所得之値。 本發明画化鋅酞菁素顏料的一次粒子若其縱 見比進一步為1〜3之範圍,則於各用途領域中可 度特性,並進一步提高流動性。 欲求出長寬比時’則與如前述之求取—次粒 均粒徑的情況相同,以穿透式電子顯微鏡或掃描 顯微鏡對視野内的粒子進行拍攝。 其後,針對二維影像上之構成凝聚體的一次米 個求出較長之直控(長徑)與較短之直徑(短徑)的 ,再使用此等値來算出。 之組合 所揭露 320986 較佳形 較佳為 〇 ,便可 南的彩 透式電 影像上 分別求 7値,再 橫之長 提.升黏 子之平 式電子 L 子 100 平均値 201219977 欲製得平均一次粒徑為10nm〜100nm之範圍的齒化 辞醜菁素顏料時’雖能以任何方法予以微粒子化,惟以 可容易抑制結晶生長’並可獲得平均一次粒徑較小的顏 料粒子之觀點而言’係以採用溶劑鹽磨(s〇lvent 8川 milling)處理為佳。 該「溶劑鹽磨」係指將鹵化鋅酞菁素顏料、無機鹽 及有機溶劑混練磨碎之意。 粒徑較大的i化鋅敝菁素顏料亦可進行乾式磨碎後 進行溶劑鹽磨。 具體而言,係將鹵化鋅酞菁素顏料、無機鹽及未溶 有該豳化鋅酞菁素顏料、無機鹽的有機溶劑加入至混練 機,並於其中進行混練磨碎。 此時之混練機可使用例如混練機、Mix_MuUer(商品 名)等。 &上述無機鹽可適合使用水溶性無機鹽,係以使用例 如氯化鈉、氯化鉀、硫酸鈉等無機鹽為佳。 又,更佳使用平均粒徑〇.5〜5〇μηι之無機鹽。 此類無機鹽可藉由將一般無機鹽微粉碎來容易地製 得。 j製得平均—次粒徑$ 1〇nm〜1〇〇nm之範圍的函化 鋅敗菁素顏料時’係以提高無機鹽之用量對溶劑鹽磨中 的_化鋅敌菁素顏料之用量的比例為佳。 即’以質量換算,相對函化鋅酞菁素㈣】份該無 機鹽之用量較佳為5〜2〇份,更佳為7〜15份。 201219977 有機溶劑係以使肖可抑制結日日日 ,此種有機溶劑適合使 χ、有機溶劑為佳 二乙二醇、丙三醇、乙:有機溶劍,可採用例如 ^ c —醇、.丙二醆、 液體聚丙二醇、2 之體聚乙二醇、 9 , 乳基甲軋基)乙醇、2签 七、戍氧基)乙II、2_(己氧基)乙醇、了 Κ基乙醇、 二乙二醇單乙鍵、二乙二醇單丁喊、:乙二醇單甲齡、 醇單甲越…甲氧基I丙醇、b乙氧::二醇、三乙二 醇、二丙二醇單甲_、二丙二醇等。两%、二丙二 此時之水溶性有機溶劑之用 質量換算,相對“辞酞菁素顏二:二惟以 ’更佳為0.8〜2份。 為0·〇1〜5份 進行溶劑鹽磨時之溫度較佳為3〇〜 80 1 〇〇 ◦。進行溶劑鹽磨之 更佺為 為8〜18小時。 &佳為5〜20小時,更佳 士此’便可製得含有鹵化辞駄菩去拓 有機溶劑作為主成分的混合物,惟可透過鹽及 =有機溶劑與無機鹽,並視需求對^ ^ =的固體進行清洗,、乾燥、粉碎等 支的_化鋅酞菁素顏料粉體。 採用水洗、熱水清洗的任一種。清洗次數亦 」於1〜5次之範圍内重複進行。 :為使用水溶性無機鹽及水溶性有機溶劑的前述混 口物蚪,透過水洗可容易地去除有機溶劑與無機鹽。 品上述過濾、清洗後之乾燥可列舉例如,由設置於乾 秌機之加熱源進行8〇〜12〇〇c的加熱等來進行顏料的去水Pt # (CI 4. °, in particular, for a high-purity zinc halide phthalocyanine Yankee (CI Pigment Green 5 ^ 0 ^ ), various pigments are produced (for example, refer to Patent Documents 2 to 4). p _ . , the degree of substitution of Br, Cl, the betame-type interfacial activity, the W 枓 treatment, various crystal forms, etc., and reported in the y, X-ray % spectroscopy, The Bragg angle (2θ±〇2, helmet κ 1 . . ) in the Cu-Κα line is 26.4 and 25.5. The copper phthalocyanine system with the largest diffraction peak is 5 ancient ~ & Degree (color purity and color density), and it is useful for excellent stability over time (for example, moxibustion n7) #," such as the makeup patent document 5). It is also proposed to use these pigments! A color filter with high transparency and high color purity. The toothed metal phthalocyanine pigment with the same monthly wear and high contrast has a small particle size, and has a narrower latitude than the conventional development, and sometimes occurs as a coloring photosensitive composition. Stable problem. In order to improve the stability over time, it is proposed to use a thiol compound having a branched structure (for example, refer to Patent Document 6), but the step-by-step system requires high stability over time and improvement of an operating environment such as odor, and a cured film. Solvent resistance. [Prior Art Document] [Patent Document] [Patent Document 2] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 2009-223288. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a coloring property which is excellent in stability over time in a liquid state, has a wide development latitude, is free from odor, and has a good solvent property. A colored photosensitive composition of a cured film. Further, a further object of the present invention is to provide a color filter having a high color purity and a high contrast color characteristic using the coloring photosensitive composition of the present invention, a method for producing a color filter, and a color filter. A liquid crystal display device for light sheets. [Means for Solving the Problem] As a result of intensive studies to solve the above problems, the present inventors have found that the subject of the present invention can be achieved by the following means, and the present invention has been completed. <1> A colored photosensitive composition comprising (A) a halogenated phthalocyanine pigment, (B) a polymerizable monomer having an acid group, (c) an adhesive resin, and (D) a photopolymerization initiator And (E) a chain transfer agent selected from a secondary or tertiary aliphatic thiol compound and (F) a solvent. <2> The colored photosensitive composition of <1> wherein the secondary or tertiary aliphatic thiol compound is a monofunctional or difunctional aliphatic thiol compound. <3> The colored photosensitive composition of <1> or <2>, wherein the (D) photopolymerization initiator is a hexaarylbisimidazole compound. The colored photosensitive composition according to any one of <1> to <3>, wherein the (C) adhesive resin is a resin having an acid group. The colored photosensitive composition according to any one of <1>, which further contains (G) a photosensitizer. <6> A pattern forming method comprising the step of forming a coloring layer by providing a color photosensitive composition according to any one of <1> to <5> to a substrate to form a coloring layer; An exposure step in which the formed coloring layer is exposed to the pattern to harden the exposed region; and a developing step of developing and removing the unexposed portion in the colored layer after the exposure to form a pattern. <7> A color filter manufactured by the method of <6>. <8> A liquid crystal display device comprising a color filter of <7>. [Effects of the Invention] According to the present invention, it is possible to provide a coloring photosensitive composition which is capable of forming a colored cured film which is excellent in development time and has a wide developing latitude, no odor problem, and good solvent resistance in a liquid state. Further, it is possible to provide a color filter having a high color purity and a good color contrast characteristic, and a method for producing a color filter, which is obtained by coloring a photosensitive composition of the present invention. A liquid crystal display device of a color filter. [Embodiment] Hereinafter, a coloring photosensitive composition of the present invention, a color filter using the colored photosensitive composition, and a liquid crystal display device using the color filter will be described in detail. <Coloring photosensitive composition> The colored photosensitive composition of the present invention is characterized by containing (A) a zinc halide quinococyanine pigment, (B) a polymerizable monomer having an acid group, and (C) an adhesive tree 201219977 fat (D) a photopolymerization initiator, (E) a chain transfer agent selected from a secondary or tertiary aliphatic thiol compound, and (F) a solvent. -1^· For the components of the coloring photosensitive composition of the present invention, it is explained. <(A) A zinc halide phthalocyanine pigment> The pigment used in the coloring photosensitive composition of the present invention is i. The E1/6 bromine atom and/or the chlorine atom are substituted for these hydrogen atoms. These dentate atoms may be identical or different. The number of substitutions of the dentate atom is preferably from 8 to 16 or less, more preferably from 1 to 1,500. ',, or indifference: the respective units are each a hydrogen atom, and the gas atom ϊ 4 to v _ is preferably a chlorine atom or a bromine atom. Present: The zinc phthalocyanine pigment is passed through more than 8 indifferent atoms to give a green pixel pattern with a yellow luster. It is suitable for use in the present invention because it is high in color, and is particularly suitable for the coloring of bromine atoms. For the reason of ~16, the brightness is more * The halogenation recording method used in the present invention t, the 觖 觖 觖 , 、, 辛 月 素 颜料 pigment can be, for example, qi. "A variety of well-known manufacturing methods such as ugly nitrile method, melting method, etc., which is disclosed by her newspaper, is better. The manufacturing method of 曰本特开2004-70342 is based on cost. 201219977 In terms of stability, its ancient S and S ^ ± ^, ', because of other additives, the latter steps vary, but it is better to 曰 / π 婉 曰 曰 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 Zinc phthalocyanine pigment. In particular, in order to improve the dispersibility, the phthalocyanine pigment is disclosed in the Japanese Patent Publication No. 2007-wave. The average primary particle diameter of the pigment is in the range of 1 〇 nm to 100 nm, more preferably in the range of i 〇 nm to 4 〇 nm. The dispersion stability and t color are obtained by using the average primary particle diameter of the pigment. It is excellent, and the luminance is high, and the contrast color filter is colored with a photosensitive composition. In addition, the average-secondary particle size in the present invention means that the particles in the field of view are imaged by a wear microscope, and the two-dimensional composition is condensed. The primary particles of the body of the phthalocyanine pigment The diameter of the long diameter (long diameter) and the shorter diameter (short diameter) are averaged. The primary particles of the zinc phthalocyanine pigment of the present invention have a longitudinal ratio of 1 to 3. In the field of application, the mobility characteristics are further improved, and the fluidity is further improved. When the aspect ratio is to be determined, the same as in the case of the above-mentioned subgranular average particle size, with a transmission electron microscope or a scanning microscope. Shooting the particles in the field of view. Then, find the long direct control (long diameter) and the shorter diameter (short diameter) for the primary constituting the aggregate on the two-dimensional image, and then use these.値 算出 。 320 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 986 201219977 In order to obtain a toothed ugly pigment pigment having an average primary particle diameter of 10 nm to 100 nm, 'the particle can be micronized by any method, but the crystal growth can be easily suppressed' and the average primary particle diameter can be obtained. View of pigment particles Introduction 'to employ based solvent salt milling (8 s〇lvent River Milling) process is preferred. The "solvent salt milling" refers to the halogenated zinc phthalocyanine pigment a pigment, an inorganic salt and an organic solvent kneading grinding means. The i-zinc phthalocyanine pigment having a larger particle size can also be dry-ground and subjected to solvent salt milling. Specifically, a zinc halide phthalocyanine pigment, an inorganic salt, and an organic solvent in which the zinc phthalocyanine pigment or inorganic salt is not dissolved are added to a kneader, and kneading is carried out therein. For example, a kneading machine, a Mix_MuUer (trade name), or the like can be used as the kneading machine at this time. The above inorganic salt may suitably be a water-soluble inorganic salt, and an inorganic salt such as sodium chloride, potassium chloride or sodium sulfate is preferably used. Further, it is more preferable to use an inorganic salt having an average particle diameter of 55 to 5 〇μηι. Such inorganic salts can be easily produced by finely pulverizing a general inorganic salt. j, when the average-minor particle size range of $1〇nm~1〇〇nm is used to form a functionalized zinc sulphur pigment pigment, The ratio of the amount is preferably. That is, the amount of the inorganic salt is preferably 5 to 2 parts, more preferably 7 to 15 parts, in terms of mass conversion relative to the functional zinc phthalocyanine (IV). 201219977 The organic solvent is used to make Xiao Ke inhibit the date of the day. The organic solvent is suitable for the bismuth, organic solvent is good diethylene glycol, glycerol, B: organic solvent, for example, ^ c - alcohol. Propanediol, liquid polypropylene glycol, polyethylene glycol of 2, 9, milk-based methyl alcohol, 2, 7 and decyloxy) ethyl II, 2-(hexyloxy)ethanol, mercaptoethanol, Diethylene glycol single-ethyl bond, diethylene glycol single-dial,: ethylene glycol single-aged, alcoholic mono-... methoxy I propanol, b ethoxy:: diol, triethylene glycol, two Propylene glycol monomethyl, dipropylene glycol and the like. The conversion of the water-soluble organic solvent at the time of the two-dimensional and two-propane two is relatively the same as "the phthalocyanine yan: two bis-" is preferably 0.8 to 2 parts. The solvent salt grinding is carried out for 0 〇 1 to 5 parts. The temperature is preferably from 3 〇 to 80 1 〇〇◦. The solvent salt grinding is carried out for 8 to 18 hours. & good for 5 to 20 hours, more preferably this can be obtained with halogenated words.駄 去 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到Powder. Any one of water washing and hot water washing. The number of washings is repeated in the range of 1 to 5 times. The organic solvent and the inorganic salt are easily removed by washing with water as the above-mentioned mixture of a water-soluble inorganic salt and a water-soluble organic solvent. For the drying after filtration and washing, for example, the dewatering of the pigment is carried out by heating at a temperature of 8 Torr to 12 Torr, which is provided in a heating source of a dryer.
S -11 201219977 及/或去溶劑的分加_ #々、A ± 批式或連縯式乾燥等,作 有箱型乾燥機、帶式& + ^ '、、' c刼機一般 Λ乾各機、賀霧式乾燥機等。 一 Α又乾燥後之粉碎並非為用以增大比表面積 -:人粒子的平均粒徑之操作,而是如 賣、縮小 機、帶式乾燥機進行乾焊# 1如箱型乾燥 …際用以碎解顏料並予以粉體化而進行者曲折㈦: 例如研缽及杵、鍵碎機、盤式磨機、針式球磨機了:: 磨機等所進行之粉碎等。 、噴射 本發明之(Α)鹵化鋅酞菁素顏料可由例如 來製得,枪-Γ m 上边方法 准亦可採用一般流通的豳化辞酞 料分散液產品。 月素顏枓或顏 如此所得之(A)鹵化鋅酞菁辛顏 取七k 2a 耳l顔村兵一次粒子的凝 小力杈弱,並具有較容易分 -., 負 因而易於製作薄 蓋力大且對比高的著色皮膜。 表作值 I月中,此等鹵化鋅酞菁素顏料可單獨 亦可與 臭化率或氣化率才 中心全屬由:異的其他画化鋅酞菁素顏料、 中”屬由其他金屬取代的填化駄菁素等混合使用。 糟由改變溴化率及氯化率、改變中心 料的色調便會產生變化,可夕 性。 θ加了再現之色相的多樣 成物中,將其他色材與(八)_化 色感光性組成物的色相並增大 #發明著色感光性組 辞醜菁素顏料即可調整著 穿透率。 亦可對齒化鋅酞菁素 舉例而言,為形成綠色晝素 顏料併用黃色顏料、橙色顏料。 201219977 作為黃色顏料之實例,除重氮系黃色顏料、異吲哚 系黃色顏料、啥琳黃系黃色顏料、苯并味吐酮 (benzimidaz〇1〇n)系黃色顏料、鎳偶氮系黃色顏料等黃色 顏料,外,亦可視需求使用二n各并吼洛系橙色顏料 、紫環酮(p e r i η ο n e)糸;^ A &,丨 # ;示撥色顏料等橙色顏料。 若列舉具體例,則為C丄顏料黃卜1:1、2、3、4 5 6 1〇 、 11 、 12 、 13 、 14、 15、 16、 17、 18、 20、 24 31 、 32 、 34 、 35 、 35 : 1 、 36 、 36 : 1 、 37 、 37 : 1 、40 、 42 、 43 、 53 、 55 、 60 、 61 、 62 、 63 、 65 、 73 、 74 、77 、 81 、 83 、 86 、 93 、 94 、 95 、 97 、 98 、 100 、 101 、 104、 106、 1〇8、 1〇9、 110、 113、 114、 115、 116、 117 ' 118、 119、 120、 123、 125、 126、 127、 128、 129、 137 、138' 139、 147、 148、 150、 151、 152、 153、 154、 155 ' 156、 161、 162、 164、 166、 167、 168、 169、 170、 171 、172、 173、 174、 175、 176、 177、 179、 180、 181、 182 、185、187、188、193、194、199、213、214 及 C.I.顏 料燈 2、5、13、16、17: 1、31、34、36、38、43、46 ' 48 、 49 、 51 、 52 、 55 、 59 、 60 、 61 、 62 、 64 、 71 、 73 等。 此等中較佳為C.I.顏料黃20、24、31、53、83、86 、93、94、1〇9、"〇、⑴、125、137、138、139、147 、148、150、153、154、166、173、180、185 等,更佳 為C·1.顏料黃l5〇、C.I.顏料黃185、C.I·顏料黃138、C.I. 顏料黃1 3 9。 特別是使用C.I.顏料黃150、C.I·顏料黃138、C.I. 顏料黃139時因穿透率高、對比高而較佳。 201219977 又,為形成藍色晝素,亦可對鹵化辞酞菁素顏料併 用紫色顏料。紫色顏料之實例有喹吖酮系紫色顏料、噁 嗓系紫色顏料、蒽酿系紫色顏料、散(i n d i g 〇 i d)系紫色顏 料、二笨并哌喃系紫色顏料等。 具體實例係有 C.I.顏料紫1、19、23、29、32、36 、38,特別是C.I.顏料紫23其穿透率高、對比高而較佳 〇 此等顏料的平均一次粒徑為1 〇nm〜40nm之範圍,係 因穿透率高、對比高而較佳。更佳為l〇nm〜30nm之範圍 〇 為將平均一次粒徑製成較小、較細微,則與齒化鋅 酞菁素顏料相同,鹽磨法係屬有效,可與鹵化鋅酞菁素 顏料一起進行鹽磨,亦可個別進行鹽磨。 平均一次粒徑可透過以SEM或TEM進行觀察,於 粒子未凝聚之部分量測1 00個粒子之尺寸並算出平均値 來求得。 本發明著色感光性組成物中,含有_化鋅献菁素顏 料之顏料的總量相對本發明著色感光性組成物中之溶劑 以外的總固體成分,以質量換算較佳為5〜60%,更佳為 10-50%,最佳為 15〜45%。 使用此範圍之添加量便可製得色特性優良、對比高 且輝度南的彩色濾、光片。 尚且,本發明中著色感光性樹脂組成物之「固體成 分」係包含溶劑以外之著色感光性組成物的全部成分。 £ -14- .201219977 <顏料分散組成物> 土奴調整本發明著色感光性組成物而併用多種顏料 車乂佳形態為預先將(A) _化鋅酞菁素顏料及其他顏料一 起或個別分散而製成顏料分散組成物。 / " 一 顏料刀政組成物係將前述顏料與溶劑分散,惟此 可視需求添加使用分散劑、樹脂等。 更且’其可使用顏料衍生物等,並視需求進一牛 用其他成分而構成。 乂使 -顏料分散組成物的調製_ 本發明之顏料分散組成物的調製形態並未特別限制 例如可藉由對顏料、顏料分散劑與溶劑使用縱型或俨 型石)研磨機(sand grinder mill) '釘式球磨機、滾剪機、 超音波分散機等,並以粒徑〇 〇1~lmm之玻璃、氧化梦 等形成之珠粒進行微分散處理來獲得。 在進行珠粒分散前,亦可使用二輥型輥、三輥型輕 球磨機、滾筒式研磨機、分散機、混練機、共混練機 、均質機、摻合機、單轴或雙軸之擠壓機等一面施加強 烈的兔切力’ 一面進行混練分散處理。 此外,關於混練、分散之詳細内容係已記載於 T.C.Patton 所著之「paint Flow and Pigment Dispersion 」(1964 年 ’ John Wiley and Sons 公司出版)等。 -顏料濃度- 顏料在顏料分散組成物中的含量相對該組成物之溶 劑以外的總固體成分,以質量換算較佳為1 〇〜6 〇質量% ’更佳為1 5〜5 0質量%。S -11 201219977 and / or desolvent addition _ #々, A ± batch or continuous drying, etc., for box dryer, belt & + ^ ',, 'c 刼 machine generally dry Each machine, He fog dryer, etc. The pulverization after drying and drying is not the operation for increasing the specific surface area -: the average particle diameter of human particles, but the dry welding such as selling, reducing machine, and belt dryer # 1 such as box drying... The twists and turns of the pigments are powdered and twisted (7): For example, mortar and pestle, key crusher, disc mill, needle ball mill:: grinding by a mill or the like. Spraying The (Α) zinc halide phthalocyanine pigment of the present invention can be obtained, for example, by using a general-flowing sputum-dispersing liquid dispersion product. (A) The zinc halide phthalocyanine Xinyan takes seven k 2a ear l Yancun bing's primary particle's coagulation is weak and weak, and it is easier to divide--, negative and easy to make thin cover force Large and contrasting color film. In the first month of the table, these zinc halide phthalocyanine pigments can be used alone or in combination with the stineration rate or gasification rate: all other painted zinc phthalocyanine pigments, in the "general" from other metals Substituted filled phthalocyanin or the like is used in combination. The bromine conversion rate and the chlorination rate are changed, and the color tone of the center material is changed, which may change. θ adds various colors of the reproduced hue, and other The color material and the color spectrum of the (eight)-color-sensitive photosensitive composition are increased. The coloring photosensitive group can be adjusted to have a transmittance. The zinc-based phthalocyanine can also be exemplified by In order to form a green alizarin pigment and use a yellow pigment or an orange pigment. 201219977 As an example of a yellow pigment, in addition to a diazo yellow pigment, an isoindole yellow pigment, a phthalocyanine yellow pigment, a benzoxanthin (benzimidaz〇1) 〇n) is a yellow pigment such as a yellow pigment or a nickel azo yellow pigment. In addition, it is also possible to use two kinds of yttrium-yellow-yellow orange pigments, peri η ο ne 糸; ^ A &#; shows orange pigments such as color pigments. , is C 丄 pigment yellow 1:1, 2, 3, 4 5 6 1 〇, 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 20 , 24 31 , 32 , 34 , 35 , 35 : 1, 36, 36 : 1 , 37 , 37 : 1 , 40 , 42 , 43 , 53 , 55 , 60 , 61 , 62 , 63 , 65 , 73 , 74 , 77 , 81 , 83 , 86 , 93 , 94 , 95, 97, 98, 100, 101, 104, 106, 1〇8, 1〇9, 110, 113, 114, 115, 116, 117 '118, 119, 120, 123, 125, 126, 127, 128 , 129, 137, 138' 139, 147, 148, 150, 151, 152, 153, 154, 155 '156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174 , 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 and CI pigment lamps 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46 '48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. Preferred among these are CI Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 1〇9, "〇, (1), 125, 137, 138, 139, 147, 148, 150, 153 154, 166, 173, 180, 185, etc., more preferably C·1. Pigment Yellow l5〇, CI Pigment Yellow 185, CI·Pig Yellow 138, CI Pigment Yellow 139. In particular, the use of C.I. Pigment Yellow 150, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139 is preferred because of high penetration and high contrast. 201219977 In addition, in order to form blue halogen, it is also possible to use a purple pigment for halogenated phthalocyanine pigment. Examples of the purple pigment include a quinacridone violet pigment, an anthraquinone violet pigment, a brewing violet pigment, a disperse (i n d i g 〇 i d) violet pigment, a dipyridamole violet pigment, and the like. Specific examples are CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, especially CI Pigment Violet 23, which has high penetration rate and high contrast, and the average primary particle size of these pigments is 1 〇. The range of nm to 40 nm is preferred because of high transmittance and high contrast. More preferably, the range of l〇nm~30nm is that the average primary particle diameter is made smaller and finer, and is the same as the toothed zinc phthalocyanine pigment. The salt milling method is effective and can be combined with the zinc halide phthalocyanine pigment. Salt grinding is carried out together, and salt milling can also be carried out separately. The average primary particle diameter can be obtained by observing by SEM or TEM, measuring the size of 100 particles in the non-agglomerated portion of the particles, and calculating the average enthalpy. In the coloring photosensitive composition of the present invention, the total amount of the pigment containing the zinc-containing phthalocyanine pigment is preferably 5 to 60% by mass, based on the total solid content of the solvent in the coloring photosensitive composition of the present invention. More preferably, it is 10-50%, and the best is 15 to 45%. By using the addition amount in this range, a color filter and a light sheet having excellent color characteristics, high contrast, and high luminance can be obtained. Further, the "solid component" of the colored photosensitive resin composition of the present invention contains all the components of the colored photosensitive composition other than the solvent. £-14-.201219977 <Pigment Dispersion Composition> The earth color adjustment of the coloring photosensitive composition of the present invention and the use of a plurality of pigments in a preferred form are (A) _ zinc phthalocyanine pigment and other pigments together or individually Dispersed to form a pigment dispersion composition. / " A pigment knife composition disperses the above pigments and solvents, but dispersants, resins, etc. may be added as needed. Further, it is possible to use a pigment derivative or the like, and it is formed by using other components as needed. Modification of the pigment-dispersed composition of the present invention - The preparation form of the pigment dispersion composition of the present invention is not particularly limited, for example, by using a vertical or stellite stone for a pigment, a pigment dispersant, and a solvent (sand grinder mill) ) 'Nail ball mill, rolling shear, ultrasonic disperser, etc., and obtained by microdispersion treatment of beads formed of glass having a particle diameter of 1-1 mm, oxidized dreams, and the like. Before the bead dispersion, a two-roll type roll, a three-roll type light ball mill, a drum type grinder, a dispersing machine, a kneading machine, a blending machine, a homogenizer, a blending machine, a single shaft or a double shaft may be used. A strong rabbit shear force is applied to one side of the press, and the mixing and dispersing treatment is performed. In addition, the details of the kneading and dispersion are described in "Paint Flow and Pigment Dispersion" by T.C. Patton (published by John Wiley and Sons in 1964). - Pigment Concentration - The content of the pigment in the pigment dispersion composition is preferably from 1 〇 to 6 〇% by mass, more preferably from 1 5 to 50% by mass, based on the total solid content of the solvent of the composition.
S -15- 201219977 "顏料之含量若處於前述範圍β,則於色濃度充足, 並可確保優良之色特性方面係屬有效。 -分散劑- 顏料分散組成物係含有分散劑的至少丨種。 由於含有該分散劑,故可提高顏料之分散性。 分散劑可適當選擇例如週知之顏料分散劑、界面活 性劑而使用》 具體而言,可使用多種化合物,可列舉例如有機矽 氧烷聚合物ΚΡ341(信越化學工業(股)製)、(曱基)丙烯酸 系(共)聚合物 Polyflow Νο·75、Νο.90、ν〇.95(以上為共 榮社化學工業(股)製)、W001(裕商(股)製)等陽離子系界 面活性劑;聚氧乙烯月桂醚、硬脂酸聚氧乙烯醚、油酸 聚氧乙烯醚、聚氧乙烯辛基苯醚、聚氧乙烯壬基苯醚' 聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、山梨醇酐 脂肪酸酯等陰離子系界面活性劑;W 0 0 4、W 0 0 5、W 0 1 7 ( 以上為裕商(股)製)等非離子系界面活性劑;具有叛基甜 菜鹼構造、胺基甜菜鹼構造、磺基甜菜鹼構造、羥基甜 菜驗構造等的兩性界面活性劑;Μ E G A F A C F 1 7 1、F 1 7 2 ,F173(以上為DIC(股)製)等氟系界面活性劑;EFKA-46 、EF K A - 4 7、EF K A-4 7 E A、EFK A Polymer 100、EFKA Polymer 400、EFKA Polymer 401、EFKA Polymer 450( 以上為 Ciba Speciality Chemicals 公司製)、分散 Aid6 、分散 Aid8、分散 Aidl5、分散 Aid9100(以上為SAN NOPCO公司製)等高分子分散劑;Solsperse 3000、5000 、9000 ' 12000 ' 13240 > 13940 ' 17000、24000、26000 -16 - 201219977 、28000等各種Solsperse分散劑(以上為曰本Lubrizol( 股)製);Adeka Pluronic L31、F3 8、L42、L44、L61、L64 、F68 、 L72 、 P95 、 F77 、 P84 、 F87 、 P94 、 L101 、 P103 、F108、L121、P-123(以上為旭電化(股)製)及ISONET S-20(三洋化成(股)製)、Disperbyk 101、103、106、108 、109、 111、 112、 116 、 130 、 140 、 142、 162、 163 、 164 、166 、 167 、 170 、 171 、 174 ' 176 > 180 、 182 、 2000 、 2001、2050、2150(以上為 BYK(股)製)。 其他可例舉丙烯酸系共聚合物、分子末端或側鏈上 具有N,N-二取代胺基或酸性基團等極性基團之低聚物或 聚合物、以三級胺改性之聚胺基曱酸酯樹脂、日本特開 2009-52010號公報所記載之AB型、ΑΒΑ型嵌段共聚合 物等。 分散劑在顏料分散組成物中的含量相對顏料的總質 量’較佳為1〜1 0 0質量% ’更佳為3〜7 〇質量%。 -顏料衍生物- 顏料分散組成物可視需求添加顏料衍生物。 使與分散劑具親和性之部分、或導入有極性基團之 顏料衍生物吸附於顏料表面,並將其作為分散劑的吸附 點使用,由此便可使顏料以細微粒子形式分散於著色感 光性組成物中並防止其再次凝聚’對構成對比高、透明 性優良之彩色濾光片而言係屬有效。 顏料衍生物具體而言係為以有機宛社& β械顋枓為母體骨架, 並於側鏈上導入有酸性基團、鹼性基團、— 八 方杳基團作為 取代基之化合物。S -15- 201219977 " If the content of the pigment is in the aforementioned range β, it is effective in terms of sufficient color density and ensuring excellent color characteristics. - Dispersant - The pigment dispersion composition contains at least a seed of a dispersant. Since the dispersant is contained, the dispersibility of the pigment can be improved. The dispersing agent can be appropriately selected, for example, by using a known pigment dispersing agent or a surfactant. Specifically, a plurality of compounds can be used, and examples thereof include an organic siloxane polymer ΚΡ 341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Acrylic (co)polymers Polyflow Νο·75, Νο.90, ν〇.95 (above is Kyoritsu Chemical Industry Co., Ltd.), W001 (Yushang (manufacturing)) and other cationic surfactants Polyoxyethylene lauryl ether, stearic acid polyoxyethylene ether, oleic acid polyoxyethylene ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether' polyethylene glycol dilaurate, polyethylene Anionic surfactants such as alcohol distearate and sorbitan fatty acid ester; nonionic interfacial surfactants such as W 0 0 4, W 0 0 5, and W 0 1 7 (the above are manufactured by Yushang Co., Ltd.) An amphoteric surfactant having a tetrandrine structure, an aminobetaine structure, a sulfobetaine structure, a hydroxy beet structure, etc.; Μ EGAFACF 1 7 1 , F 1 7 2 , F173 (above DIC) ))) Fluorine-based surfactants; EFKA-46, EF KA - 4 7, EF KA -4 7 EA, EFK A Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (above, Ciba Speciality Chemicals), dispersed Aid6, dispersed Aid8, dispersed Aidl5, dispersed Aid9100 (above, manufactured by SAN NOPCO Co., Ltd.) Polymer dispersant; Solsperse 3000, 5000, 9000 ' 12000 ' 13240 > 13940 ' 17000, 24000, 26000 -16 - 201219977, 28000 and other Solsperse dispersants (above is 曰本Lubrizol (share)); Adeka Pluronic L31, F3 8, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above is Solectron) and ISONET S-20 (Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174 ' 176 > 180, 182, 2000, 2001, 2050, 2150 (above is BYK (share) system). Other examples thereof include an acrylic copolymer, an oligomer or a polymer having a polar group such as an N,N-disubstituted amino group or an acidic group at a molecular terminal or a side chain, and a polyamine modified with a tertiary amine. The phthalic acid ester resin, the AB type, the fluorene type block copolymer described in JP-A-2009-52010, and the like. The content of the dispersant in the pigment dispersion composition is preferably from 1 to 100% by mass, more preferably from 3 to 7 % by mass, based on the total mass of the pigment. - Pigment Derivative - The pigment dispersion composition may be added with a pigment derivative as needed. The portion having affinity with the dispersing agent or the pigment derivative into which the polar group is introduced is adsorbed on the surface of the pigment and used as a point of adsorption of the dispersing agent, whereby the pigment is dispersed in the form of fine particles in the coloring photosensitive It is also effective in the color filter which is excellent in contrast and high in transparency. Specifically, the pigment derivative is a compound in which an organic group and an oxime group are used as a matrix, and an acidic group, a basic group, and an octagonal group are introduced as a substituent on the side chain.
S -17- 201219977 料二機顏料具體上可列舉彻系顏 ::素糸顏料、偶氮系顏料、啥琳黃系顏料…丨 °木糸顏枓、異°引°朵酮系顏料,顏料、二酮吼… 洛顏=苯并㈣酮顏料等…般未被稱為色素的萘系 二二“、三氣雜笨系,系等淡黃色芳香族多環化 合物亦包含在内。 顏料衍生物可使用日本特開平 々刊開十1 1-49974號公報、日 本特開平1 1- 1 89732號公報、曰太牲Μ τ , m 9本特開平10-245501號 公報、日本特開2006_265528號公報、日本特開平 8-2958 10號公報、日本特開平u_199796號公報、日本 特開2005-234478號公報、日本特開2〇〇3_24〇93 8號公 報、曰本特開2001-3562 10號公報等所記載者。 顏料衍生物在顏料分散組成物中的含量相對顏料的 總質量,較佳為1〜30質量%,更佳為3〜2〇質量%。 顏料衍生物之含量若處於此範圍内時,可壓低顏料 分散組成物之黏度並可良好地進行分散,同時可提升分 散後的分散穩定性。 由此便可製得穿透率高且具有優良色特性的著色感 光性組成物,因此將該著色感光性組成物應用於例如彩 色渡光片之製作用途時,可製得具有良好色特性且對比 高的彩色渡光片。 又,顏料分散組成物中亦可進一步添加後述鹼可溶 性樹脂等高分子化合物等。 兹認為鹼可溶性樹脂所含之酸基等極性基團亦有助 於顏料的分散’且對顏料分散液之分散穩定性而言大多 係屬有效。 -18- 201219977 -溶劑_ 顏料分散組成物中的溶劑只要是一般顏料分散性組 成物所使用的有機溶劑則未特別限定。 可列舉例如乙酸-1 -甲氧基-2-丙酯、1 -曱氧基-2-丙醇 、乙二醇單甲醚、二乙二醇單甲醚、乙酸乙酯、乙酸丁 酉旨、乳酸乙酯、丙酮、曱乙酮、甲基異丁基酮、環己酮 、正丙醇、2 -丙醇、正丁醇、環己醇、乙二醇、二乙二 醇、曱苯、二曱苯等溶劑,為調整熔點、黏度、顏料之 分散性,則此等當中亦可多種併用。 又,亦可使用調製後述著色感光性組成物時所使用 的(F)溶劑。 顏料分散組成物中的溶劑之含量可視顏料分散組成 物的用途等來適當選擇。 • 當將顏料分散組成物用於調製後述著色感光性組成 物時,由操作性觀點而言,顏料與顏料分散劑的總和相 對顏料分散組成物之溶劑以外的總質量,可含有5〜50質 量%。 本發明著色感光性組成物中的顏料分散組成物之含 量相對著色感光性組成物之溶劑以外的總固體成分之質 量,顏料之含量較佳為5〜7 0質量%之範圍的量,更佳為 15〜60質量%之範圍的量。 顏料分散組成物之含量若處於前述範圍内,於色濃 度充足,並可確保優良之色特性方面係屬有效。 本發明著色感光性組成物之(A)鹵化鋅酞菁素顏料 除上述顏料外,亦可併用染料。藉由併用染料,便可望 提升彩色濾光片的對比。 -19- 201219977 本發明著色感光性組成物所使用的染料只要是可溶 於有機溶劑之染料則未特別限定,惟,若以化學構造加 以區分,則可列舉偶氮系染料、蒽醌系染料、酞菁素系 染料、喹啉亞胺系染料、喹啉系染料、硝基系染料、羰 基系染料、次曱基系染料及此等之衍生物等。 偶氮系染料可列舉例如C.I.酸性黃1 1、C.I.酸性橙7 、C.I.酸性紅37、C.I.酸性紅180、C.I.酸性藍29、C.I. 直接紅28、C.I.直接紅83、C.I.直接黃12、C.I.直接橙 26、C.I·直接綠28、C.I.直接綠59、C.I·活性黃2、C.I. 活性紅17、C.I.活性紅120、C.I.分散橙5、C.I.分散紅 5 8、C · I ·分散藍 1 6 5、C. I.鹼性藍 4 1、C. I.鹼性紅 1 8、C. I. 媒介紅7、C. I.媒介黃5等。 蒽醌系染料可列舉例如C.I.甕藍4、C.I.酸性藍40 、C.I.酸性綠25、C.I.活性藍19、C.I.活性藍49、C.I.分 散紅60、C.I.分散藍56、C.I.分散藍60等。 其他,酞菁素系染料可列舉例如C.I.甕藍5等,喹 啉亞胺系染料可列舉例如C.I.鹼性藍3、C.I.鹼性藍9等 ,喹啉系染料可列舉例如 C.I.溶劑黃33、C.I.酸性黃3 、C.L分散黃64等,硝基系染料則可列舉例如C.I.酸性 黃1、C.I.酸性橙3、C.I.分散黃42等。 % <(B)具有酸基之聚合性單體> 本發明著色感光性組成物中係含有至少一種以上 (B)具有酸基之聚合性單體作為硬化性成分。 使用構造中具有酸基之聚合性單體由於可促進未曝 光部的顯影,故可大幅度改良顯影寬容度。其中,具有S -17- 201219977 The pigments of the second machine can be listed as follows: 糸 糸 pigment, azo pigment, 啥 黄 黄 丨 丨 丨 丨 糸 糸 糸 枓 枓 枓 枓 枓 枓 枓 枓 枓 枓, Diketone oxime... Luoyan = benzo (tetra) ketone pigments, etc., such as naphthalene-based di-n-, "three-gas heteropoly", which are not called pigments, are also included in light yellow aromatic polycyclic compounds. The article can be published in Japanese Unexamined Patent Publication No. Hei. No. 1-1-49974, Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei 8-2958 No. 10, Japanese Patent Application Laid-Open No. Hei No. Hei. No. 2005-234478, Japanese Patent Laid-Open No. Hei No. 2005-234478, Japanese Patent Laid-Open No. Hei. The content of the pigment derivative in the pigment dispersion composition is preferably from 1 to 30% by mass, more preferably from 3 to 2% by mass, based on the total mass of the pigment. The content of the pigment derivative is in this case. In the range, the viscosity of the pigment dispersion composition can be lowered and dispersed well At the same time, the dispersion stability after dispersion can be improved. Thus, a colored photosensitive composition having high transmittance and excellent color characteristics can be obtained, and thus the colored photosensitive composition can be applied to, for example, a color light-emitting sheet. In the case of the pigment dispersion composition, a polymer compound such as an alkali-soluble resin to be described later may be further added. The acid group contained in the alkali-soluble resin is considered to be the same. The polar group also contributes to the dispersion of the pigment and is mostly effective for the dispersion stability of the pigment dispersion. -18- 201219977 - Solvent_ The solvent in the pigment dispersion composition is generally a pigment dispersion composition. The organic solvent to be used is not particularly limited, and examples thereof include 1-methoxy-2-propyl acetate, 1-nonoxy-2-propanol, ethylene glycol monomethyl ether, and diethylene glycol monomethyl ether. , ethyl acetate, butyl acetate, ethyl lactate, acetone, ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol , diethylene glycol, benzene, two In order to adjust the melting point, the viscosity, and the dispersibility of the pigment, a solvent such as benzene may be used in combination with the above-mentioned (F) solvent used for preparing the coloring photosensitive composition described later. The content of the solvent can be appropriately selected depending on the use of the pigment dispersion composition, etc. • When the pigment dispersion composition is used to prepare a coloring photosensitive composition described later, the total of the pigment and the pigment dispersant is relative to the pigment from the viewpoint of workability. The total mass of the component other than the solvent of the dispersion composition may be 5 to 50% by mass. The content of the pigment dispersion composition in the coloring photosensitive composition of the present invention is relative to the mass of the total solid component other than the solvent of the coloring photosensitive composition, pigment The content is preferably in the range of 5 to 70% by mass, more preferably in the range of 15 to 60% by mass. When the content of the pigment dispersion composition is within the above range, it is effective in that the color density is sufficient and the color characteristics are ensured. (A) Zinc Halide Phthalocyanine Pigment of the Colored Photosensitive Composition of the Present Invention In addition to the above pigments, a dye may be used in combination. By using a dye together, it is possible to enhance the contrast of the color filters. -19-201219977 The dye used in the coloring photosensitive composition of the present invention is not particularly limited as long as it is a dye soluble in an organic solvent, and examples thereof include an azo dye or an anthraquinone dye. A phthalocyanine dye, a quinolineimine dye, a quinoline dye, a nitro dye, a carbonyl dye, a fluorene dye, and the like. Examples of the azo dye include CI Acid Yellow 1 1 , CI Acid Orange 7 , CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, and CI Direct Orange 26, CI·Direct Green 28, CI Direct Green 59, CI·Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Disperse Orange 5, CI Disperse Red 5 8 , C · I · Disperse Blue 1 6 5 , CI alkaline blue 4 1, CI alkaline red 18, CI medium red 7, CI medium yellow 5 and so on. Examples of the lanthanide dyes include C.I. Indigo 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Disperse Blue 60 and the like. Other examples of the phthalocyanine-based dyes include CI Indigo 5, and the quinoline-imine dyes include, for example, CI Basic Blue 3 and CI Basic Blue 9, and the quinoline-based dyes include, for example, CI Solvent Yellow 33. CI Acid Yellow 3, CL Disperse Yellow 64, etc., and examples of the nitro dye include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42. % < (B) Polymerizable monomer having an acid group> The colored photosensitive composition of the present invention contains at least one or more (B) polymerizable monomer having an acid group as a curable component. The use of a polymerizable monomer having an acid group in the structure promotes development of the unexposed portion, so that the development latitude can be greatly improved. Among them, having
S -20- 201219977 羧基、酚性羥基、磺酸基、磷酸基等酸基的聚合性單體 由於可提高鹼溶解性,並大大地有助於顯影性的提升及 殘留物的抑制而特佳。除後述(c)黏著劑樹脂之驗可溶性 賦予效果以外’再透過使用具有酸基之聚合性單體的效 果’在增南顏料濃度藉以提升輝度的著色樹脂組成物中 亦可使顯影寬容度更寬廣,而能夠製造穩定的彩色渡光 含有缓基之聚合性單體除丙稀酸、曱基丙烯酸、鄰 苯二甲酸、富馬酸、馬來酸、衣康酸、巴豆酸、肉桂酸 等不飽和脂肪酸之外,還可例舉經羧基改性之多官能丙 烯酸酯化合物。經羧基改性之多官能丙烯酸酯化合物可 例舉琥ίό酸改性新戊四醇三丙烯酸酯、琥珀酸改性三經 甲基丙烧二丙烯酸g旨、玻拍酸改性新戊四醇四丙稀酸酯 、琥珀酸改性二新戊四醇五丙烯酸酯、琥珀酸改性二新 戊四醇六丙烯酸酯、己二酸改性新戊四醇三丙烯酸酯、 己一酸改性三羥甲基丙烷三丙烯酸酯、己二酸改性新戊 四醇四丙烯酸酯、己二酸改性二新戊四醇五丙烯酸酯、 己二酸改性二新戊四醇四丙烯酸酯等,可適合使用 ARONIX M-510、ARONIX M-520、ARONIX TO-2349、 ARONIX τ〇-23 5 9(以上為東亞合成(股)製)等市售化合物 〇 含有盼性羥基之聚合性單體可例舉對羥基苯乙烯、 3’4 一 I基苯乙烯、3,5 -二羥基苯乙烯、2,4,6 -三羥基苯 乙烯、(對羥基)苯曱基丙烯酸酯、水楊酸改性新戊四醇 三丙烯酸酯、水楊酸改性三羥甲基丙烷三丙烯酸酯、水S -20- 201219977 A polymerizable monomer such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group or a phosphoric acid group is preferable because it can improve alkali solubility and greatly contribute to improvement in developability and suppression of residues. . In addition to the effect of the solubility-imparting effect of the adhesive resin described later, the effect of 're-passing the polymerizable monomer having an acid group' can also improve the development latitude in the coloring resin composition by which the pigment density is increased. Wide, and capable of producing stable color light-transmissive polymerizable monomers containing a buffer base, such as acrylic acid, mercaptoacrylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, etc. In addition to the unsaturated fatty acid, a polyfunctional acrylate compound modified with a carboxyl group can also be exemplified. The carboxyl group-modified polyfunctional acrylate compound may, for example, be a succinic acid-modified neopentyl alcohol triacrylate, a succinic acid-modified tris-methylpropane-succinic acid, or a glass-acid-modified neopentyl alcohol. Tetraacrylate, succinic acid modified dipentaerythritol pentaacrylate, succinic acid modified dipentaerythritol hexaacrylate, adipic acid modified neopentyl alcohol triacrylate, hexamic acid modification Trimethylolpropane triacrylate, adipic acid modified neopentyl alcohol tetraacrylate, adipic acid modified dipentaerythritol pentaacrylate, adipic acid modified dipentaerythritol tetraacrylate, etc. It is suitable for use as a commercially available compound such as ARONIX M-510, ARONIX M-520, ARONIX TO-2349, ARONIX τ〇-23 5 9 (above, East Asia Synthetic Co., Ltd.), and a polymerizable monomer having a desired hydroxyl group. Preferable examples are p-hydroxystyrene, 3'4-monostyrene, 3,5-dihydroxystyrene, 2,4,6-trihydroxystyrene, (p-hydroxy)phenyl acrylate, salicylic acid Modified pentaerythritol triacrylate, salicylic acid modified trimethylolpropane triacrylate, water
-21- S 201219977 楊酸改性新戊四醇四丙烯酸s旨、水楊酸改性二新戊四醇 五丙烯酸酯、水.楊酸改性二新戊四醇六丙烯酸酯等,較 佳者為水楊酸改性二新戊四醇六丙烯酸酯、水楊酸改性 二新戊四醇五丙烯酸酯。 含有磺酸基之聚合性單體係有乙烯基磺酸、烯丙基 磺酸、苯乙烯磺酸、丁基磺酸改性丙烯醯胺等。含有磷 酸基之聚合性單體可列舉乙烯基磷酸、苯乙烯磷酸、丁 基磷酸改性丙烯醯胺等。此等當中較佳者為丁基磺酸改 性丙烯醯胺,其市售化合物係有ATB S (東亞合成(股)製) 〇 此等具有酸基之聚合性單體當中,由製造適合度及 成本觀點而言較佳為具有羧基之聚合性單體、具有酚性 羥基之聚合性單體,更佳為具有羧基之聚合性單體。 本發明著色感光性組成物中,可將具有酸基之聚合 性單體作為聚合性單體單獨使用,亦可併用多種具有酸 基之聚合性單體,又可分別併用1種以上的含有酸基之 聚合性單體與未具有酸基之聚合性單體。為兼具耐溶劑 性、ITO濺鍍適合度與顯影寬容度,則較佳為除具有酸 基之聚合性單體以外,亦併用未具有酸基之聚合性單體 而使用。 (未具有酸基之聚合性單體) 本發明中可與具有酸基之聚合性單體併用的未具有 酸基之聚合性單體只要可進行聚合則未特別限制,可適 合使用具有至少1個乙烯性雙鍵的低分子化合物、二聚 體、三聚體、低聚物等可進行加成聚合之化合物。-21- S 201219977 Salicylic acid modified neopentyl alcohol tetraacrylic acid s, salicylic acid modified dine pentaerythritol pentaacrylate, water, salicylic acid modified dipentaerythritol hexaacrylate, etc., preferably It is salicylic acid modified dinonpentaerythritol hexaacrylate and salicylic acid modified dine pentaerythritol pentaacrylate. The polymerizable single system containing a sulfonic acid group is vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, butylsulfonic acid modified acrylamide or the like. Examples of the polymerizable monomer containing a phosphoric acid group include vinyl phosphoric acid, styrene phosphoric acid, and butylphosphoric acid-modified acrylamide. Preferred among these are butyl sulfonic acid-modified acrylamide, and a commercially available compound thereof is ATB S (manufactured by Toago Corporation Co., Ltd.), among which polymerizable monomers having an acid group are manufactured by suitability. From the viewpoint of cost, a polymerizable monomer having a carboxyl group, a polymerizable monomer having a phenolic hydroxyl group, and more preferably a polymerizable monomer having a carboxyl group is preferable. In the colored photosensitive composition of the present invention, a polymerizable monomer having an acid group may be used alone as a polymerizable monomer, or a plurality of polymerizable monomers having an acid group may be used in combination, and one or more kinds of acid-containing monomers may be used in combination. A polymerizable monomer based on a polymerizable monomer having no acid group. In order to have both solvent resistance, ITO sputtering suitability and development latitude, it is preferred to use a polymerizable monomer having no acid group in combination with a polymerizable monomer having an acid group. (Polymerizable monomer having no acid group) The polymerizable monomer having no acid group in combination with the polymerizable monomer having an acid group in the present invention is not particularly limited as long as it can be polymerized, and it can be suitably used to have at least 1 A compound capable of undergoing addition polymerization, such as a low molecular weight compound, a dimer, a trimer or an oligomer of an ethylenic double bond.
S -22- .201219977 乙烯性化合物可列舉例如不飽和羧酸與單經基化合 物形成的酯、脂肪族聚羥基化合物與不飽和緩酸形成的 酯、芳香族聚羥基化合物與不飽和羧酸形成的醋、不飽 和羧酸與多元羧酸及前述脂肪酸聚羥基化合物、芳香族 聚羥基化合物等多元羥基化合物經酯化反應所得的s旨、 聚異氰酸酯化合物與含有(甲基)丙烯醯基之羥基化合物 反應所得之具有胺基甲酸酯骨架的乙烯性化合物等。 具體聚合性單體可如以下所示,依1分子中的聚合 性基團數來分類而舉例,惟非限於此。 (1) 1分子中具有1個聚合性基團之化合物 1分子_具有1個聚合性基團之化合物的實例可列 舉例如(曱基)丙烯酸己酯、(甲基)丙烯酸2_乙基己酯、( 曱基)丙烯酸硬脂醯酯、(曱基)丙烯酸環己酯、(曱基)丙 烯酸4-正丁基環己酯、(甲基)丙烯酸冰片酯、(曱基)丙烯 酸異冰片酯、(曱基)丙烯酸苯曱酯、2_乙基己二醇(甲基) 丙締酸酯 '(曱基)丙烯酸丁氧乙酯、(曱基)丙烯酸入氣乙 酯、(甲基)丙烯酸氰基乙酯、(甲基)丙烯酸3甲氧基丁酯 2-(2-甲氧基乙氧基)乙基(甲基)丙烯酸酯、2,2,入四氟 乙基(甲基)丙烯酸醋、1H,1H,2H,2H全氟癸基(曱基) 敲s曰 ' (甲基)丙烯酸苯酯、2,4,5_四甲基苯基(甲基)内 馱S曰、(甲基)丙烯酸4·氯笨酯、(甲基)丙烯酸苯氧曱酯 \甲基)丙烯酸縮水甘油醋、(f基)丙烯酸縮水甘油氧基曰丁' 酯、(甲基)丙烯酸縮水甘油氧基乙醋、(曱基)丙烯 =乙§曰、(甲基)丙烯酸3_羥丙酯、(甲基)丙烯酸2、羥丙 酯、(甲基)丙烯酸2-羥丁能、(曱基)丙烯酸4_羥丁^、(S -22-.201219977 The ethylenic compound may, for example, be an ester of an unsaturated carboxylic acid with a mono-based compound, an ester of an aliphatic polyhydroxy compound with an unsaturated buffer acid, an aromatic polyhydroxy compound and an unsaturated carboxylic acid. The vinegar, the unsaturated carboxylic acid and the polyvalent carboxylic acid, and the polyhydroxy compound such as the fatty acid polyhydroxy compound or the aromatic polyhydroxy compound are esterified, and the polyisocyanate compound and the (meth)acryloyl group-containing hydroxyl group are obtained. An ethylenic compound having a urethane skeleton obtained by the reaction of the compound or the like. The specific polymerizable monomer can be exemplified by classification based on the number of polymerizable groups in one molecule, as shown below, but is not limited thereto. (1) Compound 1 having one polymerizable group in one molecule - Examples of the compound having one polymerizable group may, for example, be hexyl acrylate or 2-ethyl methacrylate Ester, stearyl phthalate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, borneol (meth) acrylate, isobornyl (mercapto) acrylate Ester, phenyl fluorenyl (mercapto) acrylate, 2-ethylhexyl diol (methyl) propionate (butoxy) butoxyethyl (meth) acrylate, ethyl (meth) acrylate, (methyl) ) cyanoethyl acrylate, 3 methoxybutyl (meth) acrylate 2-(2-methoxyethoxy) ethyl (meth) acrylate, 2, 2, tetrafluoroethyl (A) Acrylic vinegar, 1H, 1H, 2H, 2H perfluorodecyl (fluorenyl) knocked s曰' phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (methyl) yttrium曰, (meth)acrylic acid 4·chloropropionate, phenoxy methacrylate (methyl methacrylate) glycidyl vinegar, (f-) glycidyl oxy butyl acrylate, (methyl) Glycidyloxyacetate, (mercapto) propylene = ethyl hydrazine, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyrate (meth) acrylate , (fluorenyl) acrylic acid 4_hydroxybutyl ^, (
-23- '' S 201219977 甲基)丙稀酸3-經兩酯、聚環氧乙烷單甲醚(甲基)丙烯酸 g旨、寡環氧乙燒單笮醚(尹基)丙烯酸酯、聚環氧乙烷(f 基)丙烯酸酯、寡環氧乙烷(甲基)丙烯酸酯、(甲基)丙烯 酉义2-沒基-3 -笨氧丙酯、E〇改性酚(甲基)丙烯酸酯、E〇 改性甲酚(甲基)丙烯酸酯、E〇改性壬基酚(甲基)丙烯酸 醋、PO改性壬基酚(甲基)丙烯酸酯、E〇改性_2_乙基己 基(曱基)丙婦酸酯等。 (2) 1分子中具有2個聚合性基團之化合物 1分子令具有2個聚合性基團之化合物的實例可列 舉同一分子内具有2個(甲基)丙烯醯基作為聚合性基團 之化合物,例如乙二醇二(甲基)丙烯酸酯、二乙二醇二( 曱基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯 '聚乙二醇 一(甲基)丙烯酸酯、丨,3-丁二醇二(曱基)丙烯酸醋、1 4-丁一酉子一(甲基)丙烯酸酯、丨,6-己二醇二(甲基)丙烯酸酯 、新戊一醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯 L 一丙一醇二(甲基)丙烯酸醋、三丙二醇二(甲基)丙烯酸 酉曰聚丙二醇二(甲基)丙烯酸酯、2-羥基-1,3-二丙烯醯 氧丙烷、2,2-雙[4-(丙烯醯氧乙氧基)苯基]丙烷、2,2-雙 ^•(丙烯醯氧二乙氧基)苯基]丙烷、雙酚A之雙(丙烯= 氧乙基)醚、雙酚A型環氧樹脂之(曱基)丙烯酸改性物、 3甲基戊二醇二(甲基)丙烯酸酯、2羥基_3_丙烯醯氧丙 =甲基:烯酸酯、二羥曱基-三環癸烷二(甲基)丙烯酸酯 彳為一故曱基_二環癸烧一(曱基)丙稀酸酯、新戊 醇一(甲基)丙烯酸酯、乙氧基化雙酚A二(曱基)丙烯 又紛A型環氧樹脂之(曱基)丙婦酸改性物等。-23- '' S 201219977 methyl) acrylic acid 3-transester, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene bromide (yin) acrylate, Polyethylene oxide (f-) acrylate, oligo-oxirane (meth) acrylate, (meth) propylene oxime 2-diyl-3 - oxypropyl ester, E 〇 modified phenol (A Acrylate, E 〇 modified cresol (meth) acrylate, E 〇 modified nonyl phenol (meth) acrylate, PO modified nonyl phenol (meth) acrylate, E 〇 modification _ 2-ethylhexyl (indenyl) propionate or the like. (2) Compound 1 having two polymerizable groups in one molecule. Examples of the compound having two polymerizable groups may be exemplified by having two (meth)acryl fluorenyl groups in the same molecule as a polymerizable group. a compound such as ethylene glycol di(meth)acrylate, diethylene glycol di(decyl)acrylate, triethylene glycol di(meth)acrylate 'polyethylene glycol mono(meth)acrylate,丨, 3-butanediol bis(indenyl) acrylate vinegar, 1 4-butan oxime-(meth) acrylate, hydrazine, 6-hexanediol di(meth) acrylate, neopentyl alcohol II (a) Acrylate, propylene glycol di(meth)acrylate L-propanol di(meth)acrylic acid vinegar, tripropylene glycol di(meth)acrylic acid 酉曰polypropylene glycol di(meth)acrylate, 2-hydroxy- 1,3-Dipropylenepropoxypropane, 2,2-bis[4-(acryloxyethoxy)phenyl]propane, 2,2-bis(•(propyleneoxydiethoxy)phenyl] Propane, bisphenol A bis (propylene = oxyethyl) ether, bisphenol A epoxy resin (fluorenyl) acrylic acid modified, 3 methyl pentanediol di (A) Acrylate, 2 hydroxy_3_ propylene oxime = methyl: enoate, dihydroxy decyl-tricyclodecane di(meth) acrylate 彳 一 _ _ 二 二 二 二Alkyl acrylate, neopentyl alcohol mono(meth) acrylate, ethoxylated bisphenol A bis(indenyl) propylene and a type A epoxy resin Wait.
S -24- 201219977 (3) 1分子中具有3個聚合性基團之化合物 刀子中具有3個聚合性基團之化合物的實例可列舉 例如三羥甲基丙烷三(曱基)丙烯酸酯、三羥甲基乙烷三( 甲基)丙烯酸酯、三羥甲基丙烷之環氧烷改性三(甲基)丙 烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇三(曱 基)丙烯酸酯、三羥甲基丙烷三((甲基)丙烯醯氧丙基)醚、 異三聚氰酸環氧烷改性三(甲基)丙烯酸酯、丙酸二新戊四 醇三(甲基)丙稀酸醋、三((曱基)丙烯醯氧乙基)異三聚氰 酸酯、羥基三甲基乙醛改性二羥甲基丙烷三(甲基)丙烯酸 酯、山梨醇三(甲基)丙稀酸醋、丙氧基化三經甲基丙炫三 (甲基)丙烯酸醋、乙氧基化甘油三丙烯酸酯等。 (4) 1分子中具有4個以上聚合性基團之化合物 1刀子十具有4個以上聚合性基團之化合物可列舉 例如新戊四醇四(甲基)丙烯酸醋、山梨醇四(甲基)丙烯酸 酯、二三羥曱基丙烷四(甲基)丙烯酸酯、丙酸二新戊四 醇四(甲基)丙烯g文g日、乙氧基化新戊四醇四(甲基)丙烯酸 醋、二新戊四醇五(甲基)丙稀酸酉旨、二新戍四醇六(甲基) 丙烯酸醋、山梨醇五(甲基)丙稀酸酷、山梨醇六(曱基) 丙稀酸醋、偶磷氮(phosphazene)之環氧烧改性六(甲基) 丙烯酸酯、己内酯改性-热士、m t 注一新戍四醇六(甲基)丙烯酸酯、 共榮社化學(股)製UA_306h、Ua_3〇6t'ua福工等胺基 曱酸酯丙烯酸酯。 此等田巾由適當保持溶劑耐性、IT。$賤鑛適合度 之觀點而言,較佳為同—分子内具有2個以上(甲基)丙 烯醯基之(甲基)丙烯酸醋單體’更佳為具有3個以上(甲 基)丙烯醯基之(甲基)丙烯酸酯單體。 201219977 特別是具有4個以上(甲基) 酸醋單體係屬有利,例如 基之(甲基)丙烯 戊 醇 > 斤戊醇五丙烯酸酯、二新 戍四知,、丙~酸i日以溶劑耐性 言較佳,可適合使用此等 '鍍適合度觀點而 二新戍四醇五丙稀酸質!換算之混合比例為 8〜6)之混合物。 ’四醇,、丙烯酸酷=2〜4 : 當併用具有酸基之聚合性 性單體時’若設具有酸基之聚::::具有酸基之聚合 聚合性單體的總和為1 〇〇所1 ±早肢與未具有酸基之 量份之範圍併用具有酸基之則較佳為以1〜50質 量份之範圍’再更佳為5〜2〇Y旦早體」更佳為1〜40質 本發明*色感光性纽成貝里”之乾圍。 性單體與未具有酸基之聚合性單體η:基,聚合 較佳含量相對著色感光性-仵之聚合性早體的 分,較佳為5〜8〇質量%,更 之溶劑以外的總固體成 為15〜50質量%之範圍。佳為〜6〇質量% ,再更佳 <(〇)黏著劑樹脂>S-24-201219977 (3) Examples of the compound having three polymerizable groups in the compound knife having three polymerizable groups in one molecule, for example, trimethylolpropane tris(mercapto) acrylate, three Hydroxymethylethane tri(meth)acrylate, trimethylolpropane, alkylene oxide modified tri(meth)acrylate, neopentyl alcohol tri(meth)acrylate, dipentaerythritol (fluorenyl) acrylate, trimethylolpropane tris((methyl) propylene oxypropyl) ether, iso-cyanuric acid alkylene oxide modified tri(meth) acrylate, propionic acid dipentaerythritol Alcohol tris(meth)acrylic acid vinegar, tris((indenyl)acryloyloxyethyl)isophthalocyanate, hydroxytrimethylacetaldehyde modified dimethylolpropane tri(meth)acrylate , sorbitol tris(meth)acrylic acid vinegar, propoxylated trimethyl methacrylate tris(meth)acrylic acid vinegar, ethoxylated glycerin triacrylate, and the like. (4) Compound 1 having four or more polymerizable groups in one molecule. The compound having four or more polymerizable groups in the knives may, for example, be neopentyl alcohol tetrakis(meth)acrylate vinegar or sorbitol tetrakis(methyl). Acrylate, ditrihydroxydecylpropane tetra(meth)acrylate, propofol dipentaerythritol tetra(methyl)propene g, ethoxylated pentaerythritol tetra(meth)acrylic acid Vinegar, dipentaerythritol penta(methyl) acrylate acid, diterpene tetraol hexa(meth) acrylate vinegar, sorbitol penta (methyl) acrylate acid, sorbitol hexahydrate Acrylic vinegar, phosphazene, epoxy-modified hexa(meth) acrylate, caprolactone-modified, mt, neodymium tetraol hexa(meth) acrylate, total Rongshe Chemical Co., Ltd. produces UA_306h, Ua_3〇6t'ua Fugong and other amino phthalate acrylates. These turbans are properly maintained in solvent resistance and IT. From the viewpoint of the suitability of the antimony ore, it is preferred that the (meth)acrylic acid vine monomer having two or more (meth)acrylonyl groups in the molecule is more preferably having three or more (meth)acrylic groups. A mercapto (meth) acrylate monomer. 201219977 In particular, it is advantageous to have more than 4 (meth) vinegar mono-systems, such as benzyl (meth) propylene pentanol > quinolol pentaacrylate, dixin 戍 four know, c-acid i day It is better to use solvent resistance, and it is suitable to use this 'plating suitability point of view and dicaptanol penta-acrylic acid! A mixture of the converted ratios of 8 to 6). 'Tetrahydrin, Acrylic Cool = 2 to 4: When a polymerizable monomer having an acid group is used in combination' If a polymer having an acid group is formed::: The sum of polymerizable polymerizable monomers having an acid group is 1 〇 〇1± The range of the range of the early limbs and the portion having no acid group, and preferably having the acid group, is in the range of 1 to 50 parts by mass, and more preferably 5 to 2 〇Y, the early body is more preferably 1~40 quality of the present invention * color photosensitive New Zealand Bailey" dry square. Sexual monomer and polymerizable monomer without acid group η: base, better polymerization content relative coloring sensitivity - 仵 polymerizability early The fraction of the body is preferably 5 to 8 % by mass, and the total solids other than the solvent is in the range of 15 to 50% by mass. Preferably, it is ~6% by mass, and even more preferably (()) Adhesive resin gt ;
可應用於本發明之(C 劑的高分子化合物,則任何〜皆。d樹脂只要是可溶於溶 別使用單一化合物,也可併自J使用。黏著劑樹脂可分 著劑樹脂而言,若考量採用::,化合物。就較佳之黏 則較佳為具有酸基之樹脂微影法時的鹼性顯影性, J )。 下適當稱為「鹼可溶性樹脂 驗可溶性樹脂可於前述顏 添加,亦可於顏料分散組 政、,且成物的調製階段 性Μ成物的調製階段兩者夭调製階段、與著色感光 韦刀别添加。The polymer compound which can be used in the present invention (any agent of the C agent) can be used as long as it is soluble in a single compound, and can also be used from J. The adhesive resin can be used as a separating agent resin. If the consideration is::, compound, the preferred viscosity is preferably the alkali developability in the resin lithography method with an acid group, J). Appropriately referred to as "alkali-soluble resin test soluble resin can be added in the above-mentioned color, can also be in the pigment dispersion group, and the modulation phase of the preparation of the phased composition of the product, the modulation phase, and the color-sensitive Do not add a knife.
S -26 - 201219977 鹼可溶性樹脂為線狀有機高分子聚合物,其中較佳 為具有至少1個鹼可溶性基團(例如羧基'磷酸基、碏酸 基等)之鹼可溶性高分子,更佳為可溶於有機溶劑中並能 夠以弱鹼性水溶液進行顯影者。 鹼可溶性樹腊的製造可應用例如採用週知自由基聚 合法之方法。 性樹脂時的溫度、壓 ;容媒的種類等等聚合 可容易地加以設定, 就以自由基聚合法製造鹼可溶 力、自由基起始劑的種類及其量、 條件而言,本領域具有通常知識者 亦可根據實驗來設定條件。 、冰狀百機高分子聚合物 應用两驗可 為側鏈上具有羧基之聚合物。 舉例而言,可例舉如日本特開昭59 特公昭54-34327號、曰本特公昭58 號、曰本 公昭54-25957號、日本輯„ 7谠、曰本特 i 本特開昭5 9 q w上 昭59-71〇48號各公報所記栽 ?虎、日本特開 烯酸共聚合物、衣康酸共聚 土丙烯酸共聚合物、丙 來酸共聚合物、部分酿化馬:二:酸共聚合物、馬 上具有羧酸之酸性纖維素衍生/、A 5物等、以及側鏈 加成有酸酐者等,進一步亦^ 、具有羥基之聚合物中 歸喊的高分子聚合物‘為:::側鏈上具有(曱基)丙 此等當中’特佳為包含(甲其、 内烯酸共聚合物、(曱基一 烯酸笨曱醋/(甲基) 他單體之多元共聚合物。 本曱知/(曱基)丙烯酸/其S -26 - 201219977 The alkali-soluble resin is a linear organic high molecular polymer, and preferably an alkali-soluble polymer having at least one alkali-soluble group (for example, a carboxyl group, a phosphate group, a decanoic acid group, etc.), more preferably It is soluble in organic solvents and can be developed with a weakly alkaline aqueous solution. The production of the alkali-soluble tree wax can be applied, for example, by a method using a known radical polymerization. The temperature and pressure of the resin; the type of the medium, and the like can be easily set, and the type of alkali solubleness, the type and amount of the radical initiator, and conditions in the free radical polymerization method are known in the art. Those with ordinary knowledge can also set conditions based on experiments. The ice-like polymer can be used as a polymer having a carboxyl group in the side chain. For example, Japanese Unexamined Japanese Patent Publication No. Sho 54-34327, Sakamoto Tetsuo No. 58, Sakamoto Kosho 54-25957, Japanese Series „7谠, 曰本特i 本本特开昭5 9 qw Shang Zhao 59-71〇48, each bulletin is planted? Tiger, Japanese ethenoic acid copolymer, itaconic acid copolymeric acrylic copolymer, acrylic acid copolymer, partially brewed horse: two : an acid copolymer, an acid cellulose derived from a carboxylic acid, an A 5 or the like, and an acid anhydride added to a side chain, and further, a polymer which is called a polymer having a hydroxyl group. It is::: has a (fluorenyl) group in the side chain, etc., which is particularly good for inclusion (methicone, alkenoic acid copolymer, (mercapto-enoic acid awkward vinegar / (methyl)) Multi-component copolymer. This is known as /(mercapto)acrylic acid /
S -27- 201219977 此外’亦可例舉共聚合有甲基丙烯酸2 _羥乙酯者等 作為較佳者。 該聚合物能以任意量混合使用。 除上述以外’還可例舉日本特開平7_14〇654號公報 所記載之(曱基)丙烯酸2-羥丙酯/聚苯乙烯巨單體/甲基 丙稀酸笨曱自曰/甲基丙烯酸共聚合物、丙烯酸2_經基_3_ 苯氧乙醋/聚曱基丙烯酸曱酯巨單體/甲基丙烯酸苯曱酯/ 曱基丙婦酸共聚合物、甲基丙烯酸2 _羥乙酯/聚苯乙烯巨 單體/甲基丙烯酸曱酯/曱基丙烯酸共聚合物、曱基丙烯 酸2-經乙醋/聚苯乙烯巨單體/甲基丙烯酸苯甲酯/曱基丙 烯酸共聚合物等。 其他驗可溶性樹脂可使用日本特開平7 — 2072 1 1號公 報、日本特開平8-259870號公報、日本特開平10-300922 號公報、曰本特.開平1 1 _ 1 4 0 1 4 4號公報、曰本特開平 1 1 - 174224號公報、日本特開2〇〇〇 561 18號、日本特開 2003-233179號、日本特開2〇〇9_52〇2〇號公報等所記載 的週知南分子化合物。 對於驗可溶性樹脂的具體結構單位,特別是(曱基) 丙烯酸及可與其共聚合之其他單體形成的共聚合物由於 可簡便地獲得’並可容易進行鹼溶解性等之調整而適合 使用。 如述可與(甲基)丙烯酸共聚合的其他單體可例舉(曱 基)丙稀酸烷基酯、(曱基)丙烯酸芳基酯、乙烯基化合物 等。 於此’院基及芳基之氫原子可由取代基取代。S -27-201219977 Further, it is preferable to exemplify a method in which 2-hydroxyethyl methacrylate is copolymerized. The polymer can be used in any amount. In addition to the above, '2-hydroxypropyl acrylate/polystyrene macromonomer/methacrylic acid abbreviated/methacrylic acid described in JP-A-7-14-654 Copolymer, Acrylic acid 2_Phenyl-3-phenoxyethyl acetonate/Polymeryl methacrylate macromonomer/Phenyl methacrylate/mercaptopropionic acid copolymer, 2 hydroxyethyl methacrylate /Polystyrene macromonomer/methacrylate/mercaptoacrylic acid copolymer, methacrylic acid 2-acetate/polystyrene macromonomer/benzyl methacrylate/mercaptoacrylic acid copolymer Wait. For other soluble resins, Japanese Patent Laid-Open No. Hei 7-2072 1 1 , Japanese Patent Laid-Open No. Hei 8-259870, Japanese Patent Laid-Open No. Hei 10-300922, and Sakamoto Kay. 1 1 _ 1 4 0 1 4 4 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. South molecular compound. For the specific structural unit of the soluble resin, a copolymer of (mercapto)acrylic acid and other monomers copolymerizable therewith can be easily obtained because it can be easily obtained and can be easily adjusted for alkali solubility or the like. The other monomer which can be copolymerized with (meth)acrylic acid is exemplified by (alkyl)alkyl acrylate, (aryl) aryl acrylate, vinyl compound and the like. The hydrogen atom of the substituent and the aryl group may be substituted by a substituent.
S -28- 201219977 刖述(曱基)丙烯酸烷基酯及(曱基)丙烯酸芳基酯的 具貝例可例舉(甲基)丙烯酸曱酯、(曱基)丙烯酸乙酯、 (甲基)丙烯酸丙酯、(曱基)丙烯酸丁酯、(甲基)丙烯酸異 丁 s曰(甲基)丙烯酸戊酯、(曱基)丙烯酸己酯、(甲基)丙 稀辛S曰、(甲基)丙烯酸苯酯、丙稀酸苯甲酯、丙嫜酸 曱苯酯、丙烯酸萘酯、丙烯酸環己酯等。 則述乙烯基化合物可列舉例如苯乙烯、心曱基苯乙 烯乙烯曱苯、(曱基)丙烯酸縮水甘油酯、丙烯腈、乙 酸乙烯酯、Ν-乙烯吡咯啶酮、(曱基)丙烯酸四氫呋喃甲 西旨、聚苯乙烯巨單體、聚曱基丙烯酸曱酯巨單體、 CH2 = CR31R32f 此盘 R31 本-= L此處R表不虱原子或碳數1〜5之烷基, R32表=碳數6〜ίο之芳香烴環]、CH2 = c(r3丨)(c〇〇r33)[ 此處R31表示氫原子或碳數^之烷基,R33表示碳數^ 之炫基或碳數6〜12之芳院基]等。 此等可共聚合之其他單體可1種單獨使用或2種以 上組合使用。 其他單體為選自CH2 = CR31R32、 (甲基)丙烯酸笨酯、(曱基)丙烯酸 較佳之可共聚合之 ch2=c(r31)(coor33)、 苯甲酯及苯乙烯的至少丨種 CH2 = C(R31)(COOR33)。此等同義。 ’特佳為CH2 = CR31r32及/或 R 、R32及R33分別與前述 又,著色感光性組成物中夕Μ &物〒之驗可溶性樹脂等黏著劑 樹脂的含量相對著色感光性έ且成札Λ $ 、、且成物所含之溶劑以外的總 固體成分’較佳為1〜.20質量%,φ 貝里/0,更佳為2〜1 5質量%,特 佳為3〜12質量%。S -28- 201219977 The examples of the alkyl (meth) acrylate and the aryl (mercapto) acrylate are exemplified by decyl (meth) acrylate, ethyl (meth) acrylate, (methyl) ) propyl acrylate, butyl (meth) acrylate, amyl sulfonate (meth) acrylate, hexyl methacrylate, (meth) propyl sulphide, (A) Base) phenyl acrylate, benzyl acrylate, phenyl phenyl acrylate, naphthalene acrylate, cyclohexyl acrylate, and the like. Examples of the vinyl compound include styrene, fluorenyl styrene vinyl benzene, glycidyl (mercapto) acrylate, acrylonitrile, vinyl acetate, fluorene-vinyl pyrrolidone, and tetrahydrofuranyl (mercapto) acrylate. Purpose, polystyrene macromonomer, polydecyl methacrylate macromonomer, CH2 = CR31R32f This disk R31 Ben-= L where R is not a halogen atom or an alkyl group having a carbon number of 1 to 5, R32 table = carbon Number 6 to ίο of the aromatic hydrocarbon ring], CH2 = c(r3丨)(c〇〇r33) [wherein R31 represents a hydrogen atom or an alkyl group having a carbon number, and R33 represents a condensed group of carbon number ^ or a carbon number of 6 ~12 Fang Fangyuan] and so on. These other monomers which can be copolymerized may be used singly or in combination of two or more. The other monomer is at least CH2 selected from the group consisting of CH2=CR31R32, (meth)acrylic acid ester, (mercapto)acrylic acid, preferably copolymerizable ch2=c(r31)(coor33), benzyl ester and styrene. = C(R31)(COOR33). This is equivalent. 'Specially, CH2 = CR31r32 and/or R, R32, and R33, respectively, and the coloring photosensitive composition, the content of the adhesive resin such as the soluble resin, etc. Λ $ , and the total solid content other than the solvent contained in the product is preferably 1 to .20% by mass, φ Berry/0, more preferably 2 to 15% by mass, particularly preferably 3 to 12% by mass. %.
S -29- 201219977 又,加總具有酸基之聚合性單體與未具有酸基之聚 合性單體所得之聚合性單體與黏著劑樹脂的含量比,以 質量比(聚合性單體之總質量/黏著劑樹脂之質量)較佳為 0.1-10之範圍,更佳為0.4〜8之範圍,再更佳為0.5〜5 之範圍。 <(D)光聚合起始劑> 本發明著色感光性組成物中的(D)光聚合起始劑只 要是藉由曝光而開始進行聚合之化合物則未特別限定。 (D)光聚合起始劑可使用例如樟腦醌、二苯甲酮、二 苯曱酮衍生物、肟化合物、醯基膦、醯基膦衍生物、苯 乙酮、苯乙酮衍生物、六芳基雙咪唑化合物、硼酸化合 物等。 具體實例亦可使用α-羥基環烷基苯基酮類或2-羥基 -2 -曱基-1-苯基-丙酮、二烷氧基苯乙酮類、α-羥基-或4-芳醯基-1,3-二環氧乙烷類、安息香烷基醚類及苯甲基縮 酮類,例如苯甲基二曱基縮酮、乙醛酸苯酯及其衍生物 、乙醛酸笨酯二聚體、過酸酯(perester)類、例如二苯曱 酮四羧酸過酸酯類(例如,如歐洲專利申請公開第 1,1 26,54 1號說明書所記載者)、鹵曱基三氮雜苯類,例 如 2-[2-(4-甲氧基-苯基)-乙烯基]-4,6-雙-三氯曱基 [1.3.5] 三氮雜苯、2-(4-曱氧基-苯基)-4,6-雙-三氯曱基 [1.3.5] 三氮雜笨、2-(3,4-二曱氧基-苯基)-4,6-雙-三氯曱 基[1,3,5]三氮雜苯、2-甲基-4,6-雙-三氯甲基[1,3,5]三氮 雜苯、六芳基雙咪唑/共同起始劑系,例如與2-氫硫基苯 并噻唑組合而成之鄰氯六苯基-雙咪唑;二茂鐵陽離子化S -29-201219977 Further, the content ratio of the polymerizable monomer having an acid group and the polymerizable monomer having no acid group to the adhesive resin is a mass ratio (polymerizable monomer) The mass of the total mass/adhesive resin is preferably in the range of from 0.1 to 10, more preferably in the range of from 0.4 to 8, and still more preferably in the range of from 0.5 to 5. <(D) Photopolymerization Initiator> The (D) photopolymerization initiator in the coloring photosensitive composition of the present invention is not particularly limited as long as it is a compound which starts polymerization by exposure. (D) Photopolymerization initiators, for example, camphorquinone, benzophenone, benzophenone derivatives, anthraquinone compounds, mercaptophosphines, mercaptophosphine derivatives, acetophenone, acetophenone derivatives, and six An arylbisimidazole compound, a boric acid compound, or the like. Specific examples may also use α-hydroxycycloalkylphenyl ketones or 2-hydroxy-2-indolyl-1-phenyl-acetone, dialkoxyacetophenones, α-hydroxy- or 4-arylindoles. Base-1,3-dioxiranes, benzoin alkyl ethers and benzyl ketals, such as benzyldidecyl ketal, phenyl glyoxylate and its derivatives, stupaldehyde An ester dimer, a perester, for example, a benzophenone tetracarboxylic acid perester (for example, as described in the specification of European Patent Application Laid-Open No. 1,166,541), Triazines, for example 2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloroindenyl [1.3.5] triazabenzene, 2- (4-decyloxy-phenyl)-4,6-bis-trichloroindenyl [1.3.5] triazaindole, 2-(3,4-didecyloxy-phenyl)-4,6 - bis-trichloroindolyl [1,3,5]triazabenzene, 2-methyl-4,6-bis-trichloromethyl[1,3,5]triazabenzene, hexaaryl double Imidazole/co-initiator, for example, o-chlorohexaphenyl-biimidazole combined with 2-hydrothiobenzothiazole; ferrocene cationization
S -30- 201219977 合物或二茂鈦類,例如二環戊二烯基-雙(2,6-二氟-3-吡 咯-苯基)鈦;例如,與如英國專利第2,3 39,57 1號說明書 所記載之〇-醯基肟酯化合物的混合物。併用之光聚合起 始劑亦可使用硼酸化合物。 本發明著色感光性組成物中,上述(D)光聚合起始劑 當中係以使用六芳基雙咪唑化合物為佳。透過使用六芳 基雙咪唑化合物,則進行圖案成形後的著色感光性組成 物層即可顯示良好的财光性。 (六芳基雙咪唑化合物) 六芳基雙°米α坐化合物只要是由3個芳基取代之味。圭 環的二聚體則可為任意者,特別是,較佳為以下述通式 (1)表示之化合物,更佳為以通式(2)表示之化合物。S -30-201219977 or a titanocene, such as dicyclopentadienyl-bis(2,6-difluoro-3-pyrrole-phenyl)titanium; for example, as in British Patent No. 2, 3 39 , a mixture of the indole-fluorenyl ester compounds described in the specification No. 57. A boric acid compound can also be used as the photopolymerization initiator. In the colored photosensitive composition of the present invention, the (D) photopolymerization initiator is preferably a hexaarylbisimidazole compound. By using the hexaarylbisimidazole compound, the colored photosensitive composition layer after pattern formation can exhibit good visibility. (Hexaarylbiimidazole compound) The hexaarylbis-meter-α-supplement compound is a taste substituted by three aryl groups. The dimer of the guanidine ring may be any, and particularly preferably a compound represented by the following formula (1), more preferably a compound represented by the formula (2).
通式(1)中,多個 X各自獨立表示氫原子 '鹵素原 子、氰基、碳數1〜4之烷基或碳數6〜9之芳基,多個A 各自獨立表示碳數1〜12之烷氧基、或- COO-R9(其中, R9表示碳數1〜4之烷基或碳數.6〜9之芳基)。η為整數1〜3 ,m為整數1〜3。 -31 - 201219977In the formula (1), a plurality of X each independently represent a hydrogen atom 'halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, and a plurality of A each independently represent a carbon number of 1 to 1. 12 alkoxy group, or -COO-R9 (wherein R9 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms). η is an integer of 1 to 3, and m is an integer of 1 to 3. -31 - 201219977
素原子、氰基、碳數1〜4之烷基或碳數6〜9之芳基。惟 ,X1、X2及X3的2個以上非同時為氫原子。 六芳基雙咪唑化合物可列舉例如 2,2’-雙(2-氯苯基 )-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(4-乙氧基羰基苯基)雙咪唑、2,2’-雙(2-氯苯基 )-4,4’,5,5’-四(4-苯氧基羰基苯基)雙咪唑、2,2’-雙(2,4-二氣苯基)-4,4’,5,5’-四(4-乙氧基羰基苯基)雙咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四(4-苯氧基羰基苯基)雙咪 唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’-四(4-乙氧基羰基 苯基)雙咪唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’四(4-苯氧基羰基苯基)雙咪唑、2,2’-雙(2-氰基苯基)-4,4’,5,5’-四(4-乙氧基羰基苯基)雙咪唑、2,2’-雙(2-氰基苯基 )_4,4’,5,5’_四(4-苯氧基羰基苯基)雙咪唑、2,2’-雙(2-曱 基苯基)-4,4’,5,5’-四(4-甲氧基羰基苯基)雙咪唑、2,2’-雙(2-曱基苯基)-4,4’,5,5’-四(4-乙氧基羰基苯基)雙咪唑 、2,2’-雙(2-曱基苯基)-4,4’,5,5’-四(4-苯氧基羰基苯基) 雙咪唑、2,2’-雙(2-乙基苯基)-4,4’,5,5’-四(4-甲氧基羰基 201219977 苯基)雙咪唑、2,2’-雙(2-乙基苯基)-4,4’,5,5’-四(4-乙氧 基羰基苯基)雙咪唑、2,2’-雙(2-乙基苯基)-4,4’,5,5’-四 (4-苯氧基羰基苯基)雙咪。坐、2,2’-雙(2-苯基苯基 )-4,4’,5,5’-四(4-甲氧基羰基苯基)雙咪唑、2,2’-雙(2-苯 基苯基)-4,4’,5,5’-四(4-乙氧基羰基苯基)雙咪唑、2,2’-雙(2-苯基苯基)-4,4’,5,5’-四(4-苯氧基羰基苯基)雙咪唑 等雙咪唑系化合物; 2,2’-雙(鄰氯苯基)-4,4’,5,5’-四-(對甲氧基苯基)雙 咪唑、2,2’-雙(鄰氯苯基)-4,4’,5,5’-四-(間甲氧基苯基) 雙咪唑、2,2’-雙(〇-氣苯基)-4,4’,5,5’-四-(3,4-二曱氧基 苯基)雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四-(4-甲氧基 苯基)雙咪唑、2,2’-雙(2-氣苯基)-4,4’,5,5’-四-(3-曱氧基 苯基)雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四-(3,4-二曱 氧基苯基)雙咪唑; 2,2’-雙(2,4-二氯苯基)-4,4’,5,5’ -四苯基雙咪唑、 2,2’-雙(2,4,6-三氣苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,4-二溴苯基)-4,4’,5,5’ -四苯基雙咪唑、2,2’ -雙 (2,4,6-三溴苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,4-二氰基苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,4,6-三 氰基笨基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,4-二曱基 苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,4,6-三曱基苯 基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,4-二乙基苯基 )_4,4’,5,5’ -四苯基雙咪唑、2,2’-雙(2,4,6-三乙基苯基 )_4,4’,5,5’ -四苯基雙咪唑、2,2’ -雙(2,4-二笨基苯基 )_4,4’,5,5’_四苯基雙咪唑、2,2’-雙(2,4,6-三苯基苯基An atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms. However, two or more of X1, X2 and X3 are not hydrogen atoms at the same time. The hexaarylbisimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorobenzene) -4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -tetrakis(4-phenoxycarbonylphenyl)bisimidazole, 2,2'-bis(2,4-diphenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonyl) Phenyl)biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)bisimidazole, 2,2 '-Bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)bisimidazole, 2,2'-bis (2,4 ,6-trichlorophenyl)-4,4',5,5'tetrakis(4-phenoxycarbonylphenyl)bisimidazole, 2,2'-bis(2-cyanophenyl)-4,4 ',5,5'-tetrakis(4-ethoxycarbonylphenyl)bisimidazole, 2,2'-bis(2-cyanophenyl)-4,4',5,5'-tetrakis(4-benzene Oxycarbonylphenyl)biimidazole, 2,2'-bis(2-mercaptophenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)bisimidazole, 2, 2'-bis(2-mercaptophenyl)-4,4',5,5'-tetrakis(4-ethoxyl) Carbonyl phenyl)bisimidazole, 2,2'-bis(2-mercaptophenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl) bisimidazole, 2,2' - bis(2-ethylphenyl)-4,4',5,5'-tetrakis(4-methoxycarbonyl 201219977 phenyl)bisimidazole, 2,2'-bis(2-ethylphenyl) -4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)bisimidazole, 2,2'-bis(2-ethylphenyl)-4,4',5,5'- Tetrakis(4-phenoxycarbonylphenyl) bis-mi. Sodium, 2,2'-bis(2-phenylphenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)bisimidazole, 2,2'-bis(2- Phenylphenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)bisimidazole, 2,2'-bis(2-phenylphenyl)-4,4', a biimidazole compound such as 5,5'-tetrakis(4-phenoxycarbonylphenyl)bisimidazole; 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra-( p-Methoxyphenyl)biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra-(m-methoxyphenyl)bisimidazole, 2,2' - bis(indolyl-phenyl)-4,4',5,5'-tetra-(3,4-dimethoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl) -4,4',5,5'-tetra-(4-methoxyphenyl)bisimidazole, 2,2'-bis(2-phenylphenyl)-4,4',5,5'-tetra -(3-decyloxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra-(3,4-dimethoxyphenyl) Bis-imidazole; 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4,6- Tris-phenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4 ',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2, 2'-bis(2,4-dicyanophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4,6-tricyanophenyl) -4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dimercaptophenyl)-4,4',5,5'-tetraphenyl double Imidazole, 2,2'-bis(2,4,6-tridecylphenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4-di Ethylphenyl)_4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4,6-triethylphenyl)_4,4',5,5' - Tetraphenylbisimidazole, 2,2'-bis(2,4-diphenylphenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4, 6-triphenylphenyl
S -33- 201219977 )-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2-氟苯基)-4,4,,5,5,-四苯基雙咪唑、2,2’-雙(ο-氟苯基)-4,4’,5,5,-四苯基雙咪 。坐等雙味吐系化合物等。 上述當中,特佳之化合物可列舉2,2’-雙(2-氣苯基 )-4,4’,5,5’-四苯基雙咪唑(B-CIM , HADOGAYA CHEMICAL(股)製)、2,2’ -雙(鄰氯苯基)-4,4’,5,5’ -四 -(3,4-二曱氧基苯基)雙咪唑(HABI1311,Nippon Siebel Hagner(股)製)、2,2’-雙(2-曱基苯基)-4,4’,5,5’-四苯基雙 咪唑(黑金化成(股)製)。 就本發明著色感光性組成物中之光聚合起始劑的含 量而言,若設聚合性單體(加總具有酸基之聚合性單體與 未具有酸基之聚合性單體所得之聚合性單體)的含量為 100質量份時,則較佳為0.05〜30質量%左右,更佳為 0.1〜20質量%,再更佳為0.2〜10質量%。 又,就併用六芳基雙咪唑化合物與具六芳基雙咪唑 化合物以外之構造的光聚合起始劑時的含量比而言,若 設六芳基雙咪唑化合物之含量為1時,以質量為基準, 則具六芳基雙咪唑化合物以外之構造的光聚合起始劑之 含量較佳為0.1以上5 · 0以下,更佳為0.2以上3.0以下 ,特佳為0.3以上2.0以下。 透過設定為此範圍,則对光性特佳。 <(E)鏈轉移劑> 本發明著色感光性組成物其特徵為含有選自(E)二 級或三級脂肪族硫醇化合物的鏈轉移劑。二級或三級脂 肪族硫醇化合物係作為鏈轉移劑而具有氫供予性。本發 -34- 201219977 明 碳 由 構 1¾ 之 物 確 合 此 減 鹵 鋅 不 料 醇 與 容 因 經 生 中,「 數。 一般 交互作 造,且 低差異 構造, 產生交 本發 高對比 保著色 十生單體 ,鹵化 弱,而 化鋅酞 酉太菁素 穩定, 由此 使用芳 之構造 芳香族 易吸附 鹵化鋅 時性能 本發 來自上 級數」係表示與硫醇基鄰接 之碳原子所鍵結的 而言’具#_構造的化合物彼此間有 用而穩定賴向。Μ素化合物由於具 於構成的氮原子及碳原子之間存有電子 ’因此容易與具有可相對平面沿平行方 且:互補方式存有電子密度之高低差異 互作用。 明中之⑷函化鋅酞菁素顏料在高明度、 :另一方面分散性及分散穩定性不 …組成物之驗性顯影性而使用高酸 %,則會使著色感光性組成物偏向酸性 鋅酞青素顏料與分散劑之間的酸鹼交互 ::分散穩定區域會偏移”匕時若存在 、顏料產生又互作用的化合物,則認 顏料與分散劑之ρ卩 J之間的交互作用將導致分 而使得發生顏料凝聚的可能性增加。 2言,若針對本發明中娜化辞酜 私、醇化合物作為鏈轉移劑時,則認 ?香環構造之效應,1因齒化辞酞菁 醇化σ物之間的相互作用而使得硫醇 於“辞献菁素顏料的表面。此結果, :青素顏料的凝聚而發生著色感光性組 ⑽度、對比)上的問題。 =中由於係使用脂肪族硫醇化合物而 處恤合物之芳香環的作,,且係使 '35-S -33- 201219977 )-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-fluorophenyl)-4,4,5,5,-tetraphenyl Bisimidazole, 2,2'-bis(o-fluorophenyl)-4,4',5,5,-tetraphenyl dimethicone. Sit and wait for a double-sweet compound. Among the above, a particularly preferable compound is 2,2'-bis(2-phenylphenyl)-4,4',5,5'-tetraphenylbisimidazole (B-CIM, manufactured by HADOGAYA CHEMICAL Co., Ltd.). 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra-(3,4-dimethoxyphenyl)bisimidazole (HABI1311, manufactured by Nippon Siebel Hagner Co., Ltd.) 2,2'-bis(2-mercaptophenyl)-4,4',5,5'-tetraphenylbisimidazole (manufactured by Heijin Chemical Co., Ltd.). In the content of the photopolymerization initiator in the coloring photosensitive composition of the present invention, a polymerizable monomer (polymerization of a polymerizable monomer having an acid group and a polymerizable monomer having no acid group) is used. When the content of the monomer is 100 parts by mass, it is preferably about 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.2 to 10% by mass. Further, when the content ratio of the hexaarylbisimidazole compound to the photopolymerization initiator having a structure other than the hexaarylbisimidazole compound is used in combination, if the content of the hexaarylbisimidazole compound is 1, the mass is The content of the photopolymerization initiator having a structure other than the hexaarylbisimidazole compound is preferably 0.1 or more and 0.5 or less, more preferably 0.2 or more and 3.0 or less, and particularly preferably 0.3 or more and 2.0 or less. By setting this range, it is especially good for light. <(E) Chain Transfer Agent> The colored photosensitive composition of the present invention is characterized by containing a chain transfer agent selected from the group consisting of (E) a secondary or tertiary aliphatic thiol compound. The secondary or tertiary aliphatic thiol compound has hydrogen supply as a chain transfer agent.本发-34- 201219977 The carbon is composed of the structure of the material, and the halogen-reducing zinc is not suitable for the alcohol and the cause of the birth, "the number. The general interaction is made, and the low-differential structure produces a high contrast. The monomer is weakly halogenated, and the zinc ruthenium phthalocyanine is stabilized, and thus the performance of the aryl group is easy to adsorb the zinc halide, and the performance is derived from the upper number, which means that the carbon atom adjacent to the thiol group is bonded. It is said that the compounds with the #_ structure are useful and stable to each other. Since a halogen compound has an electron between a nitrogen atom and a carbon atom, it is easy to interact with a difference in electron density which is parallel to the plane and complementary to the electron density. (4) The functionalized zinc phthalocyanine pigment has a high degree of acidity, on the other hand, on the other hand, on the other hand, the dispersibility and dispersion stability are not... The acid-base interaction between the zinc anthraquinone pigment and the dispersant: the dispersion stable region shifts the interaction between the pigment and the dispersant if there is a compound present in the pigment and interacts with the pigment. The effect will lead to an increase in the possibility of pigment agglomeration. In other words, if the Naphtha and the alcohol compound are used as chain transfer agents in the present invention, the effect of the fragrance ring structure is recognized, The interaction between the phthalocyanine alcoholized sigma causes the thiol to be on the surface of the quinone pigment. As a result, the problem of the coloring sensitivity group (10 degree, contrast) occurred in the aggregation of the pigment pigment. = in the use of an aliphatic thiol compound and the aromatic ring of the composition, and made '35-
容易藉 有平面 密度之 向堆疊 的化合 高彩度 良。為 價的聚 側。由 作用便 容易與 為鹵化 散狀態 菁素顏 為因硫 素顏料 化合物 茲認為 成物之 不易產 用具有 S 201219977 菁 料 散 鋅 表 於 顏 〇〇 早 留 致 茲 化 菁 時 具 合 感 已 硫 成 醇 可 級或三級硫 素顏料間的 的凝聚,茲 鹵化鋅敝 穩定性,惟 酞菁素顏料 面的吸附點 鹵化鋅酞菁 料凝聚之虞 體作為聚合 之顏料表面 之顏料的凝 §忍為在本發 合物與具有 素顏料的表 性也劣化。 有的良好色 又,本發 物可發揮鏈 光性組成物 又,具有 知臭氣與揮 醇化合物因 物之用途, 化合物,故 製得較佳之 醇基之化合 相互作用較 認為可充分 菁素顏料的 分散劑一般 表面的所有 失活。即, 素顏料表面 。然,本發 性單體,該 的吸附點, 聚。即,為 明中透過所 酸基之聚合 面便可防止 由此,便認 特性。 明中可提供 移動作用、 0 硫原子的硫 發性相關性 其揮發性高 反之本發明 無使用著色 著色感光性 物,故硫醇 弱而不會發 發揮作為鏈 表面吸附有 為高分子5 吸附點以使 茲認為未被 ,由此便有 明中係使用 具有酸基之 而認為可防 防止_化鋅 選擇之二級 性單體的相 本發明著色 為可獲得鹵 一種二級或 感度優良、 醇化合物會 甚高,一般 而不適用於 中係使用二 感光性組成 組成物。 化合物與鹵 生鹵化鋅酞 轉移劑之功 分散劑時可 並無法吸附 鹵化鋅酞菁 吸附之吸附 經過長時間 具有酸基之 單體便吸附 止由前述硫 酞菁素顏料 或三級脂肪 乘效果,鹵 感光性組成 化辞醜脊素 ^級脂肪族 顯影性良好 發出特有的 而言,脂肪 作為著色感 級或三級脂 物時的臭氣 化鋅賦 菁素顏 能。 確保分 於鹵化 素顏料 點殘留 而發生 聚合性 於所殘 醇基所 凝聚, 族硫醇 化鋅酞 物的經 顏料所 硫醇化 的著色 臭氣。 族一級 光性組 肪族硫 問題,It is easy to borrow from a flat density to a high stack of high chroma. The side of the price. It is easy to be combined with the halogenated state of the phthalocyanine. The sulphur pigment compound is considered to be a difficult substance for the production of the sulphate. The S 201219977 phthalocyanine powder has a sensible sulphuric acid. Coagulation between gradeable or tertiary sulfur pigments, stability of zinc halides, but the adsorption point of the phthalocyanine pigment surface is the condensation of the zinc halide phthalocyanine as the pigment on the surface of the polymerized pigment. The properties of the present polymers and pigmented pigments also deteriorate. Some of the good colors, this hair can play a chain light composition, and have the use of odor and alcohol compounds, compounds, so the synthesis of the best alcohol-based interaction is considered to be sufficient The dispersant of the material generally has all the inactivation of the surface. That is, the pigment surface. However, the present monomer, the adsorption point, is polymerized. That is, it is possible to prevent the above from being transmitted through the polymerization surface of the acid group in the description. In the Ming Dynasty, the sulphur-related correlation of the 0-sulfur atom can be provided, and the volatility is high. In contrast, the present invention does not use the colored coloring photosensitive material, so the thiol is weak and does not function as a polymer adsorbed on the chain surface. In order to avoid the use of a secondary monomer having an acid group which is considered to prevent the prevention of zinc-selection, the present invention is colored to obtain a halogen, a secondary or excellent sensitivity, and an alcohol. The compound will be very high and generally not suitable for use in the middle of the two photosensitive composition. When the compound and the halogenated zinc halide bismuth transfer agent work as a dispersant, the adsorption of the zinc halide phthalocyanine can not be adsorbed. After a long period of time, the monomer having an acid group is adsorbed by the thiophthalocyanine pigment or the tertiary fat. The halogen photosensitive composition is succinctly acclaimed. The aliphatic fatty acid developability is excellent. In particular, fat is used as a coloring sensation grade or a tertiary fat odorant zinc phthalocyanine. It is ensured that the halogenated pigment is present in the residue of the halogenated pigment, and the colored odor which is thiolated by the pigment of the zinc thiolate of the group is formed. Group-level photo group, aliphatic sulfur problem,
S -36- 201219977 二級或三級脂肪族硫醇化合物可例舉 (t-butanethiol)、辛基-2-氫硫基丙酸酯、 丁酸酯、硬脂醯-2-氫硫基丙酸酯、硬脂醯 酯、2,5 -己二硫醇、2,9-癸二硫醇、1,4-丁 基丙酸酯、1,4-丁二醇雙-3-氫硫基丁酸酯 氫硫基丙酸酯、乙二醇雙-3 -氫硫基丁酸酷 烷三-2-氫硫基丙酸酯、三羥甲基丙烷三-3 、新戊四醇四-2-氫硫基丙酸酯、新戊四醇 酸酯、二新戊四醇五-2-氫硫基丙酸酯、二 氫硫基丁酸酯等。 此等當中單官能或二官能脂肪族硫醇 穩定性更為良好而較佳,特佳為三級丁烷 氫硫基丙酸酯、辛基-3 -氫硫基丁酸酯、硬 丙酸酯、硬脂醯-3 -氫硫基丁酸酯、2,5 -己 癸二硫醇、1,4-丁二醇雙-2-氫硫基丙酸酯 -3-氫硫基丁酸酯、乙二醇雙-2-氫硫基丙 _ 3 -鼠硫基丁酸S旨。 本發明著色感光性組成物中可單獨使 三級脂肪族硫醇化合物,亦可使用2種以 脂肪族硫醇化合物來作為鏈轉移劑。 本發明著色感光性組成物中之二級或 醇化合物的含量相對著色感光性組成物所 外的總固體成分,較佳為0.2〜10質量%, 質量%,特佳為0.5〜5質量%。 又,就著色感光性組成物中之二級或 .三級丁烷硫醇 辛基-3-氫硫基 -3 -氫硫基丁酸 二醇雙-2-氫硫 、乙二醇雙-2-i、三羥甲基丙 -氫硫基丁酸酯 四-3 -氮硫基丁 新戊四醇五-3 - 化合物因經時 硫醇、辛基-2-脂酸-2 -鼠硫基 ,二硫醇、2,9-、1,4-丁 二醇雙 L酯、乙二醇雙 用1種二級或 上二級或三級 三級脂肪族硫 含有之溶劑以 更佳為0.3〜8 三級脂肪族硫S-36-201219977 A secondary or tertiary aliphatic thiol compound can be exemplified by (t-butanethiol), octyl-2-hydrothiopropionate, butyrate, stearin-2-hydrothiopropyl Acid ester, stearyl ester, 2,5-hexanedithiol, 2,9-nonanedithiol, 1,4-butyl propionate, 1,4-butanediol bis-3-hydrogenthio Butyrate hydrothiopropionate, ethylene glycol bis-3 -hydrothiobutyric acid trialkyl trihydrothiopropionate, trimethylolpropane tri-3, neopentyl alcohol tetra- 2-Homothiopropionate, pentaerythritol, dipentaerythritol penta-2-hydrothiopropionate, dihydrothiobutyrate, and the like. Among these, monofunctional or difunctional aliphatic thiols are more preferably and more preferably, particularly preferably tertiary butane thiopropyl propionate, octyl-3-hydrothiobutyrate, and hard propionic acid. Ester, stearin-3-hydrothiobutyrate, 2,5-hexane dithiol, 1,4-butanediol bis-2-hydrothiopropionate-3-hydrothiobutyric acid Ester, ethylene glycol bis-2-hydrothiopropyl-3- 3 -merthiobutyric acid S. In the colored photosensitive composition of the present invention, a tertiary aliphatic thiol compound may be used alone, or two aliphatic thiol compounds may be used as the chain transfer agent. The content of the secondary or alcohol compound in the coloring photosensitive composition of the present invention is preferably 0.2 to 10% by mass, mass%, and particularly preferably 0.5 to 5% by mass based on the total solid content of the coloring photosensitive composition. Further, in the coloring photosensitive composition, the second or third-order butane thiol octyl-3-hydrothio-3-hydrothiobutyric acid diol bis-2-hydrogen sulfide, ethylene glycol bis- 2-i, trishydroxymethylpropane-hydrogenthiobutyrate tetras-3-nitrothiobutyrostitol penta-5-3 - compound due to passage of thiol, octyl-2-lipoate-2 - mouse More preferably a sulfur-based, di-thiol, 2,9-, 1,4-butanediol double L ester, ethylene glycol double solvent or a secondary or tertiary tertiary aliphatic sulfur solvent 0.3~8 tertiary aliphatic sulfur
S -37- 處於此範圍内時著色感 好 201219977 醇化合物相對(D)光聚合起始劑之總I 準較佳為5〜150質量%,更# A 夏的含量, 文佳為1〇〜〗Λλ试 10〜50質量0/〇。 0貝量°/ 處於此範圍内時可促進製成著 的聚合反應而形成感度高且ρ + 感光性紐 1且艮好的圖案。 又,就著色感光性組成物中之_卞 醇化合物相對(A) _化鋅狄菁素顏料三級 車父佳為1〜1 〇質量%,更佳為2〜8暂Θ里以 量%。 貧巧’特佳 光性組成物的保存 <(F)溶劑> 本發明著色感光性組成物係含有(F)溶劑。 可使用於本發明之(F)溶劑可例舉經分類為 類、酮類、芳香烴類等的溶劑。 (F)溶劑亦可使用於前述顏料分散組成物的 可用作(F)溶劑之酯類的實例除例如乙酸乙 正丁酯、乙酸異丁酯、曱酸戊酯、乙酸異戊酯 丁雖、丙酸丁醋、丁酸異丙酯、丁酸乙酯、丁 院基酯類、乳酸甲酯、乳酸乙酯、氧基乙酸曱 乙酸乙酯、氧基乙酸丁酯、甲氧基乙酸曱酯、 酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、 酸乙酯等之外,還可列舉3 -氧基丙酸甲酯及3-乙酯等3 -氧基丙酸烧基酯類;2 -氧基丙酸甲酯 丙酸乙酯、2 -氧基丙酸丙酯、2 -氧基-2 -甲基丙 以質量基 >,特佳為 成物層時 脂肪族硫 質量基準 為3~5質 穩定性良 酯類、峻 調製。 酯、乙酸 、乙酸異 酸丁酯、 酯、氧基 甲氧基乙 乙氧基乙 氣基丙酸 、2-氧基 酸曱酯、 201219977 2- 氧基-2-曱基丙酸乙酯等2-氧基丙酸烷基酯類;3 -曱氧 基丙酸甲酯、3 -曱氧基丙酸乙酯、3 -乙氧基丙酸曱酯、 3- 乙氧基丙酸乙酯、2-曱氧基丙酸甲酯、2-曱氧基丙酸乙 酯、2-曱氧基丙酸丙酯、2-乙氧基丙酸曱酯、2-乙氧基丙 酸乙酯、2-甲氧基-2-曱基丙酸曱酯、2-乙氧基-2-曱基丙 酸乙基等烷氧基丙酸烷基酯;丙酮酸甲酯、丙酮酸乙酯 、丙酮酸丙酯、乙醯乙酸曱酯、乙醯乙酸乙酯、2-側氧 丁酸曱酯、2 -侧氧丁酸乙酯等。 醚類之實例可列舉例如二乙二醇二曱醚、四氫°夫喃 、乙二醇單甲醚、乙二醇單***、乙酸甲賽璐蘇、乙酸 乙賽璐蘇、二乙二醇單曱醚、二乙二醇單***、二乙二 醇單丁醚、丙二醇曱醚乙酸酯、丙二醇***乙酸酯、丙 二醇丙醚乙酸酯等。 酮類之實例可列舉例如曱乙酮、環己酮' 2-庚酮、 3 -庚酮等。 芳香烴類之實例可列舉例如曱苯、二曱苯等。 此等溶劑當中,較佳為3 -乙氧基丙酸甲酯、3 -乙氧 基丙酸乙酯、乙酸乙賽璐蘇、乳酸乙酯、二乙二醇二甲 醚、乙酸丁酯、3 -曱氧基丙酸曱酯、2-庚酮、環己酮、 乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇甲醚乙 酸S旨等。 溶劑可單獨使用,亦可2種以上組合使用。 本發明著色感光性組成物中之(F)溶劑的含量可考 量著色感光性組成物的塗布性等來適當決定,一般而言 著色感光性組成物中之(F)溶劑的含量為7 6質量%〜8 8質 量%。S -37- is good in coloration in this range 201219977 The total I of the alcohol compound relative to (D) photopolymerization initiator is preferably 5 to 150% by mass, more #A Summer content, Wenjia is 1〇~ 〗 Λ Λ try 10~50 mass 0/〇. When the amount is within 0, the polymerization reaction is promoted to form a pattern having high sensitivity and ρ + photosensitive sensitization. Further, the sterol compound in the coloring photosensitive composition is preferably 1 to 1 〇 mass%, more preferably 2 to 8 Θ% by mass relative to the (A) _ zinc phthalocyanine pigment three-level car. . Preservation of a poorly desirable optical composition <(F) Solvent> The colored photosensitive composition of the present invention contains (F) a solvent. The solvent (F) which can be used in the present invention may, for example, be a solvent classified into a class, a ketone, an aromatic hydrocarbon or the like. (F) a solvent may also be used as an example of the ester-dispersible composition of the above-mentioned pigment dispersion composition which can be used as an ester of (F) solvent, for example, although ethyl n-butyl acetate, isobutyl acetate, amyl citrate, isoamyl acetate , butyl acetonate, isopropyl butyrate, ethyl butyrate, butyl ester, methyl lactate, ethyl lactate, ethyl oxyacetate, butyl oxyacetate, methoxyacetate Examples of the ester, ethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl acrylate include 3-oxypropionic acid such as methyl 3-oxypropionate and 3-ethylpropionate. An alkyl ester; a methyl 2-propoxypropionate ethyl propionate, a propyl 2-oxypropionate, a 2-methoxy-2-methylpropane in a mass group, particularly preferably a layer The aliphatic sulfur quality standard is 3~5 quality stable good esters and fine modulation. Ester, acetic acid, butyl isophthalate, ester, oxymethoxyethoxyethoxyethylpropionic acid, decyl 2-oxoate, 201219977 ethyl 2-oxo-2-mercaptopropionate Alkyl 2-oxypropionates; methyl 3-methoxypropionate, ethyl 3-methoxyoxypropionate, decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate , methyl 2-methoxypropionate, ethyl 2-decyloxypropionate, propyl 2-methoxypropionate, decyl 2-ethoxypropionate, ethyl 2-ethoxypropionate An alkyl alkoxypropionate such as 2-methoxy-2-mercaptopropionate or 2-ethoxy-2-mercaptopropionate; methyl pyruvate, ethyl pyruvate, Propyl pyruvate, decyl acetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutyrate, and the like. Examples of the ethers include, for example, diethylene glycol dioxime ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, acesulfame acetate, ethyl acesulfame acetate, diethylene glycol. Monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol oxime ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, and the like. Examples of the ketones include, for example, anthraquinone, cyclohexanone '2-heptanone, 3-heptanone, and the like. Examples of the aromatic hydrocarbons include, for example, toluene, diphenylbenzene, and the like. Among these solvents, preferred are methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acesulfame acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3 - decyloxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate S, and the like. The solvent may be used singly or in combination of two or more. The content of the solvent (F) in the coloring photosensitive composition of the present invention can be appropriately determined in consideration of the coatability of the coloring photosensitive composition, etc., and generally, the content of the solvent (F) in the coloring photosensitive composition is 76 mass. %~8 8 mass%.
S -39- 201219977 <(G)光敏化劑> 本發明著色感光性組成物可進一步含有(G)光敏化 劑。 (G)光敏化劑適合使用於35〇〜45〇nm具有極大吸收 波長之化合物。 除例如多核方香私類(例如祐、花、聯伸三苯)、二 笨并派喃類(例如螢光素、伊紅、赤藻辛、羅丹明B、孟 加拉玫紅)、花青(cyanine)類(例如硫雜羰花青、氧雜羰 花青)、部花青素類(例如部花青素、羰部花青素)、噻嗪 類(例如硫堇、亞甲基藍、甲苯胺藍)、吖啶類(例如吖啶 橙、氯黃素、吖啶黃素)、蒽醌類(例如蒽醌)、斯誇琳類 (squaryliums)(例如斯誇琳)、二苯甲酮類(例如4 4,_二乙 基胺基·一本.曱酬)寺化合物群之外,還可例舉日本特開 2007-9 1 806號公報、日本特開2008-9323號公報、日本 特開2010-49160號公報所記載之化合物。 本發明中之(D)光聚合起始劑、(E)二級或三級脂肪 族硫醇化合物及(G)光敏化劑的含有比例(質量比)較佳 為光聚合起始劑/硫醇化合物/光敏化劑=2 0〜5 0 / 3 0〜7 0 / 1 0〜30,更佳為光聚合起始劑/硫醇化合物/光敏化劑 =30〜40/40〜60/10〜20 ’再更佳為光聚合起始劑/硫醇化合 物/光敏化劑=35〜40/50〜55/10〜15。 以此等比例使用各成分可提高對g線、h線及i線的 曝光感度’且容易獲得付合曝光區域之南精度線寬的著 色圖案。S-39-201219977 <(G) photosensitizer> The colored photosensitive composition of the present invention may further contain (G) a photosensitizer. (G) The photosensitizer is suitably used for compounds having a maximum absorption wavelength of from 35 Å to 45 Å. In addition to, for example, polynuclear fragrant private (such as Youhua, flower, and extended triphenyl), diphtheria and genus (such as luciferin, eosin, red algae, rhodamine B, bengal rose), cyanine (cyanine) ) (such as thiacarbocyanine, oxacarbocyanine), procyanidins (such as procyanidins, carbonyl anthocyanins), thiazines (such as thioindigo, methylene blue, toluidine blue) , acridines (such as acridine orange, chloroflavin, acridine flavin), guanidines (such as guanidine), squaryliums (such as squary), benzophenones (for example) In addition to the temple compound group, Japanese Patent Publication No. 2007-9 1 806, JP-A-2008-9323, and JP-A-2010 A compound described in the publication No. 49160. The content ratio (mass ratio) of the (D) photopolymerization initiator, (E) secondary or tertiary aliphatic thiol compound, and (G) photosensitizer in the present invention is preferably a photopolymerization initiator/sulfur Alcohol compound / photosensitizer = 2 0~5 0 / 3 0~7 0 / 1 0~30, more preferably photopolymerization initiator / thiol compound / photosensitizer = 30~40/40~60/10 ~20 'More preferably photopolymerization initiator / thiol compound / photosensitizer = 35~40/50~55/10~15. By using each component in an equal ratio, the exposure sensitivity to the g-line, the h-line, and the i-line can be improved, and the color pattern of the south-precision line width of the bonded exposure region can be easily obtained.
S -40- 201219977 又’本發明著色感光性組成物亦以含有共敏化劑為 佳。本發明中共敏化劑具有進一步提高光敏化劑、光聚 合起始劑對活性放射線的感度、或抑制由氧引起之光聚 合性化合物的聚合阻礙等作用。 此種共敏化劑之實例為胺類,可列舉例如 M.R.Sander 等人所著「Journal of polymer s〇ciety」第 l〇卷3173頁(1972)、日本特公昭44_2〇 189號公報、曰 本特開昭5 1 - 8 2 1 0 2號公報、曰本特開昭5 2 -1 3 4 6 9 2號公 報、日本特開昭5 9 -1 3 8 2 0 5號公報 '日本特開昭6 0 - 8 4 3 0 5 號公報、曰本特開昭62-1 8537號公報 '曰本特開昭 64-33104 號公報、Research Disclosure 33825 號記載之 化合物等,具體上可列舉三乙醇胺、對二甲基胺基安息 香酸乙酯、對甲醯基二甲基苯胺、對甲基硫二曱基苯胺 等。 共敏化劑之其他實例可例舉胺基酸化合物(例如N_ 苯基甘胺酸等)、日本特公昭48-42965號公報記載之有 機金屬化合物(例如乙酸三丁基錫等)、日本特公昭 55-3 44 14號公報記載之氫供體 '日本特開平6-308727號 公報記載之硫化合物(例如三噻吭等)等。 對於共敏化劑之含量,由提高根據聚合生長速度與 鏈移動的平衡之硬化速度而言,相對感光性組成物之全 固體成分的質量較佳為0.丨〜30質量%之範圍,更佳為 1〜25質量%之範圍,再更佳為〇_5〜20質量%之範圍。 <添加劑> 本發明著色感光性組成物可視需求而含有自由基捕S - 40 - 201219977 Further, the coloring photosensitive composition of the present invention is preferably a co-sensitizer. In the present invention, the co-sensitizer further enhances the sensitivity of the photosensitizer, the photopolymerization initiator to the active radiation, or the polymerization inhibition of the photopolymerizable compound by oxygen. Examples of such a co-sensitizer are amines, and for example, "Journal of Polymer s〇ciety", Vol. 1, p. 3173 (1972) by MRSander et al., Japanese Patent Publication No. 44-2〇189, transcript JP-A-Chang No. 5 1 - 8 2 1 0 2, 曰本特开昭 5 2 -1 3 4 6 9 2, Japanese Special Open 5 9 -1 3 8 2 0 5 'Japanese Special Japanese Laid-Open Patent Publication No. SHO-62-33104, and a compound described in Research Disclosure No. 33825, and the like, specifically, triethanolamine , p-dimethylamino benzoic acid ethyl ester, p-methyl dimethyl aniline, p-methyl thiodiphenyl aniline and the like. Other examples of the co-sensitizers include an amino acid compound (for example, N-phenylglycine), an organometallic compound described in JP-A-48-42965 (for example, tributyltin acetate), and a Japanese special public 55. A sulfur compound (for example, trithiazine or the like) described in the Japanese Patent Publication No. Hei 6-308727. With respect to the content of the co-sensitizer, the mass of the total solid content of the photosensitive composition is preferably in the range of 0. 丨 30 30% by mass, and the curing speed is increased from the polymerization growth rate to the equilibrium of the chain movement. Preferably, it is in the range of 1 to 25% by mass, and more preferably in the range of 〇5 to 20% by mass. <Additive> The colored photosensitive composition of the present invention may contain free radicals depending on the demand.
C -41- 201219977 捉劑、光安定劑、硬化助南丨、 d 熱聚合起始劑、界面活性 劑、密接助劑、顯影促進劑、 ”.、聚α抑制劑、分散劑、 其他添加劑(填充劑、 系外線吸收劑、解凝劑 (defl〇CCUlatlllgagent)等)之各種添加劑。 (自由基捕捉劑) 本發明中可添加各種自由基捕捉劑以提高对光性。 自由基捕捉劑的種類並未特別限定,惟氧化偶氮系化合 物及各種光安定劑由耐熱性、_光性觀點而言較佳 化偶氮系化合物的具體實例可例舉氧偶氮苯 甲謎、氧偶氮苯***、4,4,·二辛基氧偶氮苯等。馬氮本 (光安定劑) 為提高耐光性則各種光安定劑亦可發揮效果。 光安定劑的種類並未特別限定,惟由通用性方面丄於 合使用受阻胺系光安定劑;例如雙(2,2,6,6四甲=適 啶基)己二酸醋、雙(1,2,2,6,6_五曱基_4娘咬基)己二底 、雙(2,2,6,6 -四曱基_4_哌啶基)癸二酸酯、雙 ·酉曰 土 -哌0疋基)癸二酸酯、四(2,2,6,6_四曱基_4-哌啶旯 )-1,2,3’肛四丙烯酸酯、四(1,2,2,6,6_五曱基_4_哌啶二 )-1,2,3’4-四丙烯酸酯、受阻酚系光安定劑;例如新=土 醇-四(3-(3,,5,_二_三級丁基_4、羥基苯基)丙酸鲳等。四 本發明中之光安定劑的含量相對著色感光性組私 的全固體成分,較佳為(My O質量%左右,更 0_2〜4.0士質量%,再更佳為〇 5〜2 〇質量%。若為u $量 %以下時無法獲得所要之耐光性,而為5.0質量%以/里 則感度減少而不佳。 。上時 •42· 201219977 (硬化助劑) 硬化助劑可使用具有環氧環之化合物,以提高所形 成之塗布膜的強度。使用具有環氧環之化合物便可進行 熱聚合、提高溶劑耐性並提升ITO濺鍍適合度而較佳。 具有環氧環之化合物為雙酚A型、甲酚酚醛清漆型 、聯苯型、脂環族環氧化合物等分子中具有2個以上環 氧環之化合物。 舉例而言,雙酚A型除Epotohto YD-1 15、YD-1 18T 、YD-127、YD-128、YD-134、YD-8125、YD-7011R、 ZX- 105 9、YDF-8170、YDF-170等(以上為東都化成製) 、DENACOL EX-1 101、EX-1 102、EX-1 103 等(以上為長 瀨化成製)、PRAXEL GL-61、GL-62、G101、G102(以上 為Daicel化學製)之外,亦可例舉與此等類似之雙酚f 型、雙酚S型。又可使用Ebecryl 3700、370 1、600(以 上為Daicel-UCB製)等環氧丙烯酸酯。 曱酚酚醛清漆型可例舉 Epotohto YDPN-638、 YDPN-701、YDPN-702、YDPN-703、YDPN-704 等(以上 為東都化成製)、DENACOL EM-125等(以上為長瀨化成 製)’聯苯型可例舉3,5,3,,5,-四曱基-4,4,-二縮水甘油基 聯苯等,脂環族環氧化合物可例舉CELLOXIDE 202 1、 208 1、2083、2085、EPOLEAD GT-301、GT-302、GT-401 、GT-403 ' EHPE-3150(以上為 Daicel 化學製)、Suntohto ST-3000、ST-4000、ST-5 080、ST-5 100 等(以上為東都化 成製)、Epiclon430 ' 同 673、同 695、同 850S、同 4032( 以上為DIC製)等。C -41- 201219977 Catch, light stabilizer, hardening aid, d thermal polymerization initiator, surfactant, adhesion promoter, development accelerator, "., poly alpha inhibitor, dispersant, other additives ( Various additives such as a filler, an external absorbent, a de-agglomerating agent, etc. (radical scavenger) Various radical scavengers can be added in the present invention to improve the light-receiving property. The azo compound and the various photosensitizers are preferably exemplified by heat resistance and light stability. Specific examples of the azo compound are oxyazobenzene, azobenzene. Ethyl ether, 4,4, dioctyloxyazobenzene, etc. Horse nitrogen (light stabilizer) Various light stabilizers can also exert effects in order to improve light resistance. The type of light stabilizer is not particularly limited. In terms of versatility, it is suitable for the use of hindered amine light stabilizers; for example, bis(2,2,6,6 tetramethyl=isoazide) adipic acid vinegar, double (1,2,2,6,6_pentaquinone) _4 Niangbitu) hexamidine, bis (2,2,6,6-tetradecyl _4_piperidinyl) sebacate, double Alumina-piperidinyl) sebacate, tetrakis(2,2,6,6-tetradecyl-4-piperidinium)-1,2,3' anal tetraacrylate, four (1, 2,2,6,6-penta-yl-4_piperidinedi)-1,2,3'4-tetraacrylate, hindered phenolic light stabilizer; for example, new = earth alcohol-tetra (3-(3) , 5, _ di-tertiary butyl _4, hydroxyphenyl) bismuth propionate, etc. The content of the light stabilizer in the four inventions is preferably the total solid content of the coloring photosensitive group, preferably (My O The mass% is about 0_2 to 4.0% by mass, and more preferably 〇5 to 2 〇% by mass. If it is less than u $% by weight, the desired light resistance cannot be obtained, and if it is 5.0% by mass or less, the sensitivity is reduced. It is not good. On time • 42· 201219977 (hardening aid) The hardening aid can use a compound with an epoxy ring to increase the strength of the formed coating film. Thermal polymerization can be carried out using a compound having an epoxy ring. It is preferable to improve the solvent resistance and improve the suitability of ITO sputtering. The compound having an epoxy ring has two or more molecules such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound. Epoxy ring For example, bisphenol A type except Epotohto YD-1 15, YD-1 18T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-105 9, YDF-8170 , YDF-170, etc. (above is Dongdu Chemical Co., Ltd.), DENACOL EX-1 101, EX-1 102, EX-1 103, etc. (above is Changchun Chemical System), PRAXEL GL-61, GL-62, G101, G102 (The above is manufactured by Daicel Chemical Co., Ltd.), and bisphenol f type and bisphenol S type similar to these are also exemplified. Further, an epoxy acrylate such as Ebecryl 3700, 370 1, 600 (manufactured by Daicel-UCB) can be used. The phenolic novolac type may, for example, be Epotohto YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 (the above is manufactured by Tohto Kasei Co., Ltd.), DENACOL EM-125, etc. The biphenyl type may, for example, be 3,5,3,5,-tetradecyl-4,4,-diglycidylbiphenyl or the like, and the alicyclic epoxy compound may be exemplified by CELLOXIDE 202 1 and 208 1. 2083, 2085, EPOLEAD GT-301, GT-302, GT-401, GT-403 'EHPE-3150 (above is Daicel Chemical), Suntohto ST-3000, ST-4000, ST-5 080, ST-5 100 Etc. (The above is the Dongdu Chemical System), Epiclon 430' with 673, the same 695, the same 850S, the same 4032 (the above is the DIC system).
S -43- 201219977 此外,亦可使用1,1,2,2-四(對縮水甘油氧基苯基)乙 烷、三(對縮水甘油氧基苯基)曱烷、異三聚氰酸三縮水 甘油基三(羥基乙基)酯、鄰苯二甲酸二縮水甘油酯、對 苯二曱酸二縮水甘油酯、還有屬胺型環氧樹脂之S -43- 201219977 In addition, 1,1,2,2-tetra(p-glycidoxyphenyl)ethane, tris(p-glycidoxyphenyl)decane, isomeric cyanuric acid can also be used. Glycidyl tris(hydroxyethyl) ester, diglycidyl phthalate, diglycidyl terephthalate, and an amine type epoxy resin
Epotohto YH-434、YH-434L、在雙酚A型環氧樹脂之骨 架中將二聚酸加以改質所得之縮水甘油酯等。 其中’較佳為「分子量/環氧基環之數值」為i 〇〇以 上’更佳為130〜500。若「分子量/環氧基環之數值」較 小時’則硬化性高、硬化時之收縮大;若過大時,則硬 化性不足、缺少可靠性或平坦性劣化。 具體較佳化合物可例舉Ep〇t〇hto 、YDF-170、YDPN-63 8、YDPN-701(以上為長瀨化成製) ' PRAXEL GL-61、GL-62、3,5,3,,5,-四曱基·4,4,_ 二縮 水甘油基聯苯、CELL〇XIDE 2〇21、2〇8ι、 GT-302、GT-403、EHPE-3 150(以上為 Daicel化學製)等。 本發明中之硬化助劑的含量相對著色感光性組成物 固體成分’較佳為仏增量%左右,更佳為〇2〜4〇 貝里/〇,再更佳為0.5〜2 〇質量0/若 無法獲得硬化促進H 1里%以下時 „ 進效果,而為5.0質量%以上時則右f # 性惡化之問題。 才則有耐先 (熱aK合起始劑) 本發明著色咸| 有效。埶聚入叙私、,且成物中含有熱聚合起始劑時亦 ^。起始劑可列舉例 氧化物系化合物…+、虱糸化合物、過 合物,前述過氧化I:偶氮系化合物可例舉偶氮雙系化 物糸化合物則可例舉_過氧化物、過Epotohto YH-434, YH-434L, a glycidyl ester obtained by modifying a dimer acid in a bisphenol A type epoxy resin skeleton. Wherein 'preferably, the value of the molecular weight/epoxy ring" is i 〇〇 or more and more preferably 130 to 500. When the "molecular weight/epoxy ring value" is smaller than the hour, the hardenability is high and the shrinkage at the time of hardening is large. When the value is too large, the hardenability is insufficient, and reliability or flatness is deteriorated. Specific preferred compounds are Ep〇t〇hto, YDF-170, YDPN-63 8 and YDPN-701 (the above are manufactured by Changchun Chemicals Co., Ltd.) 'PRAXEL GL-61, GL-62, 3, 5, 3, 5,-tetradecyl·4,4,_ diglycidylbiphenyl, CELL〇XIDE 2〇21, 2〇8ι, GT-302, GT-403, EHPE-3 150 (above, made by Daicel Chemical) . The content of the hardening aid in the present invention is preferably about 仏 increment % relative to the solid content of the coloring photosensitive composition, more preferably 〇 2 to 4 〇 里 〇 / 〇, and even more preferably 0.5 〜 2 〇 mass 0 /If it is impossible to obtain the effect of hardening to promote H 1 % or less, the effect is worse, and when it is 5.0% by mass or more, the right f # is deteriorated. Only the first (heat aK combined starter) is dyed in the present invention. It is effective. When it is incorporated into the private product, and the thermal polymerization initiator is contained in the product, the starting agent may be exemplified by an oxide compound...+, an anthracene compound, a per-compound, and the above-mentioned peroxidation I: The nitrogen-based compound may, for example, be an azobis compound bismuth compound, and may be exemplified by a peroxide.
S -44- 201219977 、過氧化氫、過氧化二烷基、 過氧—碳酸鹽等。 過 氧化縮酮(peroxyketal) 氧化二醯基、過氧酯、 (界面活性劑) 本發明著色感光性組成物中, 言則以使用各種界面活性劑 :::而 液時的液體特_=二性 並可改善塗布厚度的均等性、液體節省) 降低基板與塗布液的界面張力 於係 m…— 4對基板的濡渥性, 基板m故以少量液量形成 的薄膜時’仍可形成厚度不均小之厚度均等的膜,由:S-44- 201219977, hydrogen peroxide, dialkyl peroxide, peroxy-carbonate, etc. Peroxyketal Oxidized dioxime, peroxyester, (surfactant) In the colored photosensitive composition of the present invention, various surfactants are used::: liquid when liquid is _=two And can improve the uniformity of the coating thickness, liquid saving) reduce the interfacial tension between the substrate and the coating liquid, and the thickness of the substrate can be formed when the film is formed by a small amount of liquid. A film of equal thickness that is not uniform, consisting of:
屬有效。又’使用容易產生去液性的狹縫塗布 時亦屬有效。 V 陽離子系、陰離子系 系界面活性劑較佳為 界面活性劑可使用非離子系、 之各種界面活性劑。其中,非離子 具有全氟烷基的氟系界面活性劑。 氟系界面活性劑的氟含有率較佳為3〜40質量%,更 佳為5〜30質量%,特佳4 7〜25質量%。若敗含有率處於 前述範圍内,則以塗布厚度均等性、液體節省性方面而 言係屬有效’且於組成物中的溶解性亦良好。 氣系界面活性劑可列舉例如MEGAFAC F171、同 F172、同 F173、同 F177、同 F141、同 F142、同 F143 、同 F144、同 R30、同 F437(以上為 DIC(股)製)、FLORARD FC430、同FC431、同FC171(以上為住友3M(股)製)、 SURFLON S-382、同 SC-101、同 SC-103、同 SC-104、 同 SC-105、同 SC1 068、同 SC-381、同 SC-383、同 S393 、同KH-40(以上為旭硝子(股)製)等。It is valid. Further, it is also effective when using a slit coating which is liable to cause liquid removal. The V cation-based or anionic-based surfactant is preferably a non-ionic surfactant or a surfactant. Among them, a non-ionic fluorine-based surfactant having a perfluoroalkyl group. The fluorine-containing surfactant has a fluorine content of preferably 3 to 40% by mass, more preferably 5 to 30% by mass, particularly preferably 4 to 25% by mass. When the content is in the above range, it is effective in terms of coating thickness uniformity and liquid economy, and the solubility in the composition is also good. Examples of the gas system surfactant include MEGAFAC F171, F172, F173, F177, F141, F142, F143, F144, R30, F437 (above DIC), FLORARD FC430, Same as FC431, FC171 (above Sumitomo 3M), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1 068, SC-381, Same as SC-383, same as S393, and KH-40 (above is Asahi Glass Co., Ltd.).
S 201219977 氟系以外之界面活性劑的實例可例舉酞菁素衍生物 (市售品EFKA-745(森下產業公司製))、有機矽氧烷聚合 物KP341(信越化學工業公司製)、(甲基)丙烯酸系(共)聚 合物Polyflow No.75、No.90、Νο.95(共榮社油脂化學工 業公司製)、W001 (裕商公司製)等陽離子系界面活性劑; 聚氧乙烯月桂醚、硬脂酸聚氧乙烯醚、油酸聚氧乙烯醚 '聚氧乙烯辛基苯醚、聚氧乙烯壬基苯醚、聚乙二醇二 月桂駄8曰、聚乙二酵二硬脂酸酯、山梨醇酐脂肪酸酯 (BASF 公司製 Piuronic L1〇、L31、L61、L62、i〇R5、pR2 、25R2、Tetronic 304、701、704、901、904、150R1 等 非離子系界面活性劑;wo〇4、w〇〇5、W017(裕商公司製 )專陰離子系界面活性劑。 界面活性劑之添加量相對著色感光性組成物的全質 1較佳為0.001〜2.0質量%,更佳為〇 005M 〇質量%。 (密接助劑) 本發明所使用之感光性樹脂組成物中,由提高與基 板的岔接性之械點而言可添加密接助劑。密接助劑可使 用烷氧矽烷化合物,其中可使用矽烷偶合劑。 矽烷偶合劑較佳為具有烷氧矽基作為可與充當基板 之無機材料形成化學鍵的水解性基團者,較佳為罝有盥 有機樹脂之間發生交互作用或形成鍵結而顯示親和性之 (甲基)丙烯醯基、苯基、二級或三級氫硫基、環氧基、 胺基石夕烧基等基團的石夕烷偶合劑,其中更佳為(甲基)丙 歸醯丙基三甲氧基錢、環氧丙基三甲氧基#燒。此種 原材料可例舉κβΜ·303、KBM_403、KBM_5〇3(以上信越 化學工業(股)製)。S 201219977 An example of a surfactant other than a fluorine-based phthalocyanine derivative (commercial product EFKA-745 (manufactured by Morishita Sangyo Co., Ltd.)), an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), a cationic surfactant such as a methyl-acrylic (co)polymer (Polyflow No. 75, No. 90, Νο. 95 (manufactured by Kyoeisha Oil Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene Lauryl ether, stearic acid polyoxyethylene ether, oleic acid polyoxyethylene ether 'polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyethylene glycol laurel 8 曰, polyethylene lysine Nonionic interfacial activity of fatty acid esters, sorbitan fatty acid esters (Piuronic L1, L31, L61, L62, i〇R5, pR2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, manufactured by BASF Corporation) ; 、 、 ; ; 、 ; ; 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 , , , More preferably 〇005M 〇% by mass. (Close auxiliaries) Photosensitive resin used in the present invention In the composition, an adhesion aid may be added from the point of improving the adhesion to the substrate. The adhesion aid may use an alkoxysilane compound in which a decane coupling agent may be used. The decane coupling agent preferably has an alkoxy oxime. The base is a hydrolyzable group which can form a chemical bond with an inorganic material serving as a substrate, preferably a (meth) acrylonitrile group or a phenyl group which exhibits an affinity or an bond between the ruthenium-containing organic resins and exhibits a bond. , a secondary or tertiary hydrogenthio group, an epoxy group, an amine group, a base group, etc., wherein the (meth) propyl hydrazide propyl trimethoxy valency, propylene propylene The base material may be exemplified by κβΜ·303, KBM_403, and KBM_5〇3 (manufactured by Shin-Etsu Chemical Co., Ltd.).
S -46- 201219977 使用矽烷偶合劑時之添加量在本發明著色感光性組 成物中的全固體成分中,較佳為0.2質量%〜5.0質量%之 範圍,更佳為0.5質量%〜3.0質量%。 (顯影促進劑) 又,欲促進著色感光性組成物層之未硬化部分的鹼 溶解性,並進一步提高著色感光性組成物的顯影性時, 可將顯影促進劑使用於著色感光t生組成物中。 此種顯影促進劑為有機羧酸,較佳為分子量1 000以 下的低分子量有機羧酸。具體而言可列舉例如曱酸、乙 酸、丙酸'丁酸、纈草酸、三曱基乙酸、己酸、二乙基 乙酸、庚酸、辛酸等「脂肪族一元羧酸」;草酸、丙二 酸、玻ίό酸、戊二酸、己二酸、庚二酸、辛二酸、壬二 酸、癸二酸、十三烷二酸(巴西二酸)、曱基丙二酸、乙 基丙二酸、二曱基丙二酸、甲基琥珀酸、四甲基琥珀酸 、檸康酸等「脂肪族二元羧酸」;1,2,3-丙三曱酸、烏頭 酸、降莰三酸等「脂肪族三元羧酸」;苯甲酸(安息香酸 )、鄰曱苯曱酸、枯茗酸、2,3-二曱基苯甲酸、3,5-二曱 基苯甲酸等「芳香族一元羧酸」;鄰苯二甲酸、間苯二 曱酸、對苯二甲酸、1,2,4-苯三曱酸(偏苯三甲酸)、1,3,5-苯三曱酸(均苯三甲酸)、1,2,3,5-苯四曱酸(偏苯四甲酸) 、焦蜜石酸(均苯四曱酸)等「芳香族多元羧酸」;苯基 乙酸、氫阿托酸、氫桂皮酸、苦杏仁酸(苯乙醇酸)、苯 基琥珀酸、阿托酸、桂皮酸、桂皮酸甲酯、桂皮酸苯曱 酯、亞桂皮基乙酸、香豆酸、繳形酸等其他羧酸。S-46-201219977 The amount of addition of the decane coupling agent is preferably from 0.2% by mass to 5.0% by mass, more preferably from 0.5% by mass to 3.0% by mass, based on the total solid content of the coloring photosensitive composition of the present invention. %. (Development Accelerator) When the alkali solubility of the uncured portion of the coloring photosensitive composition layer is promoted and the developability of the coloring photosensitive composition is further improved, the development accelerator can be used for the coloring photosensitive composition. in. Such a development accelerator is an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1,000 or less. Specific examples thereof include "aliphatic monocarboxylic acids" such as capric acid, acetic acid, propionic acid 'butyric acid, shikimic acid, tridecyl acetic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid; oxalic acid and propylene Acid, boric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid (Brazil diacid), mercaptomalonic acid, ethyl propyl "aliphatic dicarboxylic acid" such as diacid, dimercaptomalonic acid, methyl succinic acid, tetramethyl succinic acid, citraconic acid; 1,2,3-propanetricarboxylic acid, aconitic acid, and bismuth "aliphatic tricarboxylic acid" such as tribasic acid; benzoic acid (benzoic acid), o-phthalic acid, dry acid, 2,3-dimercaptobenzoic acid, 3,5-dimercaptobenzoic acid, etc." Aromatic monocarboxylic acid"; phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,3,5-benzenetricarboxylic acid "Aromatic polycarboxylic acid" such as (isophthalic acid), 1,2,3,5-benzenetetradecanoic acid (p-tetracarboxylic acid), pyromic acid (pyromellitic acid); phenylacetic acid, Hydrogen ato acid, hydrogen cinnamic acid, bitter almond acid (phenylglycolic acid) Other succinic acid phenylmethyl group, atropic acid, cinnamic acid, cinnamic acid methyl ester, cinnamic acid benzyl ester Yue, cinnamylideneacetyl acid, coumaric acid, acid and the like pay-shaped.
S -47- 201219977 (熱聚合抑制齊|j ) 本發明著色感光性組成物中係以進一步預先添加熱 聚合抑制劑為佳’有用者為例如氫酿(h y d r 〇 q u i η ο n e)、對 曱氧基酚、二-三级丁基-對-甲酚、五倍子酚、三級丁基 兒茶紛、苯酿、4,4’-硫基雙(3_曱基-6-三級丁基齡)、2,2,-亞曱基雙(4 -曱基三級丁基酚)、2 -氫硫基苯并咪唑等。 (分散劑) 除上述以外’著色感光性組成物中可添加「顏料分 散組成物」項所述之顏料分散劑。 (其他添加劑) 可例舉玻璃、氧化鋁等填充劑;2-(3-三級丁基-5-曱基-2-羥基苯基)-5-氣苯并***、烷氧基二苯曱酮等紫 外線吸收劑;及聚丙烯酸納等解凝劑。 本發明著色感光性組成物係含有以上所述之各成分 ,即(A)鹵化辞酞菁素顏料、(B)具有酸基之聚合性單體 、(C)黏著劑樹脂、(D)光聚合起始劑、二級或三級脂 肪族硫醇化合物及(F)溶劑(甚或(G)敏化劑),旅可視需求 進一步添加混合界面活性劑等其他添加劑來調製。 <彩色濾光片及其製造方法> 本發明彩色滤光片係使用已述之本發明著色感光性 組成物,於玻璃.等基板上形成著色膜(著色圖案)來製作 ’例如可透過包含以下步驟之製造方法來製造:將本發 明著色感光性組成物塗布於基板上而形成著色層的著色 層形成步驟,針對該著色層對圖樣進行曝光以形成潛像 的曝光步驟,及使曝光後之著色層顯影而形成著色圖案 的顯影步驟。 -48- .201219977 ^著色層可於基板上直接或隔著其他層而提供,提供 著色層之方法可由旋轉塗布、狹縫塗布、流延塗布輥 塗布嘴墨塗布或轉印等方法來形成。可對所形成之著 色層隔著遮罩圖案進行曝光、曝光成圖案狀或使曝光部 分硬化後以顯影液使未曝光部分(未硬化部分)顯影並予 以去除而形成各色(例如3色或4色)著色圖案,藉此來 製作彩色濾光片。 由此,便能以較低之製程上的困難度、高品質且低 成本來製作液晶顯示裝置、圖像感測器所使用的彩色濾 光片。 此時’曝光時所採用之放射線除g線、h線、i線、 j線等紫外線之外,較佳為紫外光雷射等。 另外’曝光方式除鄰近曝光(proximity exposure)方 式、濺鍍曝光方式之外,亦可適當使用利用雷射光源之 曝光方式。 雷射曝光方式中係使用紫外光雷射作為光源。雷射 (LASER)為英語之 Light Amplification by Stimulated Emission of Radiation(激發放射所產生之光放大)的頭字 母縮略字。利用具反轉分布之物質中所產生的激發放射 現象’透過光波的放大、振堡而產生干涉性與指向性更 強之單色光的振盪器及放大器、激發媒介係有結晶、玻 璃 '液體、.色素、氣體等,由此等媒介,便可使用固體 雷射、液體雷射、氣體雷射、半導體雷射等週知之紫外 光中具有振盪波長的雷射。其中由雷射輸出及振盪波長 之觀點而言,較佳為固體雷射、氣體雷射。S-47-201219977 (Thermal polymerization inhibitory|j) The coloring photosensitive composition of the present invention is preferably further prepared by adding a thermal polymerization inhibitor in advance. For example, it is hydrogen hydrating (hydr 〇qui η ο ne), confrontation Oxyphenol, di-tertiary butyl-p-cresol, gallicol, tertiary butyl tea, benzene, 4,4'-thiobis(3_mercapto-6-tertiary butyl) , 2,2,-indenyl bis(4-indolyl tertiary butyl phenol), 2-hydrothiobenzimidazole, and the like. (Dispersant) In addition to the above, the pigment dispersant described in the item "Pigment Dispersion Composition" may be added to the colored photosensitive composition. (Other additives) A filler such as glass or alumina; 2-(3-tert-butyl-5-indenyl-2-hydroxyphenyl)-5-gasbenzotriazole or alkoxydiphenyl An ultraviolet absorber such as an anthrone; and a decondensing agent such as a polyacrylic acid. The colored photosensitive composition of the present invention contains the above-mentioned respective components, that is, (A) a halogenated phthalocyanine pigment, (B) a polymerizable monomer having an acid group, (C) an adhesive resin, and (D) light. A polymerization initiator, a secondary or tertiary aliphatic thiol compound, and (F) a solvent (or even a (G) sensitizer) may be further prepared by further adding a surfactant such as a mixed surfactant. <Color filter and method for producing the same> The color filter of the present invention is formed by using a coloring photosensitive composition of the present invention described above to form a colored film (colored pattern) on a substrate such as glass. A manufacturing method comprising the steps of: applying a coloring photosensitive composition of the present invention to a substrate to form a coloring layer forming step of the colored layer, exposing the pattern to the colored layer to form a latent image, and exposing the exposure layer The subsequent development step of developing the color layer to form a colored pattern. -48- .201219977 ^ The colored layer can be provided directly or through other layers on the substrate, and the method of providing the colored layer can be formed by spin coating, slit coating, cast coating roll coating, or transfer printing. The colored layer formed may be exposed, exposed to a pattern by a mask pattern, or the exposed portion may be hardened, and the unexposed portion (unhardened portion) may be developed and removed by a developing solution to form respective colors (for example, 3 colors or 4). Color) a coloring pattern by which a color filter is produced. As a result, the color filter used in the liquid crystal display device or the image sensor can be produced with a low degree of difficulty in processing, high quality, and low cost. At this time, the radiation used for the exposure is preferably an ultraviolet laser or the like in addition to ultraviolet rays such as g-line, h-line, i-line, and j-line. In addition, in addition to the proximity exposure method and the sputtering exposure method, an exposure method using a laser light source can be suitably used. In the laser exposure mode, an ultraviolet laser is used as a light source. Laser (LASER) is the English acronym of Light Amplification by Stimulated Emission of Radiation. An oscillator and an amplifier that excites a radiation phenomenon generated by a substance having a reversed distribution, which generates a monochromatic light having a higher interfering and directivity by amplifying and vibrating the light wave, and the excitation medium is a crystal, a glass liquid. , pigments, gases, etc., and thus, a medium having a laser having an oscillation wavelength among well-known ultraviolet light such as a solid laser, a liquid laser, a gas laser, or a semiconductor laser can be used. Among them, solid lasers and gas lasers are preferred from the viewpoint of laser output and oscillation wavelength.
S -49- 201219977 可用於本發明之雷射曝光之波長較佳為位在 300nm〜380nm之範圍的波長範圍的紫外光雷射,波長更 佳位在300nm〜360nm之範圍的紫外光雷射在符合著色 感光性組成物之感光波長方面較佳。 具體而言’特別適合使用輸出大且較為廉價之固體 雷射的Nd: YAG雷射的第三譜波(355nm)、準分子雷射 的 XeCl(308nm)、XeF(353nm)。 被曝光物(圖案)的曝光量為lmj/cm2〜1〇〇mJ/cm2之 範圍,較佳為lmJ/cm2〜50mJ/cm2之範圍。曝光量若為此 範圍,則以圖案形成的生產性方面而言較佳。S-49-201219977 The wavelength of the laser exposure which can be used in the present invention is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, and a laser having a higher wavelength in the range of 300 nm to 360 nm. It is preferable in terms of the photosensitive wavelength of the coloring photosensitive composition. Specifically, it is particularly suitable to use a third spectrum (355 nm) of a Nd:YAG laser that outputs a large and inexpensive solid laser, XeCl (308 nm) of a excimer laser, and XeF (353 nm). The exposure amount of the exposed object (pattern) is in the range of lmj/cm 2 to 1 〇〇 mJ/cm 2 , preferably in the range of lmJ/cm 2 to 50 mJ/cm 2 . If the amount of exposure is in this range, it is preferable in terms of productivity in terms of pattern formation.
可用於本發明之曝光裝置並無特殊限制,惟市售品 可使用Call is to (V Technology股份有限公司製)、EGIS(V Technology 股份有限公司製)或 dF2200G(DAINIPP〇N SCREEN股份有限公司製)等。又可適當使用上述以外之 裝置。 又可將發光二極體(LED)及雷射二極體(LD)用作活 性放射線源。特別是需要有紫外線源時可使用紫外LED 及紫外LD ^例如日亞化學(股)已上市主放射光譜為具有 365nm與420nm之間之波長的紫色LED。進一步需要更 短之波長時’美國專利號第6,084,250號說明書揭露有可 放出中心位於30〇nm與370nm之間的活性放射線的LED 。又’亦可購得其他紫外LED,而能夠照射紫外線帶域 不同的放射線。本發明中特佳之活性放射線源為UV — LED ’特佳者為於340〜370m具有峰值波長的UV-LED。 201219977 紫外先雷射因其平行度良好’於曝 用遮罩亦可拟闽+ ^ 次*之際即便未使 行曝光時,田団 田便用遮罩對圖案進 ^ ^ 升而更佳。 捉供(較佳為塗布)於基板上之本發 成物所形士 著色感光性組 =所化成之膜的乾燥(預烘烤)可利用如 ,於50〜Λ,、、、板、烘相寻 ⑥之溫度範圍、10〜300秒的條件下進行。 订員衫時’係使曝光後的未硬 液中而僅铱& 不兄化0Ρ分溶出於顯影 僅殘留硬化部分。顯影溫度一船 時間Α9Λπλ 飯為20〜3(TC’顯影 J馮20〜9〇秒。 頁〜液只要是使未硬化部分著 膜溶解 1刀 < 有巴感先性組成物的 具體而^另—方面未使硬化部分溶解者,任何皆可使用。 4 D,可使用各種有機溶劑的組合或鹼性水溶液。 成物:!有機溶劑可例舉:作為調製本發明顏料分散組 。5著色感光性組成物時可使用的已述溶劑而列舉者 、轳:述鹼性水溶液可例舉將例如氫氧化鈉、氫氧化鉀 鞍、次鈉、奴酸氯鈉、矽酸鈉、甲基矽酸鈉、氨水、乙 乙垵〜乙胺、二甲基乙醇胺、氫氧化四τ胺、氫氧化四 、膽鹼(Ch〇line)、吡咯、哌啶、丨,8二雜氮雙壤 L · 4 · 〇 】7 〇.〇〇1' — _十一稀等鹼性化合物溶解而使濃度為 0夤畺乂,較佳為〇 〇丨〜^質量%的驗性水溶液。 顯影此外,當使用鹼性水溶液作為顯影液時,一般係於 少竣以水清洗(沖洗,rinse)之。 〜舲顯影後,清洗除去剩餘之顯影液並實施乾燥之後, X係於MO〜250t 2溫度下實施加熱處理(後烘烤)。The exposure apparatus to be used in the present invention is not particularly limited, and commercially available products can be used by Call is to (V Technology Co., Ltd.), EGIS (manufactured by V Technology Co., Ltd.) or dF2200G (manufactured by DAINIPP〇N SCREEN Co., Ltd.). )Wait. Further, a device other than the above can be used as appropriate. A light-emitting diode (LED) and a laser diode (LD) can also be used as an active radiation source. In particular, ultraviolet LEDs and ultraviolet LDs can be used when an ultraviolet source is required. For example, Nichia Chemical Co., Ltd. has listed a main emission spectrum of a purple LED having a wavelength between 365 nm and 420 nm. Further, when a shorter wavelength is required, U.S. Patent No. 6,084,250 discloses an LED that emits active radiation centered between 30 〇 nm and 370 nm. In addition, other ultraviolet LEDs can be purchased, and different radiations in the ultraviolet band can be irradiated. Particularly preferred active radiation sources in the present invention are UV-LEDs, which are particularly preferred for UV-LEDs having a peak wavelength of 340 to 370 m. In 201219977, the UV-first laser has a good parallelism. When the exposure mask is also applied to ^ + ^ times*, even if the exposure is not performed, Tian Haotian uses a mask to improve the pattern. Capturing (preferably coating) the present invention on the substrate to form a color sensitive group = drying of the film formed (prebaking) can be used, for example, at 50~Λ,,,, plate, baking The temperature range of the phase 6 is 10 to 300 seconds. When ordering a shirt, it is made to expose the unhardened liquid and only the 铱& Development temperature a boat time Α9Λπλ rice is 20~3 (TC' development J von 20~9 〇 seconds. Page ~ liquid as long as the unhardened part of the film dissolves 1 knife < On the other hand, if the hardened portion is not dissolved, any one can be used. 4 D, a combination of various organic solvents or an aqueous alkaline solution can be used. The product: the organic solvent can be exemplified as a pigment dispersion group of the present invention. The solvent which can be used for the photosensitive composition is exemplified, and the alkaline aqueous solution may, for example, be sodium hydroxide, potassium hydroxide saddle, sub-sodium, sodium chlorate, sodium citrate or methyl hydrazine. Sodium, ammonia, ethyl acetoacetate, ethylamine, dimethylethanolamine, tetrahydrofurfurylamine, tetrahydric hydroxide, choline (Ch〇line), pyrrole, piperidine, hydrazine, 8 diaza double soil L · 4 · 〇] 7 〇.〇〇1' — _11 diluted basic compound is dissolved to a concentration of 0 夤畺乂, preferably 〇〇丨 ~ ^ mass % of the aqueous test solution. When an alkaline aqueous solution is used as a developing solution, it is generally washed with water (rinse). Ling After development, the developing solution and washed to remove residual embodiment, after drying, X-based heat treatment (post-baking) at a temperature MO~250t 2.
S -51 - 201219977 後烘烤為用以使硬化完全之 t抵,一 般係進仃約200。〇〜25〇t的加熱(硬烤 硌_理可 •對顯影後的塗布膜,以上述停件,:)。該後供烤 栎件使用加埶板、對流烘 相(熱風循環式乾燥機)、高 ‘、、 x ^貝力熱機寺加熱手段,以連 續式或分批(batch)式來進行。 以上λ?所要的色相數的方式’按各色依序重複進行 彩色遽光片。 …種色彩之硬化膜而成的 膜時當:::明著色感光性組成物提供至基板上而形成 厚度一般為0·3〜1.°_,較佳為〇·— 表佳為1.0〜2.5μηι。 基板可列舉例如液晶顯示裳置等所使用的盈驗玻璃 、鈉玻璃(soda glass)、Pyrex(註 及此等玻璃上附著有透明導電膜者/=、石英玻璃 等所使用的光電轉換元件基二二編 基板。此等基板上-般形成有用 =塑膠 紋。 合1素的黑色條 塑膠基板係以於其表 溶劑性層為佳。 面上具有氣體阻隔層 及/或耐 於基板上隔著其他層而提供著色感光性 其他層可例舉氣體阻隔層、耐溶劑性層等。 f [液晶顯示裝置] 為液晶顯示裝置用 的液日日I員示裝置可 本發明彩色濾光片係特別適合作 之彩色濾光片。具備此種彩色濾光片 顯示面品質之影像。 -52- 1 201219977 顯示震置的定義或各顯示裝置的說明係記載於例如 「電子顯不裝置(佐佐木昭夫著’工業調查會(股)’ 199〇 年發行)」、「顯示裝置(伊吹順章著,產業圖書(股),平 成7G年發行)」等。又,關於液晶顯示裝置係記載於例如 「次世代液晶顯示器技術(内田龍男編輯,工業調查會( 版)’ 1 994年發行)」。本發明可應用的液晶顯示裝置並 無特殊限制,可應用於例如上述「次世代液晶顯示器技 術」所記載之各種方式的液晶顯示裝置。 本發明彩色濾光片其中對彩色TFT方式的液晶顯示 裝置特別有效。關於彩色TFT方式的液晶顯示裝置,係 記载於例如「彩色TFT液晶顯示裝置(共立出版(股),1996 年發行)」。更且’本發明亦可適用於IPS等的橫電場驅 動方式、MVA等的畫素分割方式等視角放大的液晶顯示 裝置、或 STN、TN、VA、0CS、FFS 及 R_〇CB 等液晶 顯示裝置中。 又’本發明彩色濾光片亦可供明亮且高精細二 C〇A(Color-filter On Array)方式的液晶顯示裝置使用 若為COA方式的液晶顯示裝置時,對彩色濾光片層的j 求特性除如前述的一般要求特性之外’還需有對^間; 緣膜的要求特性’即低電容率及剝離液耐性。曰 晝素的硬化性 故可提两直 特別是剝離液 置。為滿足低 上設置樹脂被 本發明著色感光性組成物可形成著色 得以提升,且無缺陷或剝離、扭曲的畫素 接或間接設置於TFT基板上之著色層的, 耐性,而亦有用於COA方式的液晶顯示裴 電容率的要求特性’亦可於彩色濾光片層 臈〇S -51 - 201219977 Post-baking is used to make the hardening complete, usually about 200. 〇 ~25〇t heating (hard baking 硌 _ 可 • For the coated film after development, to stop the above, :). The post-bakeware is carried out in a continuous or batch manner using a twisting plate, a convection drying phase (hot air circulation dryer), a high ‘, and a x ^Beli heat machine temple heating means. In the above manner, the number of hue numbers required for λ is repeated by color grading in order of color. When a film of a hardened film of color is used::: a brightly colored photosensitive composition is provided on the substrate to have a thickness of generally 0.3·1 to 1.°, preferably 〇·− is preferably 1.0~ 2.5μηι. Examples of the substrate include a glass of a liquid crystal display, a soda glass, and a Pyrex (a photoelectric conversion element base used for a transparent conductive film/such as quartz glass or the like). Two or two braided substrates. These substrates are generally formed with useful = plastic grain. The black strip plastic substrate is suitable for its solvent-based layer. It has a gas barrier layer on the surface and/or is resistant to the substrate. Other layers may be provided to provide coloring sensitivity. The gas barrier layer, the solvent resistant layer, and the like may be exemplified. f [Liquid Crystal Display Device] The liquid color Japanese I member device for the liquid crystal display device may be the color filter system of the present invention. It is especially suitable for color filters. It has the image quality of such a color filter. -52- 1 201219977 The definition of the display shake or the description of each display device is described in, for example, "Electronic display device (Sasaki Sasaki) "Industrial investigations (shares) 'released in the year of 199), "display devices (Ibuki Shun, industrial books (shares), issued in Heisei 7G)", etc. For example, "Next Generation Liquid Crystal Display Technology (Editor Uchida Natsuo, Industrial Survey (version)" issued in 1994). The liquid crystal display device to which the present invention is applicable is not particularly limited and can be applied to, for example, the above-mentioned "next generation liquid crystal display technology". Various types of liquid crystal display devices are described. The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described, for example, in a "color TFT liquid crystal display device". In addition, the present invention can also be applied to a liquid crystal display device such as a horizontal electric field driving method such as IPS or a pixel division method such as MVA, or an STN, TN, or VA. In the liquid crystal display devices such as 0CS, FFS, and R_〇CB, the color filter of the present invention can also be used as a COA for a bright and high-resolution liquid crystal display device of a color-filter on Array type. In the case of the liquid crystal display device of the mode, the characteristics of the color filter layer are required to be different from the above-mentioned general requirements. 'The low capacitance rate and the resistance of the stripping liquid. The hardenability of the alizarin can be raised, especially the stripping liquid. In order to satisfy the low setting resin, the coloring photosensitive composition of the present invention can be colored, and the color can be improved without Defects or peeling, distortion of the pixel or indirect setting of the coloring layer on the TFT substrate, and the required characteristics of the liquid crystal display tantalum permittivity for the COA mode can also be applied to the color filter layer.
S -53- 201219977 為了進一步在;;{ A、y» 仕化成為COA方式之彩色濾光片用的著 色層上’使配置於荽A & 、考色層上的ITO電極與著色層下方的驅 動用TFT基板的域+ 们而子導通,則需形成邊長為1〜1 5 μιη左右 的矩形導通孔,戎县「 〜· _ 4疋〕」字型凹槽等導通路徑,使導通 路徑的尺寸(即邊具、炎 、 您我)為5μιη以下時較佳,惟使用本發明著 色感光性組成物亦可形Α 5μιη以下料通路徑。 關於此等影像顯示方式,係記載於例如「EL、PDP LCD顯不器-技術暨市場之最新動向·(東麗研究中心調 查研究7門,2001年發行)」之〇頁等。 本發明液晶顯示裝置除本發明彩色濾光片以外,還 由電極基板、❺光膜、相位差膜、t光源、間隔件、視 角補償膜等各種構件構成。本發明彩色濾光片可應用於 以此等週知構件構成的液晶顯示裝置中。 關於此等構件係記載於例如「1 994年液晶顯示器周 邊材料、化學品之市場(島健太郎,CMC (股),1994年 發行)」、「2003年液晶相關市場之現況暨未來展望(下 卷)(表良。’ Fuji Chimera Research Institute(股),2003 年發行)」。 關於背光源係記載於SID meeting Digest 1380 (2005)(Α·Κοηηο 等人)、月刊 DISPLAY,2005 年 12 月號 之18〜24頁(島康裕)’同25〜3〇頁(八木隆明)等。 若將本發明彩色濾光片用於液晶顯示裝置,則與以 往週知之冷陰極管的三波長管組合時可獲得高對比,而 進一步將紅、綠、藍led光源(rgb-led)作為背光源, 便可提供輝度高且色純度高之色再現性良好的液晶顯示 裝置。S -53- 201219977 In order to further the ITO electrode and the coloring layer disposed on the 荽A & color layer, the {A, y» is turned into a coloring layer for COA color filters When the drive is turned on by the domain of the TFT substrate, it is necessary to form a rectangular via hole having a side length of about 1 to 15 μm, and a conduction path such as a "~· _ 4疋" font groove of the Gifu County to make the conduction. It is preferable that the size of the path (i.e., the side, the inflammation, the self and the user) is 5 μm or less, but the coloring photosensitive composition of the present invention can also be used to form a material passage path of 5 μm or less. The image display methods are described in, for example, "EL, PDP LCD Display - The Latest Trends in Technology and Markets (7 pages from Toray Research Center, and released in 2001)". The liquid crystal display device of the present invention comprises, in addition to the color filter of the present invention, various members such as an electrode substrate, a calender film, a retardation film, a t light source, a spacer, and a viewing angle compensation film. The color filter of the present invention can be applied to a liquid crystal display device constituted by such a known member. These components are described, for example, in "The Market of Liquid Crystal Display Peripherals and Chemicals in 1999 (Island Kentaro, CMC (Shares), Issued in 1994)", "2003 Liquid Crystal Related Markets and Future Outlook (Volumes) ) (Former Liang. 'Fuji Chimera Research Institute (share), issued in 2003). The backlight is described in SID meeting Digest 1380 (2005) (Α·Κοηηο et al.), monthly publication DISPLAY, December 2005, pages 18 to 24 (Island Kangyu), and the same 25~3 page (Yamamu Longming), etc. . When the color filter of the present invention is used in a liquid crystal display device, high contrast can be obtained when combined with a conventional three-wavelength tube of a cold cathode tube, and a red, green, and blue led light source (rgb-led) is further used as a backlight. The source can provide a liquid crystal display device having high luminance and high color purity with good color reproducibility.
S -54- 201219977 [實施例] 以下,以實施例對本發明更具體地進行說明,惟非 限於以下實施例。此外,除非特別事先說明,否則「% 」、「份」為質量基準。 -鹵化鋅酞菁素顏料的合成- 以酞腈、氯化鋅為原料來製造鋅酞菁素。 _化反應係將硫醯氯3 · 1份、無水氯化铭3 · 7份、氯 化鈉0.46份、辞酞菁素!份於4〇t下混合,並滴入溴 2.2份而進行。於8 〇艺下反應1 5小時後,將反應混合物 置入水中以使部分溴化鋅酞菁素粗製顏料析出。將該水 性漿料過遽’進行8 0。(3的熱水清洗並於9 0 °C下予以乾燥 ’即製得2.6份之經精製的部分溴化鋅酞菁素粗製顏料 〇 將遠部分漠化鋅酞菁素粗製顏料1份、粉碎氣化鈉 7份、二乙二醇i .6份、二曱苯〇 〇9份加入至雙臂混練 機(Double Arm Kneader)中,於100。〇下進行混練6小時 。混練後取出至8(TC的水1 〇〇份中並攪拌1小時後,經 過濾、熱水清洗、乾燥、粉碎即製得部分溴化辞酞菁素 顏料。 由根據質譜分析的!|素含量分析,所得之部分溴化 鋅酜菁素顏料其平均組成為ZnPcBr1()Cl4H2(Pc為駄菁素 ),1分子中平均含有1 〇個漠。 此外’以穿透式電子顯微鏡(曰本電子(股)製 JEM-2010)所測定之一次粒徑的平均値為〇.〇65μιη。S - 54 - 201219977 [Examples] Hereinafter, the present invention will be more specifically described by way of examples, but not limited to the following examples. In addition, "%" and "parts" are quality benchmarks unless otherwise stated in advance. - Synthesis of a zinc halide phthalocyanine pigment - A zinc phthalocyanine is produced using phthalonitrile or zinc chloride as a raw material. The chemical reaction system consists of 3 · 1 part of thiopurine chloride, 3 · 7 parts of anhydrous chlorination, 0.46 parts of sodium chloride, and phthalocyanine! The mixture was mixed at 4 Torr and dropped into 2.2 parts of bromine. After reacting for 15 hours at 8 ° C, the reaction mixture was placed in water to precipitate a part of the crude zinc bromide phthalocyanine pigment. The aqueous slurry was passed through 遽' (3 hot water is washed and dried at 90 ° C) to obtain 2.6 parts of purified crude zinc bromide phthalocyanine pigment pigment, which will be partially deserted, zinc phthalocyanine crude pigment 1 part, crushed 7 parts of sodium vapor, 2 parts of diethylene glycol, and 6 parts of diphenyl hydrazine were added to a double arm kneader (Double Arm Kneader), and kneaded for 6 hours under the armpit. After mixing, take it to 8 (After stirring for 1 hour in 1 part of water of TC, it is filtered, hot washed, dried, and pulverized to obtain a partially brominated quinone pigment. According to the mass spectrometry analysis, the obtained content is obtained. Part of the zinc bromide phthalocyanine pigment has an average composition of ZnPcBr1()Cl4H2 (Pc is phthalocyanine), and an average of 1 漠1 desert in one molecule. In addition, it is made by a transmission electron microscope (Sakamoto Electronics Co., Ltd.). The average enthalpy of the primary particle diameter measured by JEM-2010) is 〇.〇65 μιη.
S -55- 201219977 -喹啉黃化合物的合成- 一面攪拌喹啉黃顏料(4,5,6,7-四氣-2-[2-(4,5,6,7-四 氯-2,3-二氫·1,3-二側氧_1H•茚-2_基卜8_喹啉基]-1H-異 吲哚-1,3(2H)-二酮)(baSF 公司製「Paliodol」黃 K0961HD)10g, 一面將其置入15〇c的發煙硫酸 (25%SO3)130g中。攪拌3小時後,添加炱冰250g上。 放置30分鐘後,將生成的懸浮液過濾,旅以水50ml清 洗所得之生成物。將前述生成物置入水33〇ml中,並以 氨水溶液中和(添加氨水溶液至pH為7)之。添加氯化銨 75g,於80。(:下攪拌30分鐘並將所析出之沉澱物於60t 製得1 7 g之嗤咐黃何 對該喹琳黃彳疗& 小時的熱處理,卽制 所得之濕結晶後,於80 C下乾燥,即 $何生物之磺化物的銨鹽。 h生物之磺化物的銨鹽於1 8 0 °c下實施3 印製得經去除銨鹽之喹淋黃衍生物之磺 化合物4)16g(產率94%)。 化物(下述構造之化 H〇3S\八八匕S -55- 201219977 - Synthesis of quinoline yellow compound - stirring quinoline yellow pigment (4,5,6,7-tetraki-2-[2-(4,5,6,7-tetrachloro-2, 3-Dihydro-1,3-di-dioxy-1H•茚-2_kib-8_quinolinyl]-1H-isoindole-1,3(2H)-dione) (Paliodol, manufactured by BaSF Corporation) 10g yellow K0961HD), placed in 15g of fuming sulfuric acid (25% SO3) in 15〇c. After stirring for 3 hours, add 250g of ice. After 30 minutes, filter the resulting suspension, travel The obtained product was washed with 50 ml of water, and the product was placed in 33 ml of water, and neutralized with an aqueous ammonia solution (addition of an aqueous ammonia solution to pH 7). 75 g of ammonium chloride was added thereto at 80°. Minutes and precipitated the precipitate at 60t to obtain 17 g of yttrium and heat treatment of the quinoline jaundice & hour after the wet crystallization obtained, and dried at 80 C, ie, The ammonium salt of the sulfonate of the organism. The ammonium salt of the sulfonate of the organism is carried out at 180 ° C. 3 The sulfonate compound of the quinone-removing yellow derivative of the ammonium salt is removed. 4) 16 g (yield 94%) Compound (the following structure of H〇3S\八八匕)
ci Cl 於氯仿、冰浴中 對磺化物(化合物4)10g添加草醯氣 2g及N,N-二曱基甲醯胺(和光純藥 (和光純藥公司製)2CiCl was added to sulfonate (Compound 4) 10 g of oxalic acid (2 g) and N,N-dimercaptocarboxamide (Wako Pure Chemicals Co., Ltd.) 2
S -56- 201219977 公司製)lm卜並於5〇〇C下攪拌2小味认丄丄 七 • τ z小訏。於冰浴中將反應 混合液添加至水1 5 0 m 1中,再將杯山 丹时析出之結晶過濾即製得 磺醯氣化合物(下述構造之化合物4 + 〇 初 5)7.4g。(產率 72%) CI、/S -56- 201219977 Company system) lm and stir at 5 ° C 2 small tastes 七 • • τ z small 訏. The reaction mixture was added to water 150 ml in an ice bath, and the crystals precipitated from the cup was filtered to obtain 7.4 g of a sulfonium gas compound (Compound 4 + 初 5 of the following structure). (yield 72%) CI, /
〇〇
CI (化合物5) 於氣仿、冰浴中對化合物5 5 〇g添加6_氣_1_己胺 (Rare Chemicals公司製)0.9g,並於室溫下攪拌、2小時。 將反應混合液添加至水150ml中,再將析出之結晶過滤 並進行水洗’於減壓下乾燥後即製得磺醯胺氯烧°化@^物\ 下述構造之化合物6)4.3g。(產率76%) 01. HN, 9CI (Compound 5) 0.9 g of 6-gas-1-hexylamine (manufactured by Rare Chemicals Co., Ltd.) was added to the compound 5 5 〇g in a gas bath and an ice bath, and stirred at room temperature for 2 hours. The reaction mixture was added to 150 ml of water, and the precipitated crystals were filtered and washed with water. After drying under reduced pressure, the compound (6) of the compound of the following structure: 4.3 g of sulfonamide chloride was obtained. (yield 76%) 01. HN, 9
0C卜-CI Ν0C卜-CI Ν
•尸 〇Η〇• corpse
丨 (化合物6) ΛCl丨 (Compound 6) ΛCl
S -57- 201219977 對化σ物6 4.3 g以過量添加水與無水亞硫酸鈉(關 東化孥製)’並於向壓釜中、18〇。。下加熱12小時。靜置 冷卻後,將結晶過據即製得磺醯胺烷基磺酸化合物(下述 1冓〇為之化合物7)3‘7g。(產率82%)S-57-201219977 Condensed sigma 6 4.3 g was added in excess with water and anhydrous sodium sulfite (manufactured by Kanto Chemical Co., Ltd.) and placed in an autoclave at 18 Torr. . Heat for 12 hours. After standing to cool, the sulfonamide alkylsulfonic acid compound (Compound 7 below) 3 '7 g was obtained by crystallizing. (yield 82%)
hnn P α、 "%, \Hnn P α, "%, \
N Ο ΛN Ο Λ
ClCl
户〇HOToho HO
CI (化合物7)CI (Compound 7)
CICI
Cl CI α -樹脂(J-1)的合成-(1)樹脂(丨-1)的合成 混合正辛酸 6 C! 4g、ε-己内酯 200g及四丁氧基鈦 (IV)5g,於 160°C 下 a 加熱8小時後,冷卻至室溫即製得聚 酯樹脂(i-Ι)。 0 少0Synthesis of Cl CI α -Resin (J-1) - (1) Synthesis of Resin (丨-1) Mixed with n-octanoic acid 6 C! 4g, ε-caprolactone 200g and tetrabutoxytitanium (IV) 5g After heating at 160 ° C for 8 hours, it was cooled to room temperature to obtain a polyester resin (i-Ι). 0 less 0
合成簡圖係以下所示 0 + Η0-^07Ηΐ5.η Tt(OBu)4 ΟThe synthetic sketch is shown below. 0 + Η0-^07Ηΐ5.η Tt(OBu)4 Ο
〇 II ^Ηί5-Π 40 (2)樹脂(J-1)的合成 混合聚乙烯亞胺(SP-(H8,數量平均分子量ijoo, 曰本觸媒製)10g及聚酯樹脂(i_1)1〇〇g,於l2〇〇c下加熱3 小時而製得中間體(J_1B) ^其後,靜置冷卻至65t,再〇II ^Ηί5-Π 40 (2) Synthesis of Resin (J-1) Mixed Polyethyleneimine (SP-(H8, number average molecular weight ijoo, manufactured by Nippon Shokubai) 10g and polyester resin (i_1) 1〇 〇g, heated at l2〇〇c for 3 hours to obtain intermediate (J_1B) ^, then left to cool to 65t, then
S 58- 201219977 缓緩添加含有無水琥珀酸3.8g之丙二醇曱醚己酸酿(以 下稱為PGMEA)200g並攪拌2小時。爾後,添加PGMEA 即製得樹脂(J-1)之PGMEA 10%溶液。樹脂(J-i)係具有來S 58-201219977 200 g of propylene glycol hexanoic acid caproic acid (hereinafter referred to as PGMEA) containing 3.8 g of anhydrous succinic acid was slowly added and stirred for 2 hours. Thereafter, PGMEA was added to prepare a PGMEA 10% solution of the resin (J-1). Resin (J-i) has come
〇 酯樹脂(i-1)之側鏈與來自無水琥珀酸之羧基 合成簡圖係以下所示。 Ο 聚乙烯亞胺 ^~~Ο^Η-ις-Π + 40 ^ -^CH2CH2-Ni|1 ^~L,A schematic diagram of the side chain of the oxime ester resin (i-1) and the carboxyl group derived from anhydrous succinic acid is shown below.聚乙烯 Polyethyleneimine ^~~Ο^Η-ις-Π + 40 ^ -^CH2CH2-Ni|1 ^~L,
OT 0 +ch2ch2-n|12 C7H15-n Η --CH2〇H2-NH2]-(Ti2 >〇fJk^^O-|^-C7H15-n 八〜〇切 [CH2CH2-NH2 〇ν。 U^O 中間體(J-1B) fcH2CH2-N^< fcH2CH2-N-jji 〇 -fcH2CH2^-)-| 〇' 卜 C7H15-n αOT 0 +ch2ch2-n|12 C7H15-n Η --CH2〇H2-NH2]-(Ti2 >〇fJk^^O-|^-C7H15-n 八~〇切[CH2CH2-NH2 〇ν. U^ O Intermediate (J-1B) fcH2CH2-N^< fcH2CH2-N-jji 〇-fcH2CH2^-)-| 〇' Bu C7H15-n α
Ή η ΗΉ η Η
、C09H -f-CH2CH2-NH2)-mi -fcH2CH2-NH2j-m2 +CH2CH2-NH土 樹脂(J-l) -含部分漠化鋅酿菁素顏料之分散組成物的調製- 混合前述部分溴化鋅酞菁素顏料(以下稱為 PG58)1 1.9份、作為喹啉黃化合物之化合物7 31份 '作 為分散劑之Solsperse 24〇〇OGR(日本Lubriz〇1公司製)9 〇 份、作為溶劑之PGMEA 76份後,用砂研磨機以3小時 予以分散,即製得含部分溴化鋅酞菁素顏料之顏料分散 組成物。以E型黏度計RE_85L(東機產業(股)製)於溫度, C09H -f-CH2CH2-NH2)-mi -fcH2CH2-NH2j-m2 +CH2CH2-NH earth resin (Jl) - Preparation of a dispersion composition containing a partially desertified zinc phthalocyanine pigment - mixing the aforementioned part of zinc bromide 1 1.9 parts of a phthalocyanine pigment (hereinafter referred to as PG58), 31 parts of a compound 7 as a quinophthalone compound, and 2 parts of Solsperse 24 〇〇 OGR (manufactured by Nippon Lubriz Co., Ltd.) as a dispersing agent, PGMEA 76 as a solvent After the portion was dispersed by a sand mill for 3 hours, a pigment dispersion composition containing a part of the zinc bromide phthalocyanine pigment was obtained. E-type viscometer RE_85L (made by Toki Sangyo Co., Ltd.) at temperature
S -59- 201219977 23 C下測定所得之顏料分散組成物之黏度的結果為 9.2mPa · s而甚為穩定,可確認獲得良好的分散穩定性 保存條件.分散後1 4天(保存溫度5。〇) -含黃色顏料ΡΥ15〇之分散組成物的調製- 將作為顏料之C.I_顏料黃15〇(平均1次粒徑6〇nrn)( 以下稱為ΡΥ1 50)40份、與前述樹脂(:1)之pGMEA 1〇% 浴液223份(以固體成分換算為22 3份)的混合液用珠粒 磨機(氧化結珠粒〇.3mm)以3小時予以混合、分散,即 調製出含黃色顏料PY1 50之分散組成物。 -含黃色顏料PY138之分散組成物的調製_ 將作為顏料之C.I.顏料黃138(平均1次粒徑60nm)( 以下稱為PY1 38)40份、與前述樹脂(j_丨)之pgmeA 10% 溶液223份(以固體成分換算為22·3份)的混合液以珠粒 磨ϋ (氧化錯珠粒〇. 3 ru m)以3小時予以混合、分散,即 調製出含黃色顏料PY1 38之分散組成物。 -作為光聚合起始劑之化合物1的合成_ (1)化合物A的合成 首先,以下述簡圖來合成化合物A。 將乙基咔岐(lOO.Og,〇.5 12mol)溶於氯苯26〇mi中並 冷卻至(TC後’添加氣化鋁(70.3g,〇.527m〇i)。接著,以 刀I里滴入鄰甲本基氣(81_5g,〇·527ιη〇1),升溫至室溫 並攪拌3小時。次之,冷卻至〇它後,添加氯化鋁(75 lg ,〇_5 63mol)。以 40 分鐘滴入 4-氯 丁醯氯(79 4g,〇 563m〇1) ,升溫至室溫益攪拌3小時。將35質量%鹽酸水溶液 1 5 6 m 1與療館水3 9 2 m 1的混合溶液冷卻至〇。〇,並滴入反S-59-201219977 23 The viscosity of the obtained pigment dispersion composition was measured and found to be 9.2 mPa·s, which was stable, and it was confirmed that good dispersion stability storage conditions were obtained. The storage temperature was 5 days after storage. 〇) - Preparation of a dispersion composition containing a yellow pigment ΡΥ 15 - - 40 parts of C.I_Pigment Yellow 15 〇 (average primary particle size 6 〇nrn) (hereinafter referred to as ΡΥ1 50) as a pigment, and the above resin (:1) pGMEA 1〇% 223 parts of the bath (22 3 parts in terms of solid content) was mixed and dispersed in a bead mill (oxidized bead 〇.3 mm) for 3 hours. A dispersion composition containing the yellow pigment PY1 50 was obtained. - Preparation of a dispersion composition containing yellow pigment PY138 - 40 parts of CI Pigment Yellow 138 (average primary particle diameter 60 nm) (hereinafter referred to as PY1 38) as a pigment, and pgmeA 10% of the above resin (j_丨) A mixture of 223 parts (in terms of solid content: 22.3 parts) of the solution was mixed and dispersed in a bead granule (oxidized wrong bead 〇. 3 ru m) for 3 hours to prepare a yellow pigment containing PY1 38. Disperse the composition. - Synthesis of Compound 1 as Photopolymerization Initiator_ (1) Synthesis of Compound A First, Compound A was synthesized by the following scheme. Ethyl hydrazine (100.Og, 12.5 12 mol) was dissolved in chlorobenzene 26 〇mi and cooled to (after TC 'addition of vaporized aluminum (70.3 g, 〇. 527 m〇i). Next, with knife I Neighboring base gas (81_5g, 〇·527ιη〇1) was added dropwise, and the mixture was heated to room temperature and stirred for 3 hours. Next, after cooling to 〇, aluminum chloride (75 lg, 〇_5 63 mol) was added. 4-chlorobutyric acid chloride (79 4g, 〇563m〇1) was added dropwise in 40 minutes, and the temperature was raised to room temperature for 3 hours. The 35 mass% hydrochloric acid aqueous solution was 156 m 1 and the therapeutic water was 3 9 2 m 1 The mixed solution is cooled to 〇.〇, and dropped into the opposite
-60- S 201219977 應溶液。將析出之固體吸引過濾後,以蒸餾水與甲醇清 洗之,再以乙腈使其再結晶後即製得下述構造之化合物 A(回收量164.4g,產率77%)。-60- S 201219977 should be a solution. The precipitated solid was suction-filtered, washed with distilled water and methanol, and recrystallized from acetonitrile to obtain Compound A (recovery amount: 164.4 g, yield: 77%).
(2)化合物B的合成 次之,利用化合物A以下述簡圖來合成化合物B。 將化合物 A(20.0g,47.9mmol)溶於 THF 64ml,並添 加 4-氯苯硫醇(7_27g,50.2mmol)與蛾化鈉(0_7g, 4.79mmol)。接著對反應液添加氫氧化鈉(2,0g,50.2mmol) 並進行迴流2小時。次之,冷卻至0°C後,以20分鐘滴 入SM-28(ll.lg,57.4mmol),升溫至室溫並攪拌2小時 。次之,冷卻至0°C後,以20分鐘滴入亞硝酸異戊酯(6.73g ,57.4mmol),升溫至室溫並攪拌3小時。於丙酮120ml 中將反應液稀釋,並將其滴入冷卻至0 °C的0.1 N鹽酸水(2) Synthesis of Compound B Next, Compound B was synthesized using Compound A in the following scheme. Compound A (20.0 g, 47.9 mmol) was dissolved in THF (64 ml), and 4-chlorobenzenethiol (7-27 g, 50.2 mmol) and sodium moth (0-7 g, 4.79 mmol) were added. Sodium hydroxide (2,0 g, 50.2 mmol) was added to the reaction mixture, followed by reflux for 2 hours. Next, after cooling to 0 ° C, SM-28 (ll.lg, 57.4 mmol) was added dropwise thereto over 20 minutes, and the mixture was warmed to room temperature and stirred for 2 hours. Next, after cooling to 0 ° C, isoamyl nitrite (6.73 g, 57.4 mmol) was added dropwise thereto over 20 minutes, and the mixture was heated to room temperature and stirred for 3 hours. The reaction solution was diluted in 120 ml of acetone and dropped into 0.1 N hydrochloric acid water cooled to 0 °C.
S -61 - 201219977 溶液中。將析出之固體吸引過濾後,以蒸餾水清洗之。 接著,以乙腈使其再結晶即製得下述構造之化合物B(回 收量17.0g,產率64%)。S -61 - 201219977 In solution. The precipitated solid was suction filtered, and washed with distilled water. Then, it was recrystallized from acetonitrile to obtain Compound B of the following structure (recovery amount: 17.0 g, yield: 64%).
HSHS
CI THF NaOH NalCI THF NaOH Nal
SM-28SM-28
ΟΝΟ THFΟΝΟ THF
化合物Β (3)化合物C的合成 接著,利用化合物B以下述簡圖來合成作為起始劑 之化合物C。 將化合物B(18.0g,32.4mmol)溶於90ml之Ν -甲基 0比σ各咬酮,並添加三乙胺(3 · 9 4 g,3 8.9 m m ο 1)。次之,冷 卻至0°C後,以20分鐘滴入乙醯氯(3.05g,38.9mmol)之 後,升溫至室溫並攪拌2小時。將反應液滴入冷卻至0°C 的蒸德水 150ml中,將析出之固體吸引過濾、(suctionCompound Β (3) Synthesis of Compound C Next, Compound C as a starter was synthesized using Compound B in the following scheme. Compound B (18.0 g, 32.4 mmol) was dissolved in 90 ml of hydrazine-methyl 0 to sigma ketone, and triethylamine (3 · 9 4 g, 3 8.9 m ο 1) was added. Next, after cooling to 0 ° C, ethyl ruthenium chloride (3.05 g, 38.9 mmol) was added dropwise thereto over 20 minutes, and the mixture was warmed to room temperature and stirred for 2 hours. The reaction solution was dropped into 150 ml of steamed water cooled to 0 ° C, and the precipitated solid was sucked and filtered, (suction
-62- S 201219977 filtration)後,以冷卻至0°C的異丙醇200ml清洗並乾燥 後,即製得下述構造之化合物C(回收量19.5g,產率99%)After -62-S 201219977 filtration), it was washed with 200 ml of isopropanol cooled to 0 ° C and dried to obtain Compound C of the following structure (recovery amount 19.5 g, yield 99%)
[實施例1] <著色感光性組成物的調製> 攪拌混合下述組成1所示之成分來調製實施例1之 著色感光性組成物。 (組成1) .含PG58之顏料分散組成物 33.0份 •含PY150之顏料分散組成物 15.2份 •溶劑(PGMEA) 20.1 份 •溶劑(3 -乙氧基丙酸乙酯) 24.6份 •黏著劑樹脂(甲基丙烯酸烯丙酯-甲基丙烯酸(=共聚合 莫耳比8 : 2)共聚合物,重量平均分子量30000) 0.78 份 -63- 201219977 .聚合性單體:ARONIX M-520(東亞合成(股)製) 4.43 份 •光聚合起始劑:2-氯苯基-4,5-雙苯基咪唑二聚體(B-CIM ,HADOGAYA CHEMICAL(股)製) 0.14 份 •光聚合起始劑:IRGACURE OXE01(Ciba Speciality Chemicals(股)製,下述構造) 1.47份 •脂肪族硫醇化合物:Karenz MT-BD1 (丁二醇雙(3-氫硫 基丁酸酯,昭和電工(股)製 0·19份 •光敏化劑:化合物8(下述構造) 0.042份[Example 1] <Preparation of coloring photosensitive composition> The coloring photosensitive composition of Example 1 was prepared by stirring and mixing the components shown in the following composition 1. (Composition 1) 33.0 parts of pigment dispersion composition containing PG58 • Pigment dispersion composition containing PY150 15.2 parts • Solvent (PGMEA) 20.1 parts • Solvent (ethyl 3-ethoxypropionate) 24.6 parts • Adhesive resin (Allyl methacrylate-methacrylic acid (= copolymerized molar ratio 8 : 2) copolymer, weight average molecular weight 30000) 0.78 parts -63 - 201219977 . Polymerizable monomer: ARONIX M-520 (East Asian synthesis) (share) system 4.43 parts • Photopolymerization initiator: 2-chlorophenyl-4,5-bisphenylimidazole dimer (B-CIM, manufactured by HADOGAYA CHEMICAL Co., Ltd.) 0.14 parts • Photopolymerization initiation Agent: IRGACURE OXE01 (manufactured by Ciba Speciality Chemicals Co., Ltd., the following structure) 1.47 parts • Aliphatic thiol compound: Karenz MT-BD1 (butanediol bis(3-hydroxythiobutyrate, Showa Denko) 0. 19 parts • Photosensitizer: Compound 8 (structure described below) 0.042 parts
.界面活性劑(氟系界面活性劑,DIC公司製MEGAFAC .03 3 份 F781-F). Surfactant (fluorine-based surfactant, MEGAFAC.03 3 parts F781-F manufactured by DIC Corporation)
IRGACURE ΟΧΕ-01IRGACURE ΟΧΕ-01
(化合物8) -64 - 201219977 <使用著色感光性組成物之著色圖案的形成> -著色感光性組成物層的形成_ 將所得之著色感光性組成物以狹缝塗布法塗布於玻 ¥ 基板(CORNING 公司製 Millennium ,'厚0.7mm)上。具 體而言’係調節狹縫噴嘴與基板的間隔、排出量並以塗 布速度120mm/秒而予以塗布成後烘烤後之著色組成物 層的膜厚為約2.4μιη。 -預烘烤步驟- 次之’以真空乾燥裝置,使真空度達到66Pa為止將 色感光性組成物層乾燥後,利用加熱板於9〇t下進行加 熱(預烘培處理)12〇秒。 -曝光步驟(鄰近曝光)_ 貫施預烘烤處理後,利用鄰近曝光機(Hitachi High-Technologies 公司製 LE5565A),以 40mJ/cm2 進行 曝光。 -顯影步驟、烘烤(後烘烤)步驟_ 其後’利用顯影裝置(Hitachi High-Technologies公 司製)’以氫氧化鉀系顯影液CDK-1(FUJIFILM Electronic(Compound 8) -64 - 201219977 <Formation of a coloring pattern using a coloring photosensitive composition> - Formation of a coloring photosensitive composition layer _ The obtained coloring photosensitive composition is applied to a glass by a slit coating method. The substrate (Millennium, manufactured by CORNING Corporation, 'thickness 0.7 mm). Specifically, the thickness of the coloring composition layer after the interval between the slit nozzle and the substrate and the discharge amount was adjusted to a coating speed of 120 mm/sec to be post-baked was about 2.4 μm. - Prebaking step - Next, the photosensitive composition layer was dried by a vacuum drying apparatus to a vacuum of 66 Pa, and then heated (prebaked) at 9 Torr for 12 seconds using a hot plate. - Exposure step (adjacent exposure) _ After the prebaking treatment, exposure was carried out at 40 mJ/cm 2 using a proximity exposure machine (LE5565A manufactured by Hitachi High-Technologies Co., Ltd.). - Developing step, baking (post-baking) step _ thereafter 'Using a developing device (manufactured by Hitachi High-Technologies Co., Ltd.)' with a potassium hydroxide-based developing solution CDK-1 (FUJIFILM Electronic
Materials(股)製)之ι·0%顯影液(將cDK-丨丨份、純水99 知稀釋所得之液體,25°C )並設噴淋壓力〇.2MPa來進行 顯影60秒,再以純水清洗之。 充分乾燥後’於2 3 0 °C烘箱中進行後烘烤4 0分鐘。 (霄施例2~ 1 2、比較例1〜8) 將實施例1之組成1中顏料分散組成物、聚合性單 體、光聚合起始劑、鏈轉移劑(脂肪族硫醇化合物)的種ι·0% developer (made of cDK-丨丨份, pure water 99, diluted at 25 ° C) and set the spray pressure 〇 2 MPa for development for 60 seconds, and then Pure water cleaning. After thorough drying, post-baking was carried out in an oven at 230 ° C for 40 minutes. (Examples 2 to 2, Comparative Examples 1 to 8) The pigment dispersion composition, the polymerizable monomer, the photopolymerization initiator, and the chain transfer agent (aliphatic thiol compound) of the composition 1 of Example 1 were used. Species
S -65- 201219977 類改為如表i所記載,除此 — 方式來調製實施例2〜丨2及比 ’、以與實施例1同樣的 成物。 交例1〜8之各著色感光性組 除利用所得之各著色感光 t的曝光方式改為如表丨所f 、、且成物,並將曝光步驟 同樣的方式來製作著色圖案。载M外,係以與實施例1 表1中,顏料分散組成物 料分散組成物。 ’、9以顏料名稱表示的顏 為二,广1中記為「鄰近」之曝光方式的詳細内容传 為貫施例1之曝光步驟中所應用的曝光方式(鄰近曝:、 。又記為「雷射」之曝光方式的詳細内容、?) -曝光步驟(雷射曝光)_ 貫施預烘烤處理後,使用作為雷射曝光穿 EGIS(V Technology(股),YAg 雷射之第 3 諧 之 3 5 5nm,脈衝寬度6nsec),對感光性樹脂組成物層矛 透過光罩進行約1 mJ/cm2的脈衝照射20次。 面 201219977 【1<】The class of S-65-201219977 is changed to the same as that of the first embodiment except that it is described in Table i, except that the embodiment 2 to 丨2 and the ratio are prepared. Each of the coloring photosensitive groups of Examples 1 to 8 was replaced with a coloring pattern in the same manner as in the exposure step, except that the exposure method of each of the obtained coloring photosensitive t was changed to the same as that of the composition. The composition of the pigment dispersion composition was dispersed in the same manner as in Example 1 except for the loading of M. The details of the exposure method of ', 9 for the pigment name, and for the "adjacent" for the wide 1 are passed as the exposure method applied in the exposure step of Example 1 (proximity exposure: , and is also recorded as Details of the exposure method of "Laser", ?) - Exposure step (laser exposure) _ After the pre-baking treatment, use as the laser exposure to wear EGIS (V Technology), the third of YAg laser Harmonic 3 5 5 nm, pulse width 6 nsec), the photosensitive resin composition layer was irradiated with a pulse of about 1 mJ/cm 2 through the reticle 20 times. Face 201219977 [1<]
曝光方式 鄰近 雷射 鄰近 鄰近 鄰近 鄰近 鄰近 鄰近 I鄰近 鄰近 鄰近 鄰近 鄰近 雷射 鄰近 鄰近 鄰近 鄰近 鄰近 鄰近 鏈轉移劑 (硫醇化合物) Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-PE1 乙二醇雙 (3-氫硫基丁酸酯) 乙二醇雙 (3-曱基-3-氫硫基丁酸酯) Karenz MT-BD1 氫硫基苯并咪唑 氫硫基苯并咪唑 氫硫基苯并味。坐 乙二醇雙 (3-氫硫基丙酸酯) Karenz MT-BD1 十二烧硫醇 十二烷硫醇 4-氣苯硫醇 光聚合起始劑2 OXE-Ol OXE-Ol OXE-Ol OXE-Ol OXE-Ol 化合物C OXE-Ol OXE-Ol OXE-Ol OXE-Ol OXE-Ol 1 OXE-Ol OXE-Ol : OXE-Ol OXE-Ol OXE-Ol OXE-Ol 化合物C 化合物C 光聚合起始劑1 B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM 1 B-CIM 1_ B-CIM B-CIM B-CIM 「B-CIM B-CIM B-CIM B-CIM 聚合性單體 ARONIXM-520 ARONIX M-520 ARONIX M-510 ARONIX TO-2349 ^ £ CL, Q ARONIX M-520 ARONIX M-520 ARONIX M-520 | ARONIX M-520 ARONIX M-520 ARONIX M-520 ARONIX M-520 ARONIX M-520 ARONIX M-520 ARONIX M-520 ARONIX M-520 DPHA ARONIX M-520 ARONIX M-520 ARONIX M-520 顏料分散組成物 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 i_ PG58/PY150 PG58 PG58/PY138 PG58/PY150 1_ PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY138 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 |實施例1 | 1實施例2 1 實施例3 |實施例4 實施例5 實施例6 實施例7 實施例8 |實施例9 1 實施例10 實施例11 實施例12 比較例1 比較例2 比較例3 比幸交例4 1比較例5 比較例6 1比較例7 1 1比較例8 I 丨L9 — s .201219977 表1中,DPHA、Karenz MT-PE1之構造係如下述所 示。 DPHA :日本化藥製’二新戊四醇六丙烯酸酯Exposure mode adjacent to laser proximity neighboring neighboring neighboring neighboring neighboring neighboring neighboring neighboring neighboring neighboring neighboring laser neighboring neighboring neighboring neighboring neighboring neighboring adjacent chain transfer agent (thiol compound) Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-BD1 Karenz MT-PE1 Glycol bis(3-hydrothiobutyrate) Glycol bis(3-mercapto-3-hydrothiobutyric acid Ester) Karenz MT-BD1 thiolbenzimidazole thiolbenzimidazole thiol benzoate. Ethylene glycol bis(3-hydrothiopropionate) Karenz MT-BD1 twelve-burning thiol dodecanethiol 4-epoxythiol photopolymerization initiator 2 OXE-Ol OXE-Ol OXE-Ol OXE-Ol OXE-Ol Compound C OXE-Ol OXE-Ol OXE-Ol OXE-Ol OXE-Ol 1 OXE-Ol OXE-Ol : OXE-Ol OXE-Ol OXE-Ol OXE-Ol Compound C Compound C Photopolymerization Starter 1 B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM B-CIM 1 B-CIM 1_ B-CIM B-CIM B-CIM "B-CIM B-CIM B-CIM B-CIM Polymeric monomer ARONIXM-520 ARONIX M-520 ARONIX M-510 ARONIX TO-2349 ^ £ CL, Q ARONIX M-520 ARONIX M-520 ARONIX M -520 | ARONIX M-520 ARONIX M-520 ARONIX M-520 ARONIX M-520 ARONIX M-520 ARONIX M-520 ARONIX M-520 ARONIX M-520 DPHA ARONIX M-520 ARONIX M-520 ARONIX M-520 Pigment dispersion Composition PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 i_ PG58/PY150 PG58 PG58/PY138 PG58/PY150 1_ PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY138 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 PG58/PY150 | Embodiment 1 | 1 Embodiment 2 1 Example 3 | Example 4 Example 5 Example 6 Example 7 Example 8 | Example 9 1 Example 10 Example 11 Example 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 1 Comparative Example 5 Comparative Example 6 1 Comparative Example 7 1 1 Comparative Example 8 I 丨L9 — s .201219977 The structure of DPHA and Karenz MT-PE1 in Table 1 is as follows. DPHA: Nippon Pentaerythritol Hexaacrylate
Karenz MT-PE1 :昭和電工(股)製,新戊四醇四(3-氫硫基 丁酸酯) 此外,表 1 中 OXE-01 係指 IRGACURE OXE-01。 <評定> 對所得之各著色感光性組成物及著色圖案,針對經 時穩定性、臭氣、顯影性、耐溶劑性之各項目進行評定 。評定方法及評定基準係以下所示。將所得之評定結果 彙整並示於表2。 1.經時穩定性的評定 經時穩定性係以液體黏度穩定性及對比穩定性之觀 點來評定。液體黏度穩定性係依據對著色感光性組成物 ,在40°C之熱條件下靜置保存7天前後的液體黏度變化 來評定。 對比定性係由此評定·將在4 〇。〇之熱條件下靜置 保存7天則後的著色感光性組成物於基板上分別塗布成 厚2 · 3 μηι ’並由各基板之對比値來算出變化率。 黏度測定係使用Ε型黏度計re_85L(東機產業(股) 製),對比測定則使用BM-5(T〇PC〇N(股)製)。 -評定基準- 〇.於熱條件靜置保存前後,以靜置前之値為基準,則 (1)黏度變化率A 10%以内,且(2)對比變化率丨1〇%以内 X:不屬於上述(1)及(2)之任一項以上者Karenz MT-PE1: Showa Denko Electric Co., Ltd., pentaerythritol tetrakis(3-hydrothiobutyrate) In addition, OXE-01 in Table 1 refers to IRGACURE OXE-01. <Evaluation> Each of the obtained coloring photosensitive composition and coloring pattern was evaluated for each item of temporal stability, odor, developability, and solvent resistance. The assessment methods and assessment criteria are shown below. The evaluation results obtained are summarized and shown in Table 2. 1. Evaluation of stability over time The stability over time is evaluated by the viewpoint of liquid viscosity stability and comparative stability. The liquid viscosity stability was evaluated based on the viscosity change of the liquid photosensitive composition before and after standing for 7 days under thermal conditions of 40 °C. The comparative qualitative system is thus assessed and will be at 4 〇. The color-sensitive photosensitive composition after standing for 7 days was applied to a substrate to have a thickness of 2 · 3 μηι ′, and the rate of change was calculated from the comparison 値 of each substrate. For the viscosity measurement, a Ε-type viscometer re_85L (manufactured by Toki Sangyo Co., Ltd.) was used, and for comparative measurement, BM-5 (T〇PC〇N (manufactured by the company)) was used. - Evaluation criteria - 〇. Before and after standing in a hot condition, based on the enthalpy before standing, (1) viscosity change rate within A 10%, and (2) contrast change rate 丨1〇% X: no Any one of the above (1) and (2)
-68- S 201219977 所產生的黏度變 而言,若以靜置 若上述項目隨著 感光性組成物形 ’便無法獲得製 就著色感光性'組成物其由時間經過 化率及由時間經過所產生的對比變化率 保存前之値為基準則較佳為1 〇 %以内。 時間經過而顯著變化,則由本發明著色 成彩色濾光片之著色圖案(畫素圖案)時 造穩定性而不適於彩色濾光片的生產。 2 ·臭氣的評定 臭氣的評定係將著色感光性組成物1 m 1 m 1滴入培養孤 中,並依據下述基準,於231:下以官能哗—七 上 叱矸疋來進行。當 臭氣甚為強烈時不僅會感到不適’且需加強排氣等設備 ’因此於實用上較為不佳。 -評定基準- 〇:10人之臭氣官能評定中,感到不適的人數為〇〜3人 X: 1 〇人之臭氣官能評定中’感到不適的人數為4人以 上。 3 ·顯影性的評定 評定對曝光步驟完成後 顯影時的顯影寬容度及顯影 窄時便無法獲得製造程序中 备缺乏顯影液溶解性,則顯 成殘留物或製程污染的原因 之玻璃基板依前述條件進行 液溶解性。當顯影寬容度較 的顯影穩定性而不佳。又, 影時會發生脫膜、剝離而形 ’而且造成問題。 評定。「斷 組成物之未 破斷時點」 針對所得之結果’依下述評定基準進行 點(breakpoint)」係指顯影步驟中著色感光性 曝光部分發生溶解、剝離的時間(秒數),「-68- S 201219977 In terms of the viscosity change, if it is left to stand still, if the above-mentioned items are in the shape of a photosensitive composition, the coloring sensitivity of the composition cannot be obtained. The resulting contrast rate of change is preferably within 1% of the baseline before storage. When the time passes and changes significantly, the colored pattern (pixel pattern) colored by the present invention into a color filter is not suitable for the production of a color filter. 2. Evaluation of odor The evaluation of the odor was carried out by dropping the coloring photosensitive composition 1 m 1 m 1 into the culture orphan and performing the function 哗-7 上 on 231: according to the following criteria. When the odor is very strong, not only will it feel uncomfortable, but it is necessary to strengthen the equipment such as exhaust gas, so it is not practically good. - Evaluation criteria - 〇: The number of people who feel uncomfortable in the odor sensory evaluation of 10 people is 〇~3 people X: 1 The number of people who feel uncomfortable in the odor sensory evaluation of the slut is more than 4 people. (3) Evaluation of developability When the development latitude at the time of development after the completion of the exposure step and the narrow development, the glass substrate which is responsible for the residue or process contamination is not obtained in the manufacturing process. Conditions for liquid solubility. When the development latitude is poor, the development stability is not good. Further, when filming occurs, peeling, peeling, and deformation occur, and problems occur. assessment. "The break point of the composition is not broken". The result of the result "breakpoint" is the time (seconds) at which the dyed photosensitive portion is dissolved and peeled off in the development step,"
S -69- .201219977 貝】^曰”頃’心步驟中著色感光性組成物之未曝光部分發生溶 解、剝離的瞬間。 -評定基準_ 〇 · (1)由斷點起經8〇sec以上未發生著色圖案的剝離, 且(2)於破斷時點在顯影液中未見到著色層的脫膜、剝離 〇 X:不屬於上述(1)及(2)之任一項以上者 4 ·耐溶劑性的評定 對形成有顯影步驟完成後之著色圖案的玻璃基板於 對机供箱中,以23〇°C x30分鐘進行後烘烤。以OLYMPUS( 月又)製OSP-SP 100測定所得之烘烤後的基板之色度,並以 3 C X 30分鐘將其浸潰於Ν·曱基-2_吡咯啶酮(以下稱為 * NMP」)中’再由浸漬前後的著色圖案之色度來求得ae ab。色度係以OLYMPUS(股)製OSP-SP 1 00來測定。 右AE * ab超過3,當製作液晶顯示裝置等時於面板 ^理所使用之各種藥液中的耐溶劑性便會不足,而發生 貫用上的問題。 —進一步透過光學顯微鏡觀察,針對浸潰於NMp前後 之著色圖案之形狀的變化進行觀察。S -69- .201219977 贝] ^曰" is the moment in which the unexposed portion of the colored photosensitive composition is dissolved and peeled off in the heart step. - Evaluation criteria _ 〇 · (1) 8 sec or more from the breakpoint (2) No peeling or peeling of the colored layer was observed in the developer at the time of breaking, and X: not belonging to any one of the above (1) and (2). Evaluation of Solvent Resistance The glass substrate on which the colored pattern after the development step was formed was subjected to post-baking in a counter box at 23 ° C for 30 minutes, and was measured by OLYMPUS OSP-SP 100. The chromaticity of the baked substrate, and immersed in 3 CX for 30 minutes in the Ν·曱-based 2-pyrrolidone (hereinafter referred to as *NMP), and then the color of the colored pattern before and after the immersion To find ae ab. The chromaticity was measured by OLYMPUS (stock) OSP-SP 100. When the right AE*ab exceeds 3, when the liquid crystal display device or the like is produced, the solvent resistance in the various chemical solutions used in the panel is insufficient, and the problem of the use is insufficient. - Further observation by a light microscope was carried out to observe changes in the shape of the colored pattern before and after immersion in NMp.
針對所得之結果’依下述評定基準來進行評定。 、評定基準- D ^(1)^心為3.〇以下,且(2)未見到著色圖案形狀的 變化。 X·不屬於上述(1)及(2)之任一項以上者The results obtained were evaluated according to the following criteria. The evaluation standard - D ^ (1) ^ heart is 3. 〇 below, and (2) no change in the shape of the colored pattern is observed. X· does not belong to any one of the above (1) and (2)
S -70- 201219977 [表2] 經時穩定性 臭氣 顯影性 财溶劑性 實施例1 〇 〇 〇 〇 實施例2 〇 〇 〇 〇 實施例3 〇 〇 〇 〇 實施例4 〇 〇 〇 〇 實施例5 〇 〇 〇 〇 實施例6 〇 〇 〇 〇 實施例7 〇 〇 〇 〇 實施例8 〇 〇 〇 〇 實施例9 〇 〇 〇 〇 實施例10 〇 〇 〇 〇 實施例11 〇 〇 〇 〇 實施例12 〇 〇 〇 〇 比較例1 X 〇 〇 〇 比較例2 X 〇 〇 〇 比較例3 X 〇 〇 〇 比較例4 X 〇 〇 〇 比較例5 〇 〇 X 〇 比較例6 〇 X 〇 X 比較例7 〇 X 〇 X 比較例8 X X 〇 〇 -71 - .201219977 如表2所示,實施例之著色感光性組成物其經時穩 定性優良、無不適之臭氣,關於耐溶劑性亦良好。與此 相對,比較例1〜4之著色感光性組成物其時間經過前後 的性能變化甚大,穩定性低劣。又,比較例5之著色感 光性組成物其顯影寬容度窄而發生問題。比較例6〜8之 著色感光性組成物其來自於硫醇化合物之臭氣甚為強烈 ,於實用上並無法而于用。 又,根據實施例2與實施例1之對照,任一實施例 中所形成之著色圖案(著色膜)關於耐溶劑性亦獲得同樣 的良好結果,如此可知當應用以雷射曝光機所進行的圖 案曝光時,亦與以高壓水銀燈所進行的曝光相同,可獲 得本發明之優良效果。 【圖式簡單說明】 〇 【主要元件符號說明】 〇 s -72-S-70-201219977 [Table 2] Time-dependent stability odor development property solvent method Example 1 〇〇〇〇 Example 2 〇〇〇〇 Example 3 〇〇〇〇 Example 4 〇〇〇〇 Example 5 〇〇〇〇 Example 6 〇〇〇〇 Example 7 〇〇〇〇 Example 8 〇〇〇〇 Example 9 〇〇〇〇 Example 10 〇〇〇〇 Example 11 〇〇〇〇 Example 12 〇〇〇〇 Comparative Example 1 X 〇〇〇 Comparative Example 2 X 〇〇〇 Comparative Example 3 X 〇〇〇 Comparative Example 4 X 〇〇〇 Comparative Example 5 〇〇X 〇 Comparative Example 6 〇X 〇X Comparative Example 7 〇 X 〇 X Comparative Example 8 XX 〇〇-71 - .201219977 As shown in Table 2, the colored photosensitive composition of the examples was excellent in stability over time and had no discomfort, and was also excellent in solvent resistance. On the other hand, the colored photosensitive compositions of Comparative Examples 1 to 4 exhibited a large change in performance before and after the passage of time, and the stability was inferior. Further, the color-sensitive photosensitive composition of Comparative Example 5 had a problem that the development latitude was narrow and caused a problem. In the colored photosensitive compositions of Comparative Examples 6 to 8, the odor derived from the thiol compound was extremely strong, and it was practically impossible to use. Further, according to the comparison between Example 2 and Example 1, the colored pattern (colored film) formed in any of the examples obtained the same good results with respect to solvent resistance, so that it was found that when applied by a laser exposure machine When the pattern is exposed, it is also the same as the exposure by a high pressure mercury lamp, and the excellent effects of the present invention can be obtained. [Simple description of the diagram] 〇 [Key component symbol description] 〇 s -72-
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CN111752091B (en) * | 2019-03-29 | 2022-09-06 | 常州正洁智造科技有限公司 | Application of HABI mixed photoinitiator in UVLED photocuring |
JP2020041154A (en) * | 2019-11-21 | 2020-03-19 | 住友化学株式会社 | Coloring curable resin composition, color filter and display device comprising the same |
WO2021235373A1 (en) * | 2020-05-22 | 2021-11-25 | 富士フイルム株式会社 | Resin composition, film, optical filter, solid image pickup element, and image display apparatus |
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JP2003161823A (en) * | 2001-11-28 | 2003-06-06 | Dainippon Ink & Chem Inc | Pigment-dispersed resist for color filter, and the color filter |
JP2003255121A (en) * | 2002-02-28 | 2003-09-10 | Toppan Printing Co Ltd | Method for manufacturing color filter and color filter |
JP4218828B2 (en) * | 2002-02-28 | 2009-02-04 | 昭和電工株式会社 | Thiol compound, photopolymerization initiator composition, and photosensitive composition |
JP2004264435A (en) * | 2003-02-28 | 2004-09-24 | Showa Denko Kk | Photosensitive composition for color filter and color filter using same |
JP4418766B2 (en) * | 2005-03-28 | 2010-02-24 | 富士フイルム株式会社 | Method for making a photosensitive lithographic printing plate |
JP4821206B2 (en) * | 2005-07-29 | 2011-11-24 | 東レ株式会社 | Photosensitive coloring composition for color filter and color filter |
JP4752590B2 (en) * | 2006-04-18 | 2011-08-17 | Dic株式会社 | Polyhalogenated zinc phthalocyanine pigment composition and color filter |
JP4992321B2 (en) * | 2006-07-18 | 2012-08-08 | Dic株式会社 | Polyhalogenated zinc phthalocyanine, photosensitive composition and color filter |
JP5459949B2 (en) * | 2007-11-21 | 2014-04-02 | 凸版印刷株式会社 | Coloring composition, color filter and method for producing the same |
JP5176468B2 (en) * | 2007-10-05 | 2013-04-03 | Jsr株式会社 | Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element |
JP4998293B2 (en) * | 2008-01-31 | 2012-08-15 | Jsr株式会社 | Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element |
JP5527965B2 (en) * | 2008-02-22 | 2014-06-25 | Jsr株式会社 | Radiation-sensitive composition for green pixel formation, color filter, and color liquid crystal display element |
JP5001326B2 (en) * | 2009-03-31 | 2012-08-15 | 大日本印刷株式会社 | Negative resist composition for color filter, color filter, and liquid crystal display device |
JP5672677B2 (en) * | 2009-08-21 | 2015-02-18 | 大日本印刷株式会社 | Photosensitive resin composition for color filter, and color filter using the photosensitive resin composition |
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2010
- 2010-09-01 JP JP2010195879A patent/JP5726462B2/en active Active
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2011
- 2011-08-18 CN CN2011102379644A patent/CN102385246A/en active Pending
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KR20120022668A (en) | 2012-03-12 |
JP5726462B2 (en) | 2015-06-03 |
CN102385246A (en) | 2012-03-21 |
JP2012053278A (en) | 2012-03-15 |
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