TW201232178A - Photosensitive resin composition, partition wall, color filter, and organic el element - Google Patents

Photosensitive resin composition, partition wall, color filter, and organic el element Download PDF

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Publication number
TW201232178A
TW201232178A TW100147486A TW100147486A TW201232178A TW 201232178 A TW201232178 A TW 201232178A TW 100147486 A TW100147486 A TW 100147486A TW 100147486 A TW100147486 A TW 100147486A TW 201232178 A TW201232178 A TW 201232178A
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Taiwan
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resin composition
group
partition wall
photosensitive resin
ink
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TW100147486A
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Chinese (zh)
Inventor
Hideyuki Takahashi
Kenji Ishizeki
Masayuki Kawashima
Masaki Obi
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Asahi Glass Co Ltd
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Publication of TW201232178A publication Critical patent/TW201232178A/en

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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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/0041—Photosensitive materials providing an etching agent upon exposure
    • 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
    • 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
    • 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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Ceramic Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

Provided is a photosensitive resin composition for forming a partition wall by a photolithography method, which is capable of forming a pattern with high resolution by improving adhesion of the pattern during the development. Also provided are: a partition wall which is formed as a pattern with high resolution; a color filter with high resolution, which uses the partition wall; and an organic EL element which uses the partition wall. Specifically provided are: a photosensitive resin composition for forming a partition wall by a photolithography method, said partition wall being arranged on a substrate so as to define a plurality of sections for the formation of pixels, which contains (A) a binder resin, (B) a photoactive agent, (C) fine particles that have a zeta potential of from -100 mV to -5 mV in a dispersion liquid as determined by an electrophoretic light scattering method, and (D) an organic solvent; a partition wall which is formed using this composition; a color filter which comprises the partition wall; and an organic EL element which comprises the partition wall.

Description

201232178 ' 六、發明說明： 【明戶斤屬:系奸旬| 3 技術領域 本發明有關於一種用於以光蝕刻法形成隔壁之感光性 樹脂組成物、使用其而形成之隔壁以及具有該隔壁之濾色 器及有機EL元件。 C先前冬奸；J 背景技術 近年來’作為形成濾色器之像素間的隔壁、有機 EL(Electro-Luminescence)元件之像素間的隔壁、有機虹照 明之元件間的隔壁、區隔有機TFT(Thin Film Transistor :薄 膜電晶體）陣列之各TFT的隔壁、液晶表示元件之ιτο電極的 隔壁以及電路佈線基板之隔壁等的永久膜之材料，感光性 樹脂組成物正受到矚目。 使用此種感光性樹脂組成物來形成光學元件之隔壁 時，隔壁係以光蝕刻法於玻璃等之透明基板上形成圖案。 之後，於已形成在基板上之隔壁間的開口部形成像素，夢 此製造出光學元件。於本發明說明書中，「圖案」表示從基 板上方俯視隔壁時之形狀。 就使用於製造上述光學元件之隔壁形成用感光性樹脂 組成物而言，為了獲得可實現高解像度之圖案，除了要求 具良好之感光性及顯像性之外’在其製裎(具體來說，則是 依序進行塗佈 '預焐、曝光、顯像及後焙的製程）中，特別 是顯像時之圖案密著性及後焙時之圖案尺寸安定性成為重 201232178 點，近年來即著眼於此來進行研究開發。 舉例來說，於專利文獻lt，為了防止隔壁形狀因後培 時之受熱損害而變形，而提出-種除了結合劑樹脂之外同 時還摻合有填料與分散劑之樹驗成物。此外，於專利文 獻2中，則特別就隔壁中之黑矩陣(b丨提出一種黑 色光阻(black⑽ist)用感紐樹脂組成物，其作為圖案尺寸 女疋!·生優異、顯像界限及隔壁密著性良好且即使於後培後 亦可保持表面平滑性之感光性樹脂組成物，而含有光硬化 性樹脂與遮光性顏料，且㈣於遮紐顏料更以特定比例 3有特疋粒徑之粒狀二氧化矽。然而，以此等例示而言， 難謂其等已獲得夠高解像度之圖案。 此外，在與上述者不同之其他目的下除了著色顏料 以外，亦對隔壁形成用感光性樹脂組成物進行填料之摻 合。舉例來說，專利文獻3記載到—種感光性樹脂組成物之 技術，該感光性樹脂組成物可用於以噴墨法形成像素來製 造光學元件之際，且含有用以形成隔壁之撥墨劑，於此， 使用摻合有特定粒徑之微粒子的隔壁形成用感光性樹脂組 成物而於隔壁上形成微細孔，以使其吸收墨水之溶劑，藉 此可防止墨水之混色。 再者，專利文獻4則記載到，將微粒子（特別是帶負電 之从粒子）添加至換合有黑色顏料以及具有用以分散該顏 料之鹼性官能基之高分子分散劑的隔壁形成用感光性樹脂 組成物，可獲得具有充分撥液性之隔壁並玎防止墨水混 201232178 然而，專利文獻3及專利文獻4所記載之隔壁形成用感 光性樹脂組成物雖透過摻合微粒子而改善撥墨性，但並未 獲得解像度特別高之圖案。 先行技術文獻 【專利文獻】 【專利文獻1】日本特開2006-284674號公報 【專利文獻2】日本特開2008-304583號公報 【專利文獻3】日本特開2006-163233號公報 【專利文獻4】國際公開第2008/133312號 【發明内容】 發明概要 發明欲解決之課題 本發明係鑑於上述觀點而為者，目的在於提供一種感 光性樹脂組成物，其係用於以光蝕刻法形成隔壁，且透過 改善隔壁之顯像密著性而可形成高解像度之圖案。此外， 目的亦在於提供一種可形成為高解像度之圖案的隔壁、使 用其之高解像度濾色器以及有機EL元件。 用以解決課題之手段 本發明提供一種具有下述[1]〜[12]之結構的感光性樹 脂組成物、隔壁、濾色器及有機EL元件。 [1]一種感光性樹脂組成物，係用於以光蝕刻法形成隔 壁者，該隔壁係配設成使基板上區隔出用以形成像素之多 數區塊的·形狀；且，該感光性樹脂組成物含有：結合劑樹 脂(A);光活性劑(B);微粒子(C)，其係以有機溶劑作為分 201232178 散介質之分散液中的微粒子(c)，且該分散液中之微粒子（c) 以電泳光散射法所測定之ξ電位為-100〜-5mv;及，有機溶 劑(D) ’其至少一部分為前述分散液之有機溶劑。 [2] 如[1]之感光性樹脂組成物，其中前述微粒子（c)之平 均粒徑為5〜i〇〇nm。 [3] 如[1]或[2]之感光性樹脂組成物，其中前述微粒子（c) 之分散液中的分散介質係具有至少1個羥基且SP值為9〜 2〇MW严之有機溶劑。 ’ [4] 如[1]至[3]中任一項之感光性樹脂組成物，其中前述 微粒子(C)為二氧化矽微粒子。 [5] 如[4]之感光性樹脂組成物，其中前述二氧化矽微粒 子為膠體二氧化矽。 [6] 如[1]至[5]中任一項之感光性樹脂組成物，其中前述 微粒子（c)之含量相對於組成物之總固體含量為3〜35質量 %。 [7] 如[1 ]至[6]中任一項之感光性樹脂組成物，其更含有 著色劑(E)。 [8] 如[7]之感光性樹脂組成物，其中前述著色劑係選 自於由碳黑、鈦黑、黑色金屬氧化物顏料、銀錫合金及有 機顏料所構成群組中之至少1種物質。 [9] 如[1]至[8]中任—項之感光性樹脂組成物，其中前述 基板之隔壁形成面具有下述表面特性：其與用於前述光蝕 刻法之鹼性顯影液的親和性良好。 [10] 一種隔壁’係形成為使基板上區隔出用以形成像素 201232178 之多數區塊的形狀者，其特徵在於：該隔壁係使用如[1]至 [9]中任一項之感光性樹脂組成物並以光蝕刻法形成者。 Π1] —種濾色器，係在基板上具有多數像素及位在鄰接 像素間之隔壁者，且該隔壁係如[10]之隔壁。 [12]—種有機EL元件，係在基板上具有多數像素及位 在鄰接像素間之隔壁者，且該隔壁係如[10]之隔壁。 發明效果 若依本發明，則可提供一種感光性樹脂組成物，其係 用於以光蝕刻法形成隔壁’且藉由隔壁之顯像密著性獲得 改善而可形成高解像度之圖案。此外’可提供一種使用該 感光性樹脂組成物而形成為高解像度之圖案的隔壁、使用 其之高解像度濾色器及有機EL元件。 圖式簡單說明 第l(al)至(C2)圖係模式性地顯示使用本發明之感光性 樹脂組成物來形成隔壁之步驟者。 第2(a)、（b)圖係顯示墨水層厚度之測定位置者，該墨 水層厚度係用於評估：使用本發明之感光性樹脂組成物所 形成之喷墨用隔壁來形成像素時的墨水層均勻性。 【實施方式3 本發明之實施形態 茲將本發明之實施形態說明如下。但本發明並不询限 在下述之實施形態。 另，於本發明說明書中，在未特別說明之情況下， 表示質量％。（曱基）丙烯醯基一詞係作為意指丙烯醯基與甲 7 201232178 基丙烯醯基雙方之總稱來使用。 再者，從感光性樹脂組成物(含有機溶劑(D)之組成物) 去除有機溶細)後之組成物稱為感紐組成物。感光性樹 脂組成物含有與有機溶劑(D)同樣之低彿點成分時，感光性 組成物即是該低沸點成分亦被連同去除之組成物。又，該 感光性組成物相當於感光性樹脂組成物之固體成分。 此外’於基料之表面塗佈感紐樹脂組成物而獲得 之感光性樹脂組成物膜(含有機溶劑(D)之組成物膜)稱為濕 =膜。又，從濕_去除有機㈣(晴之揮發性成分而獲 得的感光性組成物膜亦稱為感光性膜。 [感光性樹脂組成物] 本發明之感光性樹脂組成物係—種用於以光敍刻法形 成隔壁且顧魏設成縣板上區Μ “形成像素之多 數區塊的減者’其特徵在於含有：結合賴脂(Α广光活 性劑(B);微粒子(C)，其係以有機溶劑作為分散介質之分散 液中的微粒子(C)，且該分散液中之微粒子(c)以電泳光散射 法所測定之ξ電位為_100〜_5mV ;及，有機溶劑⑼，其至 少一部分為前述分散液之有機溶劑。 微粒子(C)係作為令有機溶劑成為分散介質之分散液 (以下，亦稱為有機溶劑分散液）而摻合至本發明之感光性樹 脂組成物中，該有機溶劑分散液中之微粒子（(：)的€電位為 -10 0〜-5 m V。本發明之感光性樹脂組成物中含有有機溶劑 (D)，且該有機溶劑(D)之至少一部分係源自微粒子〇之有 機溶劑分散液的有機溶劑。於感光性樹脂組成物中，亦可 201232178 00 Λ 4劑可域級樹脂組成物之製造過程中作 :掺合之有機_，而在感紐樹脂組成物中之成分被 k成有機溶劑溶液或有機溶劑分散液時，亦可是伴隨著 錢分之摻合而被摻和的有機溶劑。本發明中之有機溶劑 (D)係^本發明之感級樹脂組成物所含有的有機溶劑整 體。 …本發明之感紐樹脂組成物巾，所含有之上述特定㉘ 位範圍之難子(〇會在組成物中_邊保持分散性一邊與 構成感光性樹脂組成物之其他成分相互拉扯地發揮作用。 此外’由於與基板(特別是諸如表面存有減之絲)具有強 烈之相互密著作用，在絲刻法中，可有效地防止已形成 之隔壁從基板！彳離’此種在m貞像時容$發生的現象。 結果，可一邊保持隔壁對基板之密著性，一邊提高鹼性顯 像之顯像性，而可獲得高解像度之圖案。 本發明之感光性樹脂組成物只要是用於以光蝕刻法形 成隔壁且該隔壁配設成使基板上區隔出用以形成像素之多 數區塊的形狀者’則可為負型感光性樹脂組成物，亦可為 正型感光性樹脂組成物。 此等感光性樹脂組成物均含有由結合劑樹脂(A)與光 活性劑(B)之組合所構成的成分，且在有機溶劑(D)去除後， 光活性劑(B)會因光或電子線之照射（曝光）而活性化並對結 合劑樹脂(A)發生作用，具有使感光性組成物之溶解性等物 性發生變化之特性。 201232178 負型感光性樹脂組成物所形成之感光性組成物中，藉 由曝光而活性化之光活性劑（B )會對結合劑樹脂（A)作用而 引起硬化’未受曝光之部分（未硬化部分）則會因顯像而被去 除，進而形成圖案。依其硬化之種類，即結合劑樹脂(A)與 光活性劑(B)之組合種類，而可分類為自由基硬化型及酸硬 化型等類型。 此外’於正型感光性樹脂組成物所形成之感光性組成 物中，藉由曝光而活性化之光活性劑（B)會對結合劑樹脂（A) 作用’其對顯像液之溶解性增加，已曝光之部分會因顯像 而被去除’進而形成圖案。依光活性劑(B)及結合劑樹脂（A) 之種類而定’舉例來說，可分類為含有鄰醌二疊氮化物 (o-quinone diazide)之類型、含有業經封端化之酸性基的類 型等。 以下’針對本發明之感光性樹脂組成物，分別按上述 類別來說明負型感光性樹脂組成物及正型感光性樹脂組成 物0 (1)自由基硬化型之負型感光性樹脂組成物 從自由基硬化型之負型感光性樹脂組成物去除有機溶 劑^>)之感光性組成物即是自由基硬化性感光性組成物。以 下’將會成為自由基硬化性感光性組成物之此一自由基石更 化型的負型感光性樹脂組成物稱為樹脂組成物(NR)。 樹脂組成物(NR)含有：作為結合劑樹脂(A)之光自由基 聚合性結合劑樹脂(A1);作為光活性劑(B)之光聚合起始劑 (B1);前述微粒子(〇 ;及，有機溶劑(D)。作為此種光自由 201232178 基承合性結合劑树脂(A1)與光聚合起始劑(B1)，可無特別限 制地使用在習用公知之樹脂組成物(NR)中所使用的光自由 基聚合性之結合劑樹脂(A1)與光聚合起始劑(b丨）之組合，且 5玄習用公知之樹脂組成物(NR)係用以形成光學元件之隔壁 者。 (1-1)結合劑樹脂(A):光自由基聚合性之結合劑樹脂 本發明之負型感光性樹脂組成物為樹脂組成物（NR) 時，樹脂組成物(NR)所含之結合劑樹脂(A1)係光自由基聚 合性之結合劑樹脂（A1)，其未硬化物為鹼可溶性，且其聚 合、硬化之硬化物則為驗不溶性。由於結合劑樹脂(A1)會 成為鹼不溶性之硬化物，而宜具有乙烯性雙鍵，此外，由 於結合劑樹脂（A1)為鹼可溶性，而宜具有酸性基。乙烯性 雙鍵會透過屬於光活性劑（B)之光聚合起始劑所發生之自 由基而聚合’樹脂藉由該聚合而硬化。 含有未硬化之結合劑樹脂(A1)的感光性組成物可藉由 鹼性顯像液而去除，而藉由結合劑樹脂（A1)之硬化，含有 其之感光性組成物亦會硬化，感光性組成物之硬化物不會 因鹼性顯像液而被去除。藉此，含有結合劑樹脂（A1)之感 光性組成物所構成的感光性膜因曝光部分硬化成鹼不溶性 另一方面未曝光部分則為鹼可溶性，可於曝光後使用鹼性 顯像液進行顯像，藉此可選擇性地除去膜之未曝光部分。 結合劑樹脂(A1)所具有之酸性基並未特別受限，但可 列舉如羧巧、酚性羥基、磺酸基、磷酸基等，亦可併用2種 以上。 11 201232178 結合劑樹脂（A1)所具有之 但可列舉如（曱基）丙稀酿基 1鍵並未特別受限， 之加成聚合性基所具有的雙鍵^、乙烯基及乙烯氧基等 該等加成聚合性基所具有之氫原二併用2種以上。另’ 烴基（宜為甲基)取代。 ’'的-部分或全部亦可經 結合劑樹脂(A1)並未特别受限 具有具酸性基之側鏈與具乙稀性、體來說’可列舉如 樹脂則可列舉如以下述手法製側鏈的樹脂。此種 及環氧基等反應性基之單體^ ^ΜΑΜ):使具有經基 合述酸性基之單體共聚 物，再使其與具有可収應性基:，縣之側鏈的共聚 鍵的化合物反應。其他尚可轉諸基與乙稀性雙 M . 财環氧樹脂導入乙缔性 雙鍵與酸性基之樹脂(A1_2)等。 併用2種以上。 了早獨使m種’亦可 /為樹脂(AM)之酸性基而具有键基之單體並未特 別又限’但可列舉如2·(甲基）丙_氧基乙㈣酸等。 舉例來說，可使環氧樹脂與具有絲及乙烯性雙鍵之 化合物反應後，使多_酸或其酸奸反應而合成出樹脂 (A1_2)。具體來說’可藉由令環氧樹脂與具錢基及乙稀性 雙鍵之化合物反應’而將乙烯性雙鍵導人環氧樹脂中。接 著，使多元麟或其酸針與已導人乙馳雙鍵之環氧樹脂 反應，藉此可導入羧基。 環氧樹脂並未特別受限，但可列舉如雙盼八型環氧樹 脂、雙盼F型環氧樹脂、㈣祕清漆型環氧樹脂、甲_ 12 201232178 醛清漆型環氧樹脂、三酚曱烷型環氧樹脂、具有萘骨架之 環氧樹脂、具有下述通式（1)所示聯苯骨架之環氧樹脂、下 述通式（2)及通式(3)所示環氧樹脂等。 【化1】201232178 '6. Description of the invention: [The invention relates to a photosensitive resin composition for forming a partition wall by photolithography, a partition wall formed therewith, and having the partition wall The color filter and the organic EL element. C. Previous winter rape; J. In recent years, 'the partition between pixels as a color filter, the partition between pixels of an organic EL (Electro-Luminescence) element, the partition between elements of organic rainbow illumination, and the organic TFT ( The photosensitive resin composition is attracting attention to the material of the permanent film of the TFT of the thin film transistor, the liquid crystal display element, the partition wall of the electrode, and the partition wall of the circuit board. When such a photosensitive resin composition is used to form the partition walls of the optical element, the partition walls are patterned by photolithography on a transparent substrate such as glass. Thereafter, pixels are formed in the openings formed between the partition walls on the substrate, and an optical element is produced. In the specification of the present invention, "pattern" means a shape when the partition wall is viewed from above the substrate. In order to obtain a pattern capable of achieving high resolution, in order to obtain a pattern capable of achieving high resolution, in order to obtain a pattern having high resolution, it is required to be "made" (specifically In the case of the coating process of pre-bending, exposing, developing and post-baking, in particular, the pattern adhesion during development and the dimensional stability of the post-baking pattern become heavy 201232178 points, in recent years That is to say, research and development is focused on this. For example, in the patent document lt, in order to prevent the shape of the partition wall from being deformed by heat damage during post-peeling, a tree test product in which a filler and a dispersant are blended in addition to the binder resin is proposed. Further, in Patent Document 2, in particular, a black matrix in a partition wall (b丨 proposes a sensible resin composition for black (10) ist), which is used as a pattern size 疋 · · 生 生 生 · · · · · · · · 生 生 生 生 · · · · · · · · A photosensitive resin composition which is excellent in adhesion and maintains surface smoothness even after post-peeling, and contains a photocurable resin and a light-shielding pigment, and (4) has a special particle size in a specific ratio of 3 in the matte pigment. Granular cerium oxide. However, it is difficult to say that the pattern of high resolution has been obtained by such an exemplification. Further, in addition to the coloring pigment, the sensitization for forming the partition wall is also performed for other purposes different from the above. For example, Patent Document 3 discloses a technique of a photosensitive resin composition which can be used for forming an optical element by forming a pixel by an inkjet method, and the like. Further, the ink-repellent agent for forming a partition wall is provided. Here, a photosensitive resin composition for forming a partition wall having fine particles having a specific particle diameter is used, and fine pores are formed in the partition wall so that In addition, Patent Document 4 discloses that fine particles (especially negatively charged particles) are added to a black pigment and have a base for dispersing the pigment. A photosensitive resin composition for forming a barrier layer of a polymer functional group-based polymer dispersant, and a partition wall having sufficient liquid repellency can be obtained and the ink can be prevented from being mixed 201232178. However, the photosensitive layer for forming a partition wall described in Patent Document 3 and Patent Document 4 In the resin composition, the ink repellency is improved by blending the fine particles, but a pattern having a particularly high degree of resolution is not obtained. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2006-284674 [Patent Document 2] Japan [Patent Document 3] JP-A-2006-163233 [Patent Document 4] International Publication No. 2008/133312 SUMMARY OF INVENTION Technical Problem The present invention has been made in view of the above points. It is an object of the invention to provide a photosensitive resin composition for forming a partition wall by photolithography, and improving the partition Further, the object is to provide a partition wall which can be formed into a high-resolution pattern, a high-resolution color filter using the same, and an organic EL element for solving the problem. The present invention provides a photosensitive resin composition having a structure of the following [1] to [12], a partition wall, a color filter, and an organic EL device. [1] A photosensitive resin composition for photoetching Forming the partition wall, the partition wall is disposed such that the substrate is partitioned from a shape for forming a plurality of blocks of the pixel; and the photosensitive resin composition contains: a binder resin (A); a photoactive agent ( B); fine particles (C), which are organic particles as fine particles (c) in a dispersion of 201232178 dispersion medium, and the fine particles (c) in the dispersion are determined by electrophoretic light scattering method as the zeta potential - 100~-5mv; and, the organic solvent (D)' is at least a part of the organic solvent of the above dispersion. [2] The photosensitive resin composition according to [1], wherein the fine particles (c) have an average particle diameter of 5 to i 〇〇 nm. [3] The photosensitive resin composition according to [1] or [2], wherein the dispersion medium in the dispersion of the fine particles (c) has at least one hydroxyl group and an SP value of 9 to 2 〇 MW of an organic solvent . [4] The photosensitive resin composition according to any one of [1] to [3] wherein the fine particles (C) are cerium oxide fine particles. [5] The photosensitive resin composition according to [4], wherein the cerium oxide microparticles are colloidal cerium oxide. [6] The photosensitive resin composition according to any one of [1] to [5] wherein the content of the fine particles (c) is from 3 to 35 mass% with respect to the total solid content of the composition. [7] The photosensitive resin composition according to any one of [1] to [6] which further contains a coloring agent (E). [8] The photosensitive resin composition according to [7], wherein the coloring agent is at least one selected from the group consisting of carbon black, titanium black, ferrous metal oxide pigment, silver tin alloy, and organic pigment. substance. [9] The photosensitive resin composition of any one of [1] to [8] wherein the partition wall forming surface of the substrate has surface characteristics which are compatible with the alkaline developing solution used for the photolithography method described above. Good sex. [10] A partition wall is formed such that a shape of a plurality of blocks for forming a pixel 201232178 is formed on a substrate, wherein the partition wall is photosensitive according to any one of [1] to [9]. The resin composition is formed by photolithography. Π1] A color filter having a plurality of pixels on a substrate and a spacer between adjacent pixels, and the partition is a partition wall of [10]. [12] An organic EL device having a plurality of pixels on a substrate and a spacer between adjacent pixels, and the partition wall is a partition wall of [10]. According to the present invention, it is possible to provide a photosensitive resin composition which is used for forming a partition wall by photolithography and which is improved in image-forming adhesion by a partition to form a high resolution pattern. Further, a partition wall which is formed into a high-resolution pattern using the photosensitive resin composition, a high-resolution color filter using the same, and an organic EL element can be provided. BRIEF DESCRIPTION OF THE DRAWINGS The first (al) to (C2) drawings schematically show the steps of forming the partition walls using the photosensitive resin composition of the present invention. The second (a) and (b) drawings show the measurement position of the thickness of the ink layer, and the thickness of the ink layer is used for evaluation when the pixel is formed by using the partition wall for inkjet formed by the photosensitive resin composition of the present invention. Uniformity of the ink layer. [Embodiment 3] Embodiments of the invention The embodiments of the invention are described below. However, the present invention is not limited to the embodiments described below. Further, in the specification of the present invention, the mass % is expressed unless otherwise specified. The term "fluorenyl" is used in the generic term to mean both a propylene fluorenyl group and a propylene 7 group. Further, the composition obtained by removing the organic solvent from the photosensitive resin composition (the composition containing the organic solvent (D)) is referred to as a photosensitive composition. When the photosensitive resin composition contains the same low-foam component as the organic solvent (D), the photosensitive composition is a composition in which the low-boiling component is also removed. Further, the photosensitive composition corresponds to a solid component of the photosensitive resin composition. Further, the photosensitive resin composition film (the film containing the organic solvent (D)) obtained by coating the surface of the base material with the photosensitive resin composition is referred to as a wet film. Further, the photosensitive composition film obtained by removing the volatile component of the organic (four) (clear) is also referred to as a photosensitive film. [Photosensitive Resin Composition] The photosensitive resin composition of the present invention is used for light The syllabary method forms the next door and Gu Wei is set as the county's on-board area. “The reduction of most of the blocks forming the pixel” is characterized by: combining lyophile (Α Guangguang active agent (B); fine particles (C), which is The organic solvent serves as the fine particles (C) in the dispersion of the dispersion medium, and the fine particles (c) in the dispersion have a zeta potential of _100 to _5 mV as measured by electrophoretic light scattering; and, the organic solvent (9), at least a part thereof The organic solvent of the dispersion liquid. The fine particles (C) are blended into the photosensitive resin composition of the present invention as a dispersion liquid (hereinafter also referred to as an organic solvent dispersion liquid) in which an organic solvent is a dispersion medium. The potential of the fine particles ((:) in the solvent dispersion is -10 0 to -5 m V. The photosensitive resin composition of the present invention contains an organic solvent (D), and at least a part of the organic solvent (D) Organic solvent dispersion derived from fine particles The organic solvent is used in the photosensitive resin composition, and can also be used in the manufacturing process of the 201232178 00 Λ 4 agent domain-level resin composition: the organic compound is blended, and the component in the sensitized resin composition is k-formed. In the case of an organic solvent solution or an organic solvent dispersion, it may be an organic solvent which is blended with the blending of the money. The organic solvent (D) in the present invention is an organic substance contained in the sensitive resin composition of the present invention. The solvent as a whole. The inductive resin composition of the present invention contains the above-mentioned specific 28-position hard-to-finish (the 〇 will remain in the composition while maintaining the dispersibility while pulling the other components constituting the photosensitive resin composition. In addition, because of the strong mutual interaction with the substrate (especially such as the presence of a minus wire on the surface), in the wire-cut method, the formed partition wall can be effectively prevented from the substrate! In the case of m 贞 容 容 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The material may be a negative photosensitive resin composition or may be positive as long as it is formed by a photolithography method and the partition wall is disposed such that a shape of a plurality of blocks for forming a pixel is formed on the substrate. A photosensitive resin composition. These photosensitive resin compositions each contain a component consisting of a combination of a binder resin (A) and a photoactive agent (B), and after removal of the organic solvent (D), the photoactive agent (B) It is activated by irradiation (exposure) of light or electron beam, and acts on the binder resin (A), and has properties of changing the physical properties such as solubility of the photosensitive composition. 201232178 Negative photosensitive resin In the photosensitive composition formed by the composition, the photoactive agent (B) activated by exposure acts on the binder resin (A) to cause hardening of the unexposed portion (unhardened portion). The image is removed and developed to form a pattern. Depending on the type of hardening, that is, the combination of the binder resin (A) and the photoactive agent (B), it can be classified into a radical hardening type and an acid hardening type. Further, in the photosensitive composition formed of the positive photosensitive resin composition, the photoactive agent (B) activated by exposure acts on the binder resin (A), and its solubility in the developing solution Increased, the exposed portion will be removed due to development' and then patterned. Depending on the type of the photoactive agent (B) and the binder resin (A), for example, it can be classified into a type containing o-quinone diazide and contains an acid group which is blocked. Types, etc. In the photosensitive resin composition of the present invention, the negative photosensitive resin composition and the positive photosensitive resin composition are described as follows. (1) The radically cured negative photosensitive resin composition is The radically curable negative photosensitive resin composition removes the organic solvent ^>) The photosensitive composition is a radically curable photosensitive composition. The negative photosensitive resin composition which is a radical-curable photosensitive composition which is a radical-curable photosensitive composition is referred to as a resin composition (NR). The resin composition (NR) contains: a photoradical polymerizable binder resin (A1) as a binder resin (A); a photopolymerization initiator (B1) as a photoactive agent (B); the aforementioned microparticles (〇; And the organic solvent (D). As such a light free 201232178 base-bonding binder resin (A1) and a photopolymerization initiator (B1), it can be used without any particular limitation in the conventionally known resin composition (NR). The photo-radical polymerizable binder resin (A1) and the photopolymerization initiator (b) are used in combination, and a known resin composition (NR) is used to form the optical element. (1-1) Bonding Resin (A): Photoradical Polymerizable Bonding Resin When the negative photosensitive resin composition of the present invention is a resin composition (NR), the combination of the resin composition (NR) The resin (A1) is a photo-radical polymerizable binder resin (A1), and the uncured product is alkali-soluble, and the cured and hardened cured product is insoluble. Since the binder resin (A1) becomes alkali Insoluble hardened material, preferably having an ethylenic double bond, and further, since the binder resin (A1) is alkali soluble And preferably having an acidic group. The ethylenic double bond is polymerized by a radical which is generated by the photopolymerization initiator of the photoactive agent (B). The resin is hardened by the polymerization. The uncured binder resin is contained ( The photosensitive composition of A1) can be removed by an alkaline developing solution, and by the curing of the binder resin (A1), the photosensitive composition containing the same is hardened, and the cured product of the photosensitive composition does not. The photosensitive film composed of the photosensitive composition containing the binder resin (A1) is cured to be alkali-insoluble by the exposed portion, and is alkali-soluble in the unexposed portion. After exposure, an alkaline developing solution is used for development, whereby the unexposed portion of the film can be selectively removed. The acidic group of the binder resin (A1) is not particularly limited, but may be exemplified by The phenolic hydroxyl group, the sulfonic acid group, the phosphoric acid group, and the like may be used in combination of two or more kinds. 11 201232178 The binder resin (A1) may be exemplified by a (mercapto) acrylonitrile 1 bond, which is not particularly limited. The double bond of the addition polymerizable group The hydrogen atom of the addition polymerizable group such as an alkenyl group or a vinyloxy group may be used in combination of two or more kinds. The other 'hydrocarbon group (preferably a methyl group) may be substituted. Part of or all of the '' may also be a binder resin ( A1) is not particularly limited to a side chain having an acidic group and having a vinyl group, and the term "a resin" may, for example, be a resin having a side chain formed by the following method. The monomer of the group is a compound obtained by reacting a monomer copolymer having a base group having an acid group and reacting with a compound having a recombinable group: a side chain of the county. Others can be transferred to the base and the ethylene double epoxy resin. The epoxy resin is introduced into the ethylenic double bond and the acid group resin (A1_2). Use two or more types. The monomer having a key group which is an acid group of the resin (AM) and which has a bond group is not particularly limited, but may be, for example, 2·(methyl)propoxy-(tetra) acid. For example, an epoxy resin can be reacted with a compound having a silk and an ethylenic double bond to react a poly-acid or an acidity thereof to synthesize a resin (A1_2). Specifically, the ethylenic double bond can be introduced into the epoxy resin by reacting the epoxy resin with a compound having a benzyl group and an ethylene double bond. Then, the polynuclear or its acid needle is reacted with an epoxy resin which has been subjected to a double bond, whereby a carboxyl group can be introduced. The epoxy resin is not particularly limited, but may be exemplified by a double-seeking type epoxy resin, a double-presence F type epoxy resin, (4) a secret varnish type epoxy resin, a _ 12 201232178 aldehyde varnish type epoxy resin, and a trisphenol. a decane type epoxy resin, an epoxy resin having a naphthalene skeleton, an epoxy resin having a biphenyl skeleton represented by the following formula (1), and an epoxy represented by the following formula (2) and formula (3) Resin, etc. 【化1】

(1) (於式（1)中，s為1〜50且宜為2〜10。此外，苯環之氫原 子可各自獨自經碳數1〜12之烷基、鹵素原子或亦可具有取 代基之苯基所取代。） 【化2】(1) (In the formula (1), s is 1 to 50 and preferably 2 to 10. Further, the hydrogen atoms of the benzene ring may each independently pass through an alkyl group having 1 to 12 carbon atoms, a halogen atom or may be substituted. Substituted by phenyl group.) [Chemical 2]

(於式(2)中，R31、R32、R33及R34各自獨立為氫原子、 鹵素原子或碳數1〜5之烷基，t為0〜10。） 【化3】 13 201232178(In the formula (2), R31, R32, R33 and R34 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and t is 0 to 10.) [Chemical 3] 13 201232178

(於式（3)中’苯環之氫原子可各自獨立經碳數1〜12之烧 基、齒素原子或亦可具有取代基之苯基所取代。u為0~ 1 〇。） 此外’使通式(2)、通式(3)所示環氧樹脂與具有羧基及 乙烯性雙鍵之化合物反應後，使多元叛酸酐反應時，多元 羧酸酐宜使用二羧酸酐與四羧酸二酐之混合物。此時，可 使二叛酸酐與四效酸二酐之比率發生變化以藉此控制分子 量。 已於環氧樹脂中導入酸性基與乙烯性雙鍵之樹脂 (八卜2)可使用市售品。以商品名而言，此種市售品之任一者 均可列舉如KAYARAD PCR-1069、K-48C、CCR-1105、 CCR-1115、CCR-1163H、CCR-1166H、CCR-1159H、 TCR-1025、TCR-1064H、TCR-1286H、ZAR-1535H、 ZFR-1122H、ZFR-1124H、ZFR-1185H、ZFR-1492H、 ZCR-1571H、ZCR-1569H、ZCR-1580H、ZCR-1581H、 ZCR-1588H、ZCR-1629H、ZAR-2001H(以上為日本化藥社 製）及EX1010(Nagase ChemteX Corporation製）等。 已於環氧樹脂導入酸性基與乙烯性雙鍵之樹脂（A1-2) 以下述者為宜：已於式（1)所示聯苯骨架之環氧樹脂中導入 酸性基與乙烯性雙鍵之樹脂；已於式（2)所示環氧樹脂中導 入酸性基與乙烯性雙鍵之樹脂；或，已於式(3)所示環氧樹 14 201232178 如τ導入酸性基與乙烯性雙鍵 至組成物中時，可藉由使 曰。:：色著色劑摻合 劑，進而可提高隔壁之遮光性及光合更多黑色著色 感光性膜硬化部分之離 二’ X ° *彳’顯像時 圖案。另-方面，線之直線制:可 像後之感光性膜硬化部分所構而車乂為理想。再者，顯 外觀，容賴得平躲在姐㈣後可維持 用於本發明之上述結合劑樹脂⑷）的質量平均分子量 = 1°3〜_3’且更宜為2._3一。若” :如子量小於丨·5,3，則曝光時之硬化有時會變得不 若超過3_3 ’則顯像性有時會降低。此外，於本 5月θ中’ $量平均分子量意指：膠透層析法並以聚 乙烯作為標準物質所測得之值。 Α 一結合劑樹脂（Α1)所具有之乙烯性雙鍵數，以平均而 2於1分子内宜為3個以上，且更宜為_以上。該乙稀性 ，鍵數若為3個以上’則曝光部分與未曝光部分之驗溶解度 4易出現差異，可於更少之曝光量下形成微細圖案。 結合劑樹脂(Α1)之酸價宜為1〇〜3〇〇mgK〇H/g，且更宜 為30〜15〇mgKOH/g。若為1〇〜3〇〇mgKOH/g，則感光性組成 物之顯像性會變得良好。此外，酸價係指：欲中和試料lg 中之樹脂酸等時’所必須之氫氧化鉀毫克數。 本發明之樹脂組成物(NR)中，上述結合劑樹脂(A1)含 里相對於組成物之全固體成分宜為5〜80質量％，且更宜為 10〜60質量％。若為5〜80質量％，則感光性組成物之顯像性 15 201232178 會變得良好。 (1-2)光活性劑（B):光聚合起始劑 作為樹脂組成物（NR)所含光活性劑（B)之光聚合起始 劑（B1)，可無特別限制地使用一般用於自由基硬化型感光 性樹脂組成物之光聚合起始劑。 光聚合起始劑（B1)只要是可利用光之照射而發生自由 基之化合物即不特別受限，但具體而言，可列舉如：苄基、 二乙醯基、曱基苯基乙醛酸酯、9, 10-菲醌等之a-二酮類； 安息香等之醇酮（acyloin)類；安息香曱醚、安息香***、安 息香異丙醚等之醇酮醚類；氧硫aal_(thioxanthone)、2-氣 氧硫0山。星、2-甲基氧硫α山噬、2, 4-二曱基氧硫0山嗟、異丙基 氧硫汕嗟、2, 4-二乙基氧硫0山。星、2, 4-二氣氧硫咄。星、2, 4-二異丙基氧硫σ山嗟、氧硫β山°星-4-磺酸等之氧硫σ山°星類；二 苯基酮、4, 4’-雙（二甲基胺基）二苯基酮、4, 4’-雙(二曱基苯 基）二苯基酮等之二苯基酮類；苯乙酮、2-(4-曱苯磺醯氧 基)-2-苯基苯乙酮、對二曱基胺基苯乙酮、2, 21-二曱氧基-2-苯基苯乙酮、對曱氧基苯乙酮、2-曱基-[4-(甲基硫代）苯 基]-2-N-咮啉基-1-丙酮、2-苄基-2-二曱基胺基-1-(4-Ν-咮啉 基苯基)-丁烷-1-酮等之苯乙酮類；蒽醌、2-乙基蒽醌、樟腦 酉昆(camphor quinone)、1, 4-萘醌等之醌類；2-二曱基胺基苯 甲酸乙酯、4-二甲基胺基苯曱酸乙酯、4-二曱基胺基苯甲酸 (正丁氧基）乙酯、4-二甲基胺基苯甲酸異戊酯、4-二甲基胺 基苯甲酸2-乙基己酯等之胺基苯曱酸類；苯甲基曱醯氣 (phenacyl chloride)、三鹵曱基苯基石風等之鹵素化合物；酿 (3 16 201232178 基膦氧化物類；二第三丁基過氡化物等之過氧化物；丨，2_ 辛烷二酮、1-[4-(苯基硫代)-，2-(〇_苯曱醯基肟)]、乙酮卜^^ 乙基-6-(2-曱基苯曱醯基)_9H-肼曱醯乙醯基肟) 等之肟酯類等；且此等物質可併用2種以上。 於此等物質中，作為本發明所用之光聚合起始劑 (B1)，仍以下述通式(4)所示化合物為佳。 【化4】(In the formula (3), the hydrogen atom of the benzene ring may be independently substituted with a carbon group having 1 to 12 carbon atoms, a dentate atom or a phenyl group which may have a substituent. u is 0 to 1 〇.) When the epoxy resin represented by the general formula (2) or the general formula (3) is reacted with a compound having a carboxyl group and an ethylenic double bond, and the polyvalent carboxylic acid anhydride is reacted, the polycarboxylic acid anhydride is preferably a dicarboxylic acid anhydride and a tetracarboxylic acid. a mixture of dianhydrides. At this time, the ratio of the di-theorecanic acid to the tetra-acid dianhydride can be changed to thereby control the molecular weight. A commercially available product can be used as a resin in which an acidic group and an ethylenic double bond are introduced into an epoxy resin. In the case of a trade name, any of such commercial products can be enumerated as KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1163H, CCR-1166H, CCR-1159H, TCR-. 1025, TCR-1064H, TCR-1286H, ZAR-1535H, ZFR-1122H, ZFR-1124H, ZFR-1185H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1629H, ZAR-2001H (above, manufactured by Nippon Kayaku Co., Ltd.) and EX1010 (manufactured by Nagase ChemteX Corporation). The resin (A1-2) which has been introduced with an acidic group and an ethylenic double bond in an epoxy resin is preferably one which has introduced an acidic group and an ethylenic double bond in an epoxy resin of a biphenyl skeleton represented by the formula (1). a resin which has been introduced with an acidic group and an ethylenic double bond in the epoxy resin represented by the formula (2); or an epoxy group and an ethylenic double which have been introduced into the epoxy tree 14 201232178 as shown in the formula (3). When the bond is applied to the composition, it can be made by enthalpy. The colorant blending agent can further improve the light-shielding property of the partition wall and the more black coloration of the photosensitive film, and the pattern of the hardened portion of the photosensitive film from the two 'X ° *彳' development. On the other hand, the straight line system of the line: it can be constructed like a photosensitive film hardened part, and the rut is ideal. Further, it is apparent that the mass average molecular weight of the above-mentioned binder resin (4) used in the present invention can be maintained to be 1 to 3 to _3' and more preferably 2. _3. If the amount is less than 丨·5,3, the hardening at the time of exposure may not exceed 3_3', and the development may be lowered. In addition, the average molecular weight in this θ is ' Means: the value measured by gel permeation chromatography and using polyethylene as a standard substance. Α The amount of ethylenic double bonds in a binder resin (Α1) is, on average, 2 in 1 molecule. The above, and more preferably _ or more. If the number of bonds is three or more, the difference between the exposed portion and the unexposed portion is likely to be different, and a fine pattern can be formed with less exposure. The acid value of the resin (Α1) is preferably from 1 〇 to 3 〇〇 mg K 〇 H / g, and more preferably from 30 to 15 〇 mg KOH / g. If it is from 1 〇 to 3 〇〇 mg KOH / g, the photosensitive composition In addition, the acid value refers to the number of milligrams of potassium hydroxide necessary to neutralize the resin acid or the like in the sample lg. In the resin composition (NR) of the present invention, the above The binder resin (A1) is preferably contained in an amount of 5 to 80% by mass, and more preferably 10 to 60% by mass, based on the total solid content of the composition. If it is 5 to 80% by mass, The development of the optical composition 15 201232178 will become good. (1-2) Photoactive agent (B): Photopolymerization initiator as photopolymerization of photoactive agent (B) contained in resin composition (NR) The photopolymerization initiator which is generally used for the radically curable photosensitive resin composition can be used without any particular limitation. The photopolymerization initiator (B1) is free to be irradiated with light. The compound of the group is not particularly limited, but specifically, for example, a-diketone such as benzyl, diethylidene, nonylphenylglyoxylate or 9,10 phenanthrene; benzoin Such as acyloin; benzoin ether, benzoin ethyl ether, benzoin isopropyl ether and other alcohol ketone ethers; oxygen sulfur aal_ (thioxanthone), 2-oxygen sulfur 0 mountain. Star, 2-methyl oxysulfide山山噬, 2, 4-dimercaptooxy oxysulfonate, isopropyl oxysulfonium, 2, 4-diethyloxysulfur 0. Star, 2, 4-dioxathiazide. Star , 2, 4-diisopropyloxysulfur sigma, oxysulfide, beta sulphate-4-sulfonic acid, etc., oxygen sulphur σ mountain ° star; diphenyl ketone, 4, 4'-bis (dimethyl Aminophenyl)diphenyl ketone, 4,4'-bis(dimercaptobenzene a diphenyl ketone such as diphenyl ketone; acetophenone, 2-(4-nonylbenzenesulfonyloxy)-2-phenylacetophenone, p-didecylaminoacetophenone, 2, 21-dimethoxy-2-phenylacetophenone, p-decyloxyacetophenone, 2-mercapto-[4-(methylthio)phenyl]-2-N-indolyl-1 - acetophenones such as acetone, 2-benzyl-2-didecylamino-1-(4-indole-phenyl-phenyl)-butan-1-one; anthracene, 2-ethyl醌, camphor quinone, 1,4-naphthoquinone, etc.; 2-didecylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-di Aminobenzoic acid such as decylaminobenzoic acid (n-butoxy)ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester a halogen compound such as phenacyl chloride or trihalofluorenyl phenyl stone; a peroxide (3 16 201232178-based phosphine oxide; a peroxide such as a di-t-butylperoxylate; , 2_octanedione, 1-[4-(phenylthio)-, 2-(indolyl hydrazinyl)], ethyl ketone b ^^ ethyl-6-(2-mercaptophenyl hydrazine醯 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) These materials may be used in combination of two or more kinds. Among these, the photopolymerization initiator (B1) used in the present invention is preferably a compound represented by the following formula (4). 【化4】

(式(4)中’ R21為氫原子、碳數卜12之烷基、碳數3〜8 之環烷基、碳數2〜5之烯基、經烷基取代或非經取代之碳數 6〜20之苯基或是經院基取代或非經取代之碳數6〜2〇之苯氧 基；R22為氫原子、碳數1〜2〇之烷基、碳數3〜8之環烷基、 經烷基取代或取代之碳數6〜20之苯基、碳數2〜20之烷醯 基、經烷基取代或非經取代之碳數7〜20之苯甲醯基、碳數 2〜12之烷氧羰基或是經烷基取代或非經取代之碳數7〜2〇之 苯氧羰基；R23為碳數1〜12之烷基；R24、R25、R26及R2? 各自獨立為氫原子、碳數1〜12之烷基、經烷基取代或非經 取代之碳數3〜8之環己基、經烷基取代或非經取代之碳數 6~20之笨基、碳數2〜20之烷醯基、經烷基取代或非經取代 之礙數7〜20之苯甲醯基、經烷基取代或非經取代之碳數 17 201232178 7〜20之苄羰基、碳數2〜12之烷氧羰基、經烷基取代或非經 取代之碳數7〜20之苯氧羰基、碳數1〜20之醯胺基或硝基。） 通式（4)所示化合物中，R21宜為碳數1〜10之烷基或是 經烷基取代或非經取代之碳數6〜12之苯基，且可列舉如甲 基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、 癸基及苯基等。於該等之中，以碳數1〜4之烷基為宜，且更 宜為碳數1或2之烷基，尤以曱基為佳。 通式（4)所示化合物中，R22宜為碳數1〜10之烷基或碳 數2〜5之烷氧羰基，可列舉如甲基、乙基、丙基、丁基、戊 基、己基、庚基、辛基、壬基、癸基、甲氧羰基、乙氧羰 基及丙氧羰基等。其中，以碳數1〜6之烷基為宜，且更宜為 碳數1〜3之烷基，尤以曱基為佳。 通式（4)所示化合物中，R23所示碳數1〜12之烷基可列 舉如曱基、乙基、丙基、丁基、戊基、己基、庚基、辛基、 壬基、癸基、十一烷基及十二烷基等。於該等之中，以碳 數1〜8之烷基為宜，且更宜為碳數2〜6之烷基，尤以乙基為 佳。 於通式（4)所示化合物中，R24、R2 6及R2 7以氫原子為 佳。 通式（4)所示化合物中，R25宜為經烷基取代或非經取 代之碳數7〜20之苯曱醯基或是經烷基取代或非經取代之碳 數7〜20之苄羰基，且以2-甲基苯甲醯基、苄羰基或1，3, 5-三曱基苄羰基尤佳。 e 通式（4)所示化合物之(Ο-醯基肟系化合物）並未特別受 18 201232178 限，但可列舉如下述化合物：通式⑷中，r2i為苯基，r22 為辛基，RU為乙基，r24、r26及r27為氣原子且r25為苯 甲2醯基之化合物；為甲基，r22為丁基、庚基或辛基， R23為乙基’ R24、R26及R27為氫原子且R25為苯曱醯基之 化合物；R2i為苯基，r22為辛基，r23為乙基，r24、r26 及R27為氫原子且R25為2·甲基苯甲醯基之化合物；r21為甲 基，R為曱基或辛基’ r2 3為乙基，r2 4、r2 6及r2 7為氫 原子且R為2-甲基苯甲醯基之化合物；及，R21及R22為甲 基，R23為乙基，R24、尺^及“？為氫原子，r25為2-甲基 _5_四氫呋喃基甲氧基苯曱醯基、2-曱基-4-四氫哌喃基甲氧 基苯甲醯基或2-甲基-5-四氫哌喃基f氧基苯曱醯基之化合 ' 物等。 • 光聚合起始劑（B1)可使用市售品。市售品可列舉如 OXE02(商品名 ’ Ciba Specialty Chemicals社製，乙酮i-[9-乙基-6-(2-曱基苯曱醯基)_9H-肼甲醯基-3-基]-l-(〇-乙醯基 肟）：上述通式(4)中，R21及R22為甲基，R23為乙基，R2 4、 R26及R27為氫原子且r25為2-曱基苯甲醯基之化合物）、 IRGACURE OXE01(商品名，BASF社製，相當於1，2-辛烷 二酮，1-[4-(苯基硫代）-2-(0-苯甲醯基肟）])、ADEKA OPTOMER N-1919、ADEKA ARKLS NCI-831、ADEKA ARKLSNCI-930(以上為 ADEKA 社製）等。 本發明之樹脂組成物(NR)中，上述光聚合起始劑(B1) 之摻合比例雖亦依欲使用之光學元件的種類及用途而異， 但相對於上述光自由基聚合性結合劑樹脂(A1)宜為1〜50質 19 201232178 量％，且宜為5〜25質量％。若是此種範圍，感光性杈成物 硬化性及顯像性會變得良好。 此外，在本發明之樹脂組成物(NR)之全固體成分中 光聚合起始劑（B1)之含量宜為1〜4〇質量％，且更宜為^ 質量％。若是此種範圍，則感光性組成物之硬化性會變〜 良好，可利用曝光、顯像來形成接近光罩圖案之圖案卞 此外，右在使用光聚合起始劑(Β〇時同時使用2 、,， 埽衣并 咪唑、2-酼苯并噚唑、2-Μ苯并噻唑、丨4_丁醇蝕 四 果。 丁酸酯）、參(2_巯基丙醯基氧乙基）三聚異氰酸酯、新戊 醇肆(3-酼基丁酸酯）等之硫醇化合物，有時會表現出增 U-3)微粒子(〇 本發明之樹脂組成物(NR)含有微粒子作為、、/ 分，且於分散液中該微粒子（C)以電泳光散射法測^項成 仇為-i 00〜-5mV。此外，於本說明書中，只要未有特另^^電 有關該微粒子（C)之以下記述内容不限於樹脂組’ (Nr)，而與本發明之全部感光性樹脂組成物共通。、成物 作為微粒子(c)，可使用以下述說明之電泳光散射法测 定之ξ電位為-100〜-5mV的各種無機系微粒子及有機系忾粒 子。微粒子（C)之ξ電位宜為-80〜_8 v， ” 且吏宜為 ~5〇〜-10mV，以-35〜-12mV尤佳。 > ξ電位之測定方法： 將已使微粒子(C)分散至分散介質之分散液調整成微 20 201232178 料以）相對於分散液全量之比例為6.〇xl〇·4質量°/。的試 〆 "'電子社製之ζ電位測定系統(ELSZseries)測定ξ電 外’則定值係藉由用於上述試料製作之分散介質的 #值(折射率、黏度及相對介電係數），從以下之Huckel 數算出ξ電位(ζ)者。此外’測定用試料之調製僅需使用 人刀放液所用者相同之分散介質並將濃度調製成如上述般 即可。從微粒子(C)之單體調製測定試料時，顚應微粒子 之表面狀態（例如微粒子（C)之羥基濃度）等，選擇該微粒子 (C)可充分進行分散之分散介質，製作出上述濃度之分散液 並用作測定用試料。 【數1】(In the formula (4), 'R21 is a hydrogen atom, a carbon number 12 alkyl group, a carbon number 3 to 8 cycloalkyl group, a carbon number 2 to 5 alkenyl group, an alkyl group or a non-substituted carbon number. a phenyl group of 6 to 20 or a substituted or unsubstituted phenoxy group having a carbon number of 6 to 2; R22 is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and a cycloalkane having 3 to 8 carbon atoms. a phenyl group having 6 to 20 carbon atoms, an alkyl group substituted or substituted with an alkyl group, an alkyl fluorenyl group having 2 to 20 carbon atoms, an alkyl group or an unsubstituted benzoyl group having a carbon number of 7 to 20, and a carbon number 2 to 12 alkoxycarbonyl or an alkyl-substituted or unsubstituted phenyloxycarbonyl group having 7 to 2 carbon atoms; R23 is an alkyl group having 1 to 12 carbon atoms; and R24, R25, R26 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl-substituted or unsubstituted carbon group having 3 to 8 carbon atoms, an alkyl group or a non-substituted carbon group having 6 to 20 carbon atoms, carbon a 2 to 20 alkyl alkoxy group, an alkyl substituted or unsubstituted benzylidene group having 7 to 20 alkyl groups, an alkyl substituted or unsubstituted carbon number 17 201232178 7 to 20 benzyl carbonyl, carbon Number of alkoxycarbonyl groups of 2 to 12, alkyl substituted or unsubstituted carbon number 7~ a phenoxycarbonyl group of 20, a decylamino group having a carbon number of 1 to 20 or a nitro group. In the compound of the formula (4), R21 is preferably an alkyl group having 1 to 10 carbon atoms or an alkyl group or a non- The substituted phenyl group having 6 to 12 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or a phenyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferred, and an alkyl group having 1 or 2 carbon atoms is more preferred, and a mercapto group is preferred. In the compound of the formula (4), R22 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl, heptyl, octyl, decyl, decyl, methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl. Among them, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred, and a mercapto group is preferred. In the compound of the formula (4), the alkyl group having 1 to 12 carbon atoms represented by R23 may, for example, be an alkyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group or a decyl group. Mercapto, undecyl and dodecyl groups. Among these, an alkyl group having 1 to 8 carbon atoms is preferred, and an alkyl group having 2 to 6 carbon atoms is more preferred, and particularly preferably an ethyl group. In the compound of the formula (4), R24, R2 6 and R2 7 are preferably a hydrogen atom. In the compound of the formula (4), R25 is preferably an alkyl-substituted or unsubstituted phenylene group having 7 to 20 carbon atoms or an alkyl-substituted or unsubstituted benzyl group having 7 to 20 carbon atoms. The carbonyl group is preferably 2-methylbenzylidene, benzylcarbonyl or 1,3,5-trimethylbenzylcarbonyl. e (Ο-mercapto lanthanide compound) of the compound of the formula (4) is not particularly limited to 18 201232178, but may be exemplified by the following compounds: in the formula (4), r2i is a phenyl group, and r22 is an octyl group, RU a compound wherein ethyl, r24, r26 and r27 are a gas atom and r25 is a benzylidene group; a methyl group, r22 is a butyl group, a heptyl group or an octyl group, and R23 is an ethyl group 'R24, R26 and R27 are hydrogen. a compound in which R25 is a phenyl group; R2i is a phenyl group; r22 is an octyl group; r23 is an ethyl group; r24, r26 and R27 are a hydrogen atom and R25 is a 2:methylbenzhydryl group; Methyl, R is a fluorenyl or octyl 'r2 3 is an ethyl group, r 2 4, r 2 6 and r 2 7 are hydrogen atoms and R is a 2-methylbenzhydryl group; and R21 and R22 are methyl groups. , R23 is ethyl, R24, 尺^ and "? is a hydrogen atom, r25 is 2-methyl-5-tetrahydrofuranylmethoxyphenyl fluorenyl, 2-mercapto-4-tetrahydropyranyl methoxy A benzylidene group or a 2-methyl-5-tetrahydropyranylf-oxyphenyl fluorenyl group, etc. • A commercially available product can be used as the photopolymerization initiator (B1). For example, OXE02 (trade name 'Ciba Specialty Chemicals Co., Ltd., Ethyl ketone i-[9-ethyl-6-(2-mercaptobenzoyl)_9H-indolyl-3-yl]-l-(indolyl-indole): the above formula (4) In the formula, R21 and R22 are a methyl group, R23 is an ethyl group, R2 4, R26 and R27 are a hydrogen atom and r25 is a 2-mercaptobenzylidene group), and IRGACURE OXE01 (trade name, manufactured by BASF Corporation) 1,2-octanedione, 1-[4-(phenylthio)-2-(0-benzylidenehydrazine)]), ADEKA OPTOMER N-1919, ADEKA ARKLS NCI-831, ADEKA ARKLSNCI In the resin composition (NR) of the present invention, the blending ratio of the photopolymerization initiator (B1) varies depending on the type and use of the optical element to be used. However, the photoradical polymerizable binder resin (A1) is preferably 1 to 50 mass 19 201232178% by weight, and preferably 5 to 25% by mass. If it is such a range, the photosensitive composition is hardenable and imaged. In addition, the content of the photopolymerization initiator (B1) in the total solid content of the resin composition (NR) of the present invention is preferably from 1 to 4% by mass, and more preferably from 5% by mass. If it is such a range, the hardenability of the photosensitive composition may change. Good, exposure and development can be used to form a pattern close to the reticle pattern. In addition, the photopolymerization initiator is used right (when Β〇, 2, ,, 咪唑, imidazole, 2-indole benzoxazole, 2-indole benzothiazole, 丨4_butol eclipse four fruits. a thiol compound such as butyrate), ginseng (2-mercaptopropenyloxyethyl)trimeric isocyanate or neopentyl hydrazine (3-mercaptobutyrate), sometimes exhibits an increase in U-3) The fine particles (the resin composition (NR) of the present invention contains fine particles as , , and /, and the fine particles (C) are measured by electrophoretic light scattering in the dispersion to be -i 00 to -5 mV. In the present specification, the following description of the fine particles (C) is not limited to the resin group '(Nr), and is common to all the photosensitive resin compositions of the present invention. (c) Various inorganic fine particles and organic cerium particles having a zeta potential of -100 to -5 mV measured by an electrophoretic light scattering method described below can be used. The zeta potential of the fine particles (C) is preferably -80 to _8 v, And it is preferably ~5〇~-10mV, especially -35~-12mV. > Determination of zeta potential: The dispersion which has dispersed the fine particles (C) into the dispersion medium is adjusted to micro 20 201232178 ) The ratio of the total amount of the dispersion to the amount of 6.〇xl〇·4 mass °/. (ELSZseries) The measurement of the external potential is based on the # value (refractive index, viscosity, and relative dielectric constant) of the dispersion medium used for the above-mentioned sample, and the zeta potential (ζ) is calculated from the following Huckel number. In addition, the measurement of the measurement sample requires only the same dispersion medium as that used for the human knife discharge, and the concentration can be adjusted as described above. When the sample is prepared from the monomer (C), the surface state of the microparticles is measured. (For example, the hydroxyl group concentration of the fine particles (C)), the dispersion medium in which the fine particles (C) can be sufficiently dispersed is selected, and a dispersion liquid having the above concentration is prepared and used as a sample for measurement.

U 2 ε 〇ε Γξ 377 2ε〇εΓ (式中，ε0、&、η分別表示分散介質於25。〇下之真空介 電率、相對介電係數、減(mPa · s)。電位。） 本說明書巾’餘子(C)之ξ電位係指上述方法所測定 之ξ電位。本發明之感光性樹脂組成物摻合有微粒子(c)之 分散液，且所摻合之分散液中之微粒子（c)的$電位為 -100〜-5mV。 本發明之感光性樹脂組成巧所含有之微粒子（c)為上 述分散液中之微粒子，藉此，微粒子(c)會於組成物中—邊 21 201232178 保持分散性’-邊與構成感光性樹脂組成物之其他成分互 相拉扯地發揮作用，更因為與基板(特別是表面存有超基之 基板m有強烈之相互密㈣用，卿成之㈣與基材二面 之密著性_甚高’顯料不易觸。結果，可獲得高解 像度之圖案。此外，微粒子(c)於感紐樹脂組成物中具有 優異之分散性，因此本發明之感光,_難成物顯示出優 異之儲藏安定性。 此外，就本發明之感光性樹脂組成物而言由於含有 上述微粒子(C)，在使用感光性黯組成物而以紐刻法形 成隔J時’亦可藉此獲得下述效果^對於顯像後進行之後 焙步驟之加熱，圖案的形狀安定性提升。 就上述微粒子（C)除了ξ電位以外之特性而言，從曝光 之觀點來看’其宜為透明微粒子。此外，從顯像密著性及 所形成之隔壁的表面平滑性等觀點來看，微粒子(c)以雷射 繞射散射法求出之平均粒徑宜為5〜100nm，更宜為 10〜80nm ’且以20〜50nm尤佳。 此外，為了不使感光性組成物之感度降低，微粒子(c) 宜為對於曝光步驟中所照射之光波長不具吸收者，且尤以 對超高壓水銀燈之主發光波長丨線(36511〇1)、h線(4〇5nm)、g 線(436nm)不具吸收者收為佳。 在微粒子(C)之中，無機系微粒子可列舉如二氧化矽' 氧化锆、氟化鎂、ITO(氧化銦錫）及AT0(氧化錫銻）等之微 粒子。有機系微粒子可列舉如聚乙烯及PMMA等之微粒 子。從耐熱性(7)觀點來看，本發明所用之微粒子(c)宜▲無 201232178 機系微粒子，更從分散安定性之觀點來看，二氧化石夕微粒 子及氧化锆微粒子更佳，從取得容易性之觀點來看，則以 一氧化>5夕微粒子尤佳。 在本發明之感光性樹脂組成物中，上述微粒子（c)係以 分散狀態含於感光性樹脂組成物中。於此，具體來說，「分 散狀態」係指藉由靜電性之相互作用（推斥力）而£現分散之 狀態。本發明之感光性樹脂組成物係摻合有微粒子(c)之分 散液的組成物，該分散液中之微粒子（C)的ξ電位為 -100〜-5mV。藉由摻合具有此種特性之微粒子(c)，於感光 性樹脂組成物中上述微粒子(c)不會沈降或凝集，可於安定 狀態下分散在感光性樹脂組成物中。 此種微粒子(C)分散液中之分散介質可具體列舉如：選 自具有至少1個羥基且SP值為9〜之有機溶劑 中的1種或2種以上者。此種分散介質之sp值宜為 9~18(cal/cm3),/2，£ S ^ 10~15(cal/cm3)'/2 〇 於此，溶劑之SP值（溶解性參數）係該溶劑之凝集能密 度（即1分子之每單位體積的蒸發能）乘1/2次方的數值，顯示 母單位體積之極性大小。單位為（cal/cm3)i/2，只要無特別 聲明，在本說明書中係指25°C下之值。SP值可藉以心仍法 箅出（參照文獻.R.F.Fedros, Polym.Eng.Sci., 14[2]147(1974))。 此種有機溶劑可具體列舉如下述表1所示之有機溶 * .劑。有機溶劑以碳數4以下之烷醇、碳數2或3之伸烷基二醇 或其2量體以及該伸烷基二醇或其2量體之單烷基醚（烷基 23 201232178 喊部分之碳數為4以下）尤佳。 表1 有機溶劑 ---—-- (SP 值） (cal/cm3)I/2 乙醇 '— 一 ___—. 12.6 f醇 --—〜. 13.8 卜丙醇 11.8 上^醇(IPA) 11.6 “丁醇 11.3 17.8 乙二醇單曱醚 ~~ 12.0 乙一醇單*** ~ 11.5 乙一醇單丙謎 11.1 ΙΓΖϊϊΓ單異丙醚 ~~ - 11.1 乙二醇單丁醚 " — 10.8 丙二醇 — 15.9 丙一醇單曱醚 11.3 丙二醇單*** 一- 10.9 3二醇單丙醚(NPC) 10.7 丙二醇單異丙醚 " - 10.5 丙二醇單丁謎 10.4 —丙二醇 13.3 二醇單甲驗 - 10.4 ~~ 醇單乙鱗 卜 10.3 ~~ 二醇單丙崎 ' Τ〇Ί ~ ~ΞΓ^~二醇單異丙縫 —- 10.0 一丙二醇單丁趟 - ~10.0 ~~ 此外，用作上述微粒子(C)之分散介質的有機溶劑亦可 為該等中之2種以上混合物’只要混合溶劑之SP值在 9〜20(Cal/em3)w之範圍’亦可是與其他溶劑之混合物。該 等物質中’以甲醇、2-丙醇及乙二醇單丙基驗為佳。此外， 上述微粒子(c)使用二氧化雜粒子時，以2_丙醇及乙二醇 早丙轉尤佳β 微粒子(C)宜祕體二氧切。虹财機溶劑分散液 且二氧切微粒子之ξ電位L_5mV之膠體二氧化石夕可 24 201232178 之有機一氧化砂溶 列舉如將上述有機溶劑用作分散介質 膠。 此種有機二氧化砂溶膝可使用市售品，市售品可列兴 如NPCST(商品名，日產化學工#社製，ξ電位：_15睛，; 均粒徑：24nm，分散介質：乙二醇單㈣，SI體成分：3〇 質量％)、IPAST(商品名，日產化學工業社製，ξ電位： -28mV ’平均純：45nm，分散介質：2_丙醇固體成分： 3〇質量％)等。 ’ 本發明之感光性樹脂組成物之全固體成分中，以感光 性樹脂組成物之固體成分合計量為_質量％，微粒子\c) 之含有比例宜為3〜35質量％，且較宜為5〜3〇質量％，更宜為 7 了 25質量。/。’以1G〜23f量％尤佳。若含量過少，則抑制上 述形成之職Η案化層在祕顯料_之效果較差，若 含量過多則組成物之液體安定性會有降低的傾向。 此外’對感光性樹餘成物摻合微粒子(c)具有提高圖 案對於後財驟加熱之形狀妓性的作用。雖亦依上述結 合劑樹脂㈧之種類及加熱條件等而異，為了獲得充分之圖 案形狀t定性’餘子(C)之摻合量以感紐樹脂組成物之 Q體成分合计董作⑽質量％計，宜為12〜3G質量％，更宜為 15〜25質量％，且以18〜23質量％尤佳。 (1-4)有機溶劑(D) 本發明之感光性樹脂組成物含有有機溶劑(D)。有機溶 劑(D)之至少-部分為微粒子(C)分散液的分散介質。此外， 只要說明t中無特別聲明，有關該有機溶劑(D)之以下記述 25 201232178 不限於樹脂組成物（NR)，而與本發明之全部感光性樹脂組 成物共通。 有機溶劑（D)之一部分亦可含有不同於微粒子（C)分散 液之分散介質的其他有機溶劑。此種有機溶劑可與分散介 質為同一有機溶劑，亦可為不同之有機溶劑。舉例來說， 只摻合微粒子（C)之分散液會使感光性樹脂組成物之固體 成分濃度過高時，可使用與分散液之分散介質相同或不同 之有機溶劑，將固體成分濃度調整至預定濃度。此外，使 用與分散介質相同或不同之有機溶劑來調整分散液之微粒 子（C)的濃度後，亦可藉由使用該分散液來同樣地進行感光 性樹脂組成物之固體成分濃度的調整。 使用與分散液之分散介質不同的有機溶劑時，由於感 光性樹脂組成物中之有機溶劑（D)會成為分散介質之有機 溶劑與其他有機溶劑的混合物，已分散於感光性樹脂組成 物之有機溶劑（D)的微粒子（C)會有分散安定性降低之虞。因 此，使用與分散介質不同之有機溶劑時，宜使用藉由下述 手段而使分散安定性降低較少之有機溶劑：為減少ξ電位變 化而使用與分散介質之有機溶劑具有類似特性（介電率、相 對介電係數、黏度等）之有機溶劑；降低與分散介質不同之 有機溶劑的使用量。 與分散介質各別使用之有機溶劑宜為前述分散介質所 列舉之有機溶劑。以下述有機溶劑為宜：與所使用之分散 液中的分散介質相同或不同，具有至少1個羥基且SP值為 9〜20(cal/cm3)1/2。 r3 26 201232178 有機溶劑⑼除了作為分散介質而換合於感光性樹脂 組成物者以及另行單獨摻合者H可錢同其他成分 之摻合而被摻合者。舉例來說可列舉如，前述光活性劑⑻ 以溶液形式作摻合的情況、後述之著色劑⑹以分散劑形式 作摻合的情況以及後述之撥墨劑以溶劑形式作摻合的情況 等。連同其他成分之摻合而被摻合之有機溶劑在其換合量 較少之情況下則種類不特別受限。但是，與作為前述分散 介質而摻合者及另行摻合者的合計量對比下相對較多時， 宜為前述分散介質所列舉種類之有機溶劑，且更宜為與所 用分散介質相同之有機溶劑’或是與有毅前述分散介質 而另行摻合者相同之有機溶劑。 就有機溶劑(D)之總量，宜以令感光性樹脂組成物中之 固體成分濃度成為5〜40質量％之方式來調整溶劑量，且宜 調整成10〜25質量％。 且 (1-5)任意成分 本發明之樹脂組成物(NR)除了上述(A)成分〜(c)成分 等之必須成分之外，亦可適當地依需要而摻合著色劑作卜 撥墨劑、用以增加硬化物之交聯密度的自由基交聯劑或熱 交聯劑、用以獲得基材密著性之矽烷偶合劑、磷酸化合物、 界面活性劑、硬化促進劑、增黏劑、可塑劑、消泡劑、碉 平劑、防塌凹劑、紫外線吸收劑及溶劑等。 (著色劑(E)) 本心明之感光性樹脂組成物中，隔壁為具有遮光性之 遮光層時’即用作黑矩陣(biack matrix)時，本發明之效果 27 201232178 會更為顯著。因此，在製造隔壁為遮光層之光學元件上， 本發明之感光性樹脂組成物可適用良好。 由本發明之樹脂組成物(NR)形成之隔壁如前述般用作 黑矩陣時，感光性樹脂組成物宜含有黑色著色劑。此種黑 色著色劑可具體列舉如碳黑、笨胺黑、蒽醌系黑色顏料、 鈦黑等之金屬氧化物粒子、黑色金屬氧化物顏料、銀錫合 金等之合金粒子、花系黑色顏料例如C.I. .pigment black 1、 6 、 7 、 12 、 20 、 31等。 此外’黑色著色劑亦可使用紅色顏料、藍色顏料、綠 色顏料、黃色顏料等之有機顏料、次曱基偶氮(azomethine) 系黑色顏料及無機顏料之混合物。再者，上述黑色著色劑 以價格及遮光性大小之觀點來看宜為碳黑，且碳黑亦可藉 樹脂等作表面處理。此外，為了調整色調，亦可併用藍色 顏料或务、色顏料。就黑矩陣陣列（black matrix on array)型之 濾色器及有機EL元件而言，其需求低介電率及高阻抗之膜 及隔壁。為了製得該膜及隔壁，宜使用上述有機顏料之混 合物及次甲基偶氮系黑色顏料。 黑色著色劑之摻合量雖亦依所用光學元件之種類及用 途而異，但舉例來說，隔壁用作濾色器之黑矩陣時，相對 於感光性樹脂組成物之全固體成分量，宜將1〇〜5〇質量％之 ^色著色劑與依需要而定之適當分散介質、分散劑一起調 屣並摻合成分散液。黑色著色劑之摻合量若在該範圍内， 斤知感光性樹脂組成物之感度會變得良好，且形成之隔壁 具優異遮光性。 · Γο !發' 28 201232178 (撥墨劑） 就本發明之感光性樹脂組成物而言，使用其以光蝕刻 法形成隔壁’藉此基板上被區隔出多數區塊，形成光學元 件之像素形成用區域（以下，有時稱為「點（dot)」）。於此， 该隔壁被用作以噴墨法形成像素之光學元件的隔壁時，本 發明之感光性樹脂組成物宜含有賦予所得隔壁之上部表面 撥墨性的撥墨劑。於此，所謂撥墨性係依墨水組成而異， 指撥水性或撥油性’甚或兼具撥水性與撥油性雙方之性 貝。更具體來說，指彈開用於墨水之水或有機溶劑等之溶 劑的性質，一般而言，分別可以水或適當之有機溶劑（例 如，1-甲氧基-2-乙氧基丙烷或丙二醇單甲醚2_乙酸酯 (PGMEA)等’-般用於噴墨法之墨水所含有的有機溶劑) 之接觸角來評估。 叩〜个货π<埶光性樹脂組成物的撥墨劑即是：在含 有其之感光性樹脂組成物形成隔壁時，可賦予隔壁之上部 表面所需求撥墨性（即，將用於墨水之水或有機溶劑等溶劑 彈開的性質）的化合物。 ~ 此種藉由換合至感光性樹脂組成物而在形成隔壁時賦 予隔壁上料面撥墨性之撥墨劑，較佳者可列舉如 合物、含魏合物及兼魏好 3軋化 用作上述撥墨劑之含氣化合物可不受限 = :::Γ 此外，可㈣增嫩她咖無特别限制 29 201232178 地列舉習用公知之撥墨劑用含矽化合物，例如具有二曱基 石夕氧院基之聚合物等。 可用作上述撥墨劑之兼有氟原子與矽原子的化合物可 不受特別限制地列舉習用公知之撥墨劑用含氟^石夕化合物， 例如’含氟矽烷偶合劑即兼有氟烷基與二曱基矽氧烷基之 聚合物等。 此種撥墨劑之中，側鏈具有氟烷基之聚合物由於賦予 撥墨性之能力較高而可列為較佳態樣。此種於側鏈具有氟 炫基之聚合物可藉習用公知方法來製造，例如日本特開 2000-102727號公報及日本特開2002-249706號公報等所揭 不之方法。 只要在本說明書中未有特別聲明，以上載述之撥墨劑 可不拘感光性樹脂組成物之種類來使用。 此外，為樹脂組成物(NR)時，撥墨劑之較佳態樣可列 舉在側鏈具有氟烷基與乙烯性雙鍵之聚合物。其理由在 於’若將側鏈具有氟烷基與乙烯性雙鍵之該聚合物用作撥 墨劑，在後述利用光蝕刻法形成隔壁之曝光步驟及後焙步 驟中，上述撥墨劑會與負型感光性樹脂組成物中之其他摻 合成分反應，而在隔壁上部表面固定化。 此種側鏈具有氟烷基與乙烯性雙鍵之聚合物的較佳態 樣之一可列舉如含有下述聚合單元之聚合物：具有至少1個 (更宜全部）氫原子經氟原子取代之碳數20以下的直鏈狀或 分枝狀烷基(但烷基包含醚性之具有氧者）的聚合單元；及’ 具有（曱基）丙稀醯基、稀丙基、乙稀、乙烯趟基等之乙稀性 30 201232178 ' 雙鍵的聚合單元。 適宜用作上述撥墨劑且側鏈具有氟烷基與乙烯性雙鍵 之上述聚合物的數平均分子量宜為5〇〇〜15〇〇〇〇，更宜為 1，000〜100,000，且質量平均分子量宜為1〇〇〇〜3〇〇〇〇〇，更 宜為5,000〜150,000。若在此範圍内，則鹼溶解性及顯像性 會變得良好。又，從撥墨性與隔壁成形性之觀點來看，該 聚合物中之氟含量宜為5〜5〇質量％，更宜為1〇〜40質量％， 且以12〜30質量°/〇尤佳。再者，該聚合物在側鏈具有之乙稀 性雙鍵數宜為0.5〜5_0m〇l/g，更宜為1.0〜3_0mol/g。若在此 範圍内則顯像性會變得良好。 再者，上述聚合物可在側鏈具有矽數200以下程度之聚 矽氧(silicone)鏈(直鏈）。此外，聚合物之矽含量從撥墨性與 _ 隔壁成形性之觀點來看，宜為0.5〜30質量％，更宜為0.5〜1〇 質量％。 於此，用作撥墨劑之上述聚合物宜具有酸性基，舉例 來說，即選自羧基、酚性羥基及磺酸基之群組中的至少1個 酸性基。其理由在於，藉由具有鹼可溶性，基板上之隔壁 所區隔出的區域(dot)内不易殘留撥墨劑，以喷墨法注入墨 水時之墨水濕潤擴張性良好。從此種觀點來看，聚合物之 酸價宜為5~200mgKOH/g ’更宜為l〇~l〇〇mgKOH/g，且以 20 〜60mgKOH/g尤佳。 上述說明之側鏈上具有氟烷基與乙烯性雙鍵及任擇之 聚矽氧鏈且宜更具有酸性基之聚合物可藉習用公知方法來 製造，具體來說，則是國際公開第2004/042474號、國際公 31 201232178 開第2007/069703號、國際公開第2008/149776號等所揭示之 方法。 含有上述撥墨劑之樹脂組成物(NR)的固體成分中，撥 墨劑之含有比例相對於組成物固體成分全量宜在0.01〜30 質量％之範圍内。其理由在於，所得隔壁之撥墨性良好， 且以喷墨法注入之墨水在點（dot)内之濕潤擴張性良好，注 入之墨水層之均勻性良好。 作為上述撥墨劑而摻合至感光性樹脂組成物之含有I 原子及/或矽原子之聚合物通常亦具有界面活性劑之作 用。因此，感光性樹脂組成物含有撥墨劑時，除了特別需 要追加之情況，不會更摻合界面活性劑。形成以噴墨法以 外之方法進行像素形成之光學元件用隔壁的感光性樹脂組 成物通常不含撥墨劑，因此宜添加界面活性劑。界面活性 劑使用與上述撥墨劑同樣之聚合物亦可，但也可使用市售 品0 此種界面活性劑有聚矽氧系界面活性劑及丙烯酸系界 面活性劑等。市售品可具體列舉如BYK-3 06(商品名，BYK Japan KK製，聚醚改質聚二曱基矽氧烷之12質量％溶液(二 甲苯/單苯基二醇(7/2))、BYK-323(商品名，BYK Japan KK 製，芳烷基改質聚甲基烷基矽氧烷）、BYK-320(商品名，BYK Japan KK製，聚醚改質聚甲基烷基矽氧烷之52%溶液（白油 溶劑（white spirit)/PGMEA(9/l))及BYK-350(商品名，BYK Japan KK製，丙烯酸系共聚物）等。 此外，就界面活性劑之配合量而言，雖亦依所用界面U 2 ε 〇 ε 377 377 2ε〇εΓ (wherein ε0, &, η respectively represent the dispersion medium at 25. The vacuum dielectric constant, relative dielectric constant, and subtraction (mPa · s). Potential.) The potential of the remainder of the specification (C) is the zeta potential measured by the above method. The photosensitive resin composition of the present invention is blended with the dispersion of fine particles (c), and the potential of the fine particles (c) in the blended dispersion is -100 to -5 mV. The fine particles (c) contained in the photosensitive resin composition of the present invention are fine particles in the above dispersion liquid, whereby the fine particles (c) remain dispersed in the composition - edge 21 201232178 and constitute a photosensitive resin The other components of the composition play a role in pulling each other, and because of the strong mutual mutuality with the substrate (especially the substrate m having a superbase on the surface), the adhesion between the two sides of the substrate (4) and the substrate is very high. 'The material is not easily touched. As a result, a high resolution pattern can be obtained. Further, the fine particles (c) have excellent dispersibility in the sensory resin composition, and thus the photosensitive, _ difficult-to-obtains of the present invention exhibit excellent storage stability. Further, in the case where the photosensitive resin composition of the present invention contains the fine particles (C), when the photosensitive ruthenium composition is used and the spacer J is formed by the ruthenium method, the following effects can be obtained. After the development, the heating of the post-baking step is carried out, and the shape stability of the pattern is improved. In view of the characteristics of the fine particles (C) other than the zeta potential, it is preferably transparent particles from the viewpoint of exposure. The average particle diameter of the fine particles (c) determined by the laser diffraction scattering method is preferably from 5 to 100 nm, more preferably from 10 to 80 nm, from the viewpoints of adhesion and surface smoothness of the formed partition walls. Further, in order to prevent the sensitivity of the photosensitive composition from being lowered, the fine particles (c) are preferably not absorbed for the wavelength of the light irradiated in the exposure step, and particularly for the main light-emitting wavelength of the ultrahigh pressure mercury lamp. The line (36511〇1), the h line (4〇5nm), and the g line (436nm) are preferably not absorbed. Among the fine particles (C), the inorganic fine particles may be exemplified by cerium oxide, zirconia, and fluorination. Microparticles such as magnesium, ITO (indium tin oxide) and AT0 (tin oxide). Examples of the organic fine particles include fine particles such as polyethylene and PMMA. From the viewpoint of heat resistance (7), the fine particles used in the present invention (c) ) ▲ ▲ No 201232178 machine micro-particles, from the viewpoint of dispersion stability, the dioxide fine particles and zirconia fine particles are better, from the point of view of ease of use, it is oxidized > Preferably, in the photosensitive resin composition of the present invention, the above micro The sub-(c) is contained in a photosensitive resin composition in a dispersed state. Specifically, the "dispersed state" refers to a state in which it is dispersed by electrostatic interaction (repulsion force). The photosensitive resin composition is a composition in which a dispersion of fine particles (c) is blended, and the zeta potential of the fine particles (C) in the dispersion is -100 to -5 mV. By blending fine particles having such characteristics (c) The fine particles (c) do not settle or aggregate in the photosensitive resin composition, and may be dispersed in the photosensitive resin composition in a stable state. The dispersion medium in the fine particle (C) dispersion may be specific For example, one or more selected from the group consisting of organic solvents having at least one hydroxyl group and having an SP value of 9 to exemplified. The sp value of such a dispersion medium is preferably 9 to 18 (cal/cm 3 ), /2, £ S ^ 10 to 15 (cal/cm 3 ) ' / 2 , where the SP value (solubility parameter) of the solvent is The agglutination energy density of the solvent (i.e., the evaporation energy per unit volume of one molecule) is multiplied by the value of 1/2 power, indicating the polarity of the parent unit volume. The unit is (cal/cm3) i/2, and in the present specification, it means a value at 25 ° C unless otherwise stated. The SP value can be extracted by the heart (Ref. R. F. Fedros, Polym. Eng. Sci., 14 [2] 147 (1974)). Specific examples of such an organic solvent include organic solvents as shown in Table 1 below. The organic solvent is an alkanol having a carbon number of 4 or less, an alkylene glycol having a carbon number of 2 or 3 or a dimer thereof, and a monoalkyl ether of the alkylene glycol or a divalent amount thereof (alkyl 23 201232178) Part of the carbon number is 4 or less). Table 1 Organic Solvent-----(SP value) (cal/cm3) I/2 Ethanol '- one___-. 12.6 f alcohol---~. 13.8 propanol 11.8 upper alcohol (IPA) 11.6 "butanol 11.3 17.8 ethylene glycol monoterpene ether ~~ 12.0 ethyl alcohol monoethyl ether ~ 11.5 ethyl alcohol monopropyl mystery 11.1 ΙΓΖϊϊΓ monoisopropyl ether ~ ~ - 11.1 ethylene glycol monobutyl ether " — 10.8 propylene glycol — 15.9 Alcohol monoterpene ether 11.3 Propylene glycol monoethyl ether mono- 10.9 3 glycol monopropyl ether (NPC) 10.7 Propylene glycol monoisopropyl ether " - 10.5 Propylene glycol monobutyl mystery 10.4 - Propylene glycol 13.3 diol monomethyl test - 10.4 ~~ Alcohol single B Scale 10.3 ~~ diol monopropanol Τ〇Ί ~ ~ ΞΓ ^ ~ diol monoisopropyl sulphide - 10.0 propylene glycol monobutyl hydrazine - ~10.0 ~ ~ In addition, used as the dispersion medium of the above microparticles (C) The organic solvent may be a mixture of two or more of the above 'as long as the SP value of the mixed solvent is in the range of 9 to 20 (Cal/em3) w' or a mixture with other solvents. 2-propanol and ethylene glycol monopropyl is preferred. In addition, when the above microparticles (c) use oxidized particles, 2-propanol and B are used. The diol is changed to the bismuth sulphide (C), and the sulphur dioxide is dissolved in the solvent. The solvent dispersion of the sulphuric acid and the sputum potential of the sulphur dioxide microparticles L_5mV are colloidal sulphur dioxide. For example, the above-mentioned organic solvent is used as a dispersion medium glue. Such an organic silica sand can be used as a commercially available product, and a commercially available product can be listed as NPCST (trade name, Nissan Chemical Industry Co., Ltd., zeta potential: _15 eye, ; average particle size: 24 nm, dispersion medium: ethylene glycol single (four), SI body composition: 3 〇 mass%), IPAST (trade name, manufactured by Nissan Chemical Industry Co., Ltd., zeta potential: -28 mV 'average purity: 45 nm, dispersion medium In the total solid content of the photosensitive resin composition of the present invention, the total solid content of the photosensitive resin composition is _ mass%, and fine particles \c) The content ratio is preferably from 3 to 35% by mass, and more preferably from 5 to 3% by mass, more preferably from 7.5 to 5% by mass. The amount of 1% to 23% is particularly preferably. If the content is too small, the above formation is inhibited. The role of the case-level layer in the secret material _ the effect is poor, if the content is too much, the composition The liquid stability tends to decrease. Further, the blending of the photosensitive resin residue into the fine particles (c) has an effect of improving the shape of the pattern for the subsequent heating, although depending on the type of the above-mentioned binder resin (8) And the heating conditions are the same, and in order to obtain a sufficient pattern shape t, the blending amount of the remainder (C) is preferably 12 to 3 G% by mass based on the total amount of the Q body component of the Inductive resin composition. More preferably, it is 15 to 25% by mass, and particularly preferably 18 to 23% by mass. (1-4) Organic solvent (D) The photosensitive resin composition of the present invention contains an organic solvent (D). At least a part of the organic solvent (D) is a dispersion medium of the fine particle (C) dispersion. In addition, unless otherwise stated in the description t, the following description of the organic solvent (D) is not limited to the resin composition (NR), and is common to all the photosensitive resin compositions of the present invention. A part of the organic solvent (D) may also contain other organic solvents different from the dispersion medium of the fine particle (C) dispersion. The organic solvent may be the same organic solvent as the dispersion medium or a different organic solvent. For example, when only the dispersion of the fine particles (C) is used, if the solid content concentration of the photosensitive resin composition is too high, the solid content may be adjusted to the same or different organic solvent as the dispersion medium of the dispersion. The predetermined concentration. Further, after adjusting the concentration of the fine particles (C) in the dispersion liquid using an organic solvent which is the same as or different from the dispersion medium, the solid content concentration of the photosensitive resin composition can be similarly adjusted by using the dispersion liquid. When an organic solvent different from the dispersion medium of the dispersion liquid is used, the organic solvent (D) in the photosensitive resin composition becomes a mixture of the organic solvent of the dispersion medium and another organic solvent, and is dispersed in the organic composition of the photosensitive resin composition. The fine particles (C) of the solvent (D) have a tendency to lower the dispersion stability. Therefore, when an organic solvent different from the dispersion medium is used, it is preferred to use an organic solvent which has less dispersion stability by the following means: a similar property to the organic solvent of the dispersion medium is used to reduce the zeta potential change (dielectric An organic solvent having a rate, a relative dielectric constant, a viscosity, etc.; and an amount of an organic solvent different from the dispersion medium. The organic solvent to be used in combination with the dispersion medium is preferably an organic solvent as exemplified in the above dispersion medium. It is preferred to use an organic solvent having at least one hydroxyl group and having an SP value of 9 to 20 (cal/cm 3 ) 1/2, which is the same as or different from the dispersion medium in the dispersion to be used. R3 26 201232178 The organic solvent (9) is blended in combination with a photosensitive resin composition as a dispersion medium, and a separate blender H can be blended with other components. For example, the case where the photoactive agent (8) is blended in a solution form, the case where the coloring agent (6) described later is blended in the form of a dispersing agent, and the case where the ink-repellent agent described later is blended in a solvent form, etc. . The organic solvent to be blended in combination with the blending of other components is not particularly limited in the case where the amount of blending is small. However, when it is relatively large in comparison with the total amount of the blending medium and the blender, it is preferably an organic solvent of the kind listed in the above-mentioned dispersion medium, and more preferably the same organic solvent as the dispersion medium used. 'Or the same organic solvent as the other dispersion of the above dispersion medium. In the total amount of the organic solvent (D), the amount of the solvent is adjusted so that the solid content concentration in the photosensitive resin composition is 5 to 40% by mass, and it is preferably adjusted to 10 to 25% by mass. (1-5) Arbitrary component In addition to the essential components of the components (A) to (c) described above, the resin composition (NR) of the present invention may be appropriately blended with a coloring agent as needed. a free radical crosslinking agent or a thermal crosslinking agent for increasing the crosslinking density of the cured product, a decane coupling agent for obtaining a substrate adhesion, a phosphoric acid compound, a surfactant, a hardening accelerator, and a tackifier , plasticizer, defoamer, sputum leveling agent, anti-collapse agent, UV absorber and solvent. (Colorant (E)) When the partition wall is a light-shielding light-shielding layer in the photosensitive resin composition of the present invention, the effect of the present invention 27 201232178 is more remarkable when it is used as a black matrix. Therefore, the photosensitive resin composition of the present invention can be suitably applied to an optical element in which the partition wall is a light shielding layer. When the partition wall formed of the resin composition (NR) of the present invention is used as a black matrix as described above, the photosensitive resin composition preferably contains a black colorant. Specific examples of such a black colorant include metal oxide particles such as carbon black, stupid amine black, fluorene black pigment, titanium black, ferrous metal oxide pigment, silver tin alloy, and the like, and flower black pigments. CI .pigment black 1, 6, 7, 12, 20, 31, etc. Further, as the black coloring agent, a mixture of an organic pigment such as a red pigment, a blue pigment, a green pigment, a yellow pigment, a azomethine-based black pigment, and an inorganic pigment may be used. Further, the black colorant is preferably carbon black from the viewpoint of the price and the light-shielding property, and the carbon black may be surface-treated with a resin or the like. In addition, in order to adjust the color tone, a blue pigment or a color pigment may be used in combination. In the case of a black matrix on array type color filter and an organic EL element, a film and a partition having a low dielectric constant and a high impedance are required. In order to obtain the film and the partition walls, it is preferred to use a mixture of the above organic pigments and a methylene azo black pigment. The blending amount of the black colorant varies depending on the type and use of the optical member to be used. For example, when the partition wall is used as a black matrix of a color filter, it is preferable to use the total solid content of the photosensitive resin composition. 1 to 5 5% by mass of the coloring agent is mixed with a suitable dispersion medium and a dispersing agent as needed, and blended into a dispersion. When the blending amount of the black coloring agent is within this range, the sensitivity of the photosensitive resin composition becomes good, and the formed partition wall has excellent light blocking properties. Γο!发' 28 201232178 (Ink-repellent) The photosensitive resin composition of the present invention is formed by photolithography to form a partition wall, whereby a plurality of blocks are partitioned on the substrate to form pixels of the optical element. The formation area (hereinafter sometimes referred to as "dot"). When the partition wall is used as a partition wall of an optical element in which a pixel is formed by an inkjet method, the photosensitive resin composition of the present invention preferably contains an ink-repellent agent which imparts ink repellent property to the upper surface of the partition wall. Here, the ink-repellent property differs depending on the ink composition, and refers to the water-repellent or oil-repellent property or even the water-repellent property and the oil-repellent property. More specifically, it refers to the properties of a solvent for ejecting water or an organic solvent or the like for the ink, and generally, water or a suitable organic solvent (for example, 1-methoxy-2-ethoxypropane or The contact angle of propylene glycol monomethyl ether 2-acetate (PGMEA) and the like (usually used in an ink for inkjet method) was evaluated. In the case of forming a partition wall of a photosensitive resin composition containing the same, it is possible to impart ink repellency to the upper surface of the partition wall (that is, to be used for ink) a compound of the nature of a solvent such as water or an organic solvent. ~ Such an ink-repellent agent which imparts ink-repellent property to the partition wall when forming a partition wall by switching to a photosensitive resin composition, preferably a compound, a Wei-containing compound, and a Wei-Wu 3 rolling The gas-containing compound used as the above-mentioned ink-repellent agent can be used without limitation = ::: Γ In addition, (4) can be used to increase the tenderness of her coffee without special limitation 29 201232178, which is a conventionally used hydrazine-containing compound, for example, having a ruthenium-based compound. Polymers such as oxygen-based hospitals. The compound having both a fluorine atom and a ruthenium atom which can be used as the above-mentioned ink-repellent agent can be exemplified by a conventionally known fluorine-containing compound for a liquid-repellent agent, for example, a fluorine-containing decane coupling agent having both a fluoroalkyl group. A polymer with a dimercaptooxyalkyl group or the like. Among such ink-repellent agents, a polymer having a fluoroalkyl group in its side chain can be classified as a preferred aspect because of its high ability to impart ink repellency. Such a polymer having a fluorinated group in the side chain can be produced by a known method, and the method disclosed in, for example, JP-A-2000-102727 and JP-A-2002-249706. As long as it is not specifically stated in the present specification, the ink-repellent agent described above may be used without depending on the type of the photosensitive resin composition. Further, in the case of the resin composition (NR), preferred examples of the ink-repellent agent may be a polymer having a fluoroalkyl group and an ethylenic double bond in a side chain. The reason for this is that if the polymer having a fluoroalkyl group and an ethylenic double bond in the side chain is used as an ink-repellent agent, the above-described ink-repellent agent may be combined with an exposure step and a post-baking step of forming a partition wall by photolithography described later. The other blending component in the negative photosensitive resin composition is reacted and immobilized on the upper surface of the partition wall. One of preferred embodiments of such a polymer having a side chain having a fluoroalkyl group and an ethylenic double bond is exemplified by a polymer containing a polymerized unit having at least one (more preferably all) hydrogen atom substituted by a fluorine atom. a polymer unit having a linear or branched alkyl group having a carbon number of 20 or less (but an alkyl group containing an ether having oxygen); and 'having a (fluorenyl) acrylonitrile group, a dilute propyl group, an ethylene group, Ethylene equivalent of ethylene sulfhydryl 30 201232178 ' Polymeric unit of double bond. The above-mentioned polymer which is suitably used as the above-mentioned ink-repellent agent and has a fluoroalkyl group and an ethylenic double bond in its side chain preferably has a number average molecular weight of from 5 Å to 15 Å, more preferably from 1,000 to 100,000, and a mass. The average molecular weight is preferably from 1 Torr to 3 Torr, more preferably from 5,000 to 150,000. If it is within this range, alkali solubility and developability will become good. Further, the fluorine content in the polymer is preferably from 5 to 5 % by mass, more preferably from 1 to 40% by mass, and from 12 to 30% by mass, from the viewpoints of ink repellent property and barrier formability. Especially good. Further, the polymer preferably has a number of ethylene double bonds in the side chain of from 0.5 to 5?m?l/g, more preferably from 1.0 to 3?mol/g. If it is within this range, the imaging performance will become good. Further, the above polymer may have a polyether chain (straight chain) having a number of turns of 200 or less in the side chain. Further, the content of the ruthenium of the polymer is preferably from 0.5 to 30% by mass, more preferably from 0.5 to 1% by mass, from the viewpoint of ink repellent property and _ barrier formability. Here, the above polymer used as the ink-repellent agent preferably has an acidic group, for example, at least one acidic group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. The reason for this is that the ink repellent is less likely to remain in the dot partitioned by the partition walls on the substrate by the alkali solubility, and the ink wettability is excellent when the ink is injected by the ink jet method. From this point of view, the acid value of the polymer is preferably from 5 to 200 mgKOH/g', more preferably from 10 to 160 mgKOH/g, and particularly preferably from 20 to 60 mgKOH/g. The polymer having a fluoroalkyl group and an ethylenic double bond and optionally a polyoxynoxy chain in the side chain described above and preferably having an acidic group can be produced by a known method, specifically, International Publication No. 2004. /042474, International Publication No. 31 201232178, No. 2007/069703, International Publication No. 2008/149776, and the like. In the solid content of the resin composition (NR) containing the above-mentioned ink repellent, the content of the ink repellent is preferably in the range of 0.01 to 30% by mass based on the total amount of the solid content of the composition. The reason for this is that the ink absorbing property of the obtained partition wall is good, and the ink which is injected by the ink jet method has good wettability in dots, and the uniformity of the ink layer to be injected is good. The polymer containing an I atom and/or a ruthenium atom which is incorporated into the photosensitive resin composition as the above-mentioned ink repellent generally also functions as a surfactant. Therefore, when the photosensitive resin composition contains an ink-repellent agent, the surfactant is not blended in addition to the case where it is particularly required to be added. The photosensitive resin composition for forming the partition wall for an optical element which is formed by the method other than the ink jet method usually does not contain an ink repellent. Therefore, it is preferable to add a surfactant. As the surfactant, a polymer similar to the above-mentioned ink-repellent agent may be used. However, a commercially available product may be used. The surfactant may be a polysiloxane surfactant or an acrylic surfactant. Commercially available products can be specifically exemplified by BYK-3 06 (trade name, manufactured by BYK Japan KK, a 12% by mass solution of polyether modified polyfluorenyl oxazane (xylene/monophenyl diol (7/2)). ), BYK-323 (trade name, BYK Japan KK, aralkyl modified polymethyl alkyl siloxane), BYK-320 (trade name, BYK Japan KK, polyether modified polymethyl alkyl) 52% solution of oxoxane (white spirit/PGMEA (9/l)) and BYK-350 (trade name, manufactured by BYK Japan KK, acrylic copolymer), etc. In addition, as for the surfactant In terms of the amount of blending, it depends on the interface used.

S 32 201232178 活性劑之種類而異，但相對於感光性樹脂組成物之全固體 成分量宜為0.1〜1〇質量％，且更宜為0_5〜5質量0/〇。 (自由基交聯劑） 本發明之樹脂組成物(NR)宜含有自由基交聯劑（具體 來說則是具有2個以上乙烯性雙鍵之自由基交聯劑）作為促 進自由基硬化之任意成分。藉此，曝光時上述結合劑樹脂 (A1)之硬化性提升，可減低形成隔壁時之曝光量。此外， 本發明所用之自由基交聯劑宜實質上不具有酸性基。 具有2個以上乙烯性雙鍵之自由基交聯劑並未特別受 限’但可列舉如二乙二醇二（曱基）丙烯酸酯、四乙二醇二（甲 基）丙烯酸酯、三丙二醇二（曱基）丙烯酸酯、新戊二醇二（甲 基）丙烯酸酯、1, 9-壬烷二醇二（甲基）丙烯酸酯、三羥甲基 • 丙烷三（曱基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、新戊 四醇四（曱基）丙烯酸酿、二三經甲基丙烧四（甲基）丙稀酸 酯、二新戊四醇六（甲基）丙烯酸酯、乙氧基化異三聚氰酸三 丙烯酸酯及胺甲酸酯丙烯酸酯等。該等可單獨使用1種，亦 可併用2種以上。 於本發明中，具有2個以上乙歸性雙鍵之自由基交聯劑 可使用市售品。此種市售品可列舉如KAYARAD DPHA(商 品名’曰本化藥社製’二新戊四醇五丙烯酸酯與二新戊四 醇六丙烯酸酯之混合物）、NKEsterA-9300(商品名，新中村 化學工業社製’乙氧基化異三聚氰酸三丙烯酸酯）、NK Ester A-9300-lCL(商品名，新中村化學工業社製，ε_己内酯改質 參-(2-丙烯氧基乙基)三聚異氰酸酯）、ΒΑΝΙ_Μ(商品名，丸 33 201232178 善石油化學社製，雙{4-(烯丙基二環[2.2.1]庚-5-烯-2，3-二 羧醯亞胺）苯基}甲烷）、BANI-X(商品名，丸善石油化學社 製’N，N’-m-二甲苯-雙（烯丙基二環[2.2.1]庚-5-烯-2, 3-二羧 醯亞胺)）等。 此外，胺曱酸酯丙烯酸酯可列舉如日本化藥社製之 KAYARAD UX series，具體商品名可列舉如UX-3204、 UX-6101、UX-0937、DPHA-40H、UX-5000、UX-5002D-P20 等。從可賦予硬化物硬度並抑制受熱損害之觀點來看，以 A-9300、BANI-M及BANI-X為佳。從可賦予硬化物柔軟性 之觀點來看’則以A-9300-1CL為佳。由於胺曱酸酯丙稀酸 酯可實現適度之顯像時間且顯像性良好，甚是理想。 本發明之樹脂組成物(NR)中，上述自由基交聯劑之含 量相對於組成物之全固體成分宜為丨〜刈質量。/。，且更宜為 5〜30質量％。若為1〜50質量％，感光性樹脂組成物之顯像性 會變得良好。 (熱交聯劑） 熱交聯劑係下述化合物：具有2個以上可與添加之感光 性樹脂組成物含有之結合劑樹脂(A1)所具有的官能基反應 的基團；’其係可藉由加減理(具體來說，則是顯像後 之後培加減理）等而與上述結合劑樹脂⑷)反應，使硬化 物之交聯密度增加，藉此謀求耐熱性提升之任意成分。 熱交聯劑雖依上述交聯硬化之結合劑樹脂(ai)所具有 之交聯反應性官能基的種類而異，因應該種類，可列舉 如胺基樹脂、具有2個以上環氧基之化合物具有2個以上 201232178 耕基之化合物、聚碳二亞胺化合物、具有2個以上噚唑啉基 之化合物、具有2個以上。丫環丙烧(aziridine)基之化合物、 多價金屬類、具有2個以上毓基之化合物及聚異氰酸酯化合 物等。該等可單獨使用，亦可併用2種以上。 作為本發明中添加至樹脂組成物(NR)之熱交聯劑，於 别述者之中，從耐溶劑性之觀點來看以胺基樹脂及具有之個 以上環氧基之化合物為宜，且以具有2個以上環氧基之化合 物尤佳。 σ 具有2個以上環氧基之化合物可具體列舉如雙酚a型環 氧樹脂、雙盼F型環氧樹脂、驗系祕清漆型環氣樹月匕= 紛祕清漆型環氧樹脂、三㈣院型環氧樹脂、演化曰 樹脂等之環氧丙基_、3, 4_環氧基環己基甲基」4 ^ 基環己驗義、雙(2,3_環氧基環戊基)_之辟二 樹脂、二環氧丙基六氫酞酸_、二環 “魏 二環氧丙級_等之環氧丙基軸、四魏^酸^ 二苯基甲烧、三環氧丙基對胺基紛 一胺基 環氧丙基三聚異氰酸料之雜環式環氧樹=基胺類、三 匕此外，亦可將具有上述通式⑴所示聯笨骨 脂（例如’ NC-3〇〇0-H(商品名，曰本化奸丨】、之展氧樹 通式(2)所示之環氧樹脂及通式（3)又’）等之市售品）、 交聯劑。 之嶮氧樹脂用作熱 胺基樹脂可列舉如：三聚氰胺系化合物 (guanamine)系化合物、尿素系化合物等 物、胍胺 部之胺基經經曱基化之化合物.十、θ 定刀或全 ，或使該業已經甲基化 35 201232178 之化合物的一部分或全部羥基藉由曱醇、乙醇、正丁醇、 2-曱基-1-丙醇等而醚化的化合物。具體來說，可列舉如： 六羥甲基三聚氰胺及烷基化六羥甲基三聚氰胺（六甲氧基 甲基三聚氰胺等）、六丁醇三聚氰胺（hexabutylol melamine)、咅p分經曱基化三聚氰胺及其烧基化物、四經甲 基苯并胍胺及烷基化四羥曱基苯并胍胺；以及，部分羥曱 基化苯并胍胺及其烷基化物等。 本發明之樹脂組成物(NR)中，上述熱交聯劑之摻合比 例雖亦依所用光學元件之種類及用途而異，但相對於組成 物之全固體成分以1〜50質量％為佳，且更宜為5〜30質量％。 若於此種範圍内，使用其所得之構成隔壁之硬化物的交聯 密度增加，可獲得具優異耐熱性之隔壁。 (矽烷偶合劑） 本發明之樹脂組成物(N R)亦可含有矽烷偶合劑作為任 意成分。藉由摻合矽烷偶合劑，可使所得隔壁對基板之密 著性更提升，甚為理想。 此種矽烷偶合劑可具體列舉如四乙氧基矽烷、3-環氧 丙氧基丙基三甲氧基矽烷、甲基三甲氧基矽烷、乙烯基三 曱氧基矽烷、3-曱基丙烯醯氧基丙基三甲氧基矽烷、3-氣丙 基三甲氧基矽烷、3-巯基丙基三甲氧基矽烷、3-胺基丙基三 乙氧基矽烷、十七氟辛基乙基三甲氧基矽烷、含有聚氧伸 烷基鏈之三乙氧基矽烷等。該等可單獨使用，亦可併用2種 以上。 6 本發明之樹脂組成物(NR)中，其全固體成分之矽烷偶 36 201232178 合劑的比例宜為0.1〜20質量％，更宜為丨〜⑺質量％。若含量 過少，則提咼感光性樹脂組成物形成之隔壁與基板間之密 著性的效果較低，若含量過多則顯像後會有容易產生殘渣 之虞，並不理想。 (磷酸化合物） 樹脂組成物(NR)亦可依需要而含有磷酸化合物。樹脂 組成物(NR)可藉由含有磷酸化合物而提高與基板之密著 性。磷酸化合物(L)可列舉如單（甲基）丙烯醯氧基乙基磷酸 酯、二（甲基）丙烯醯氧基乙基磷酸酯及參（曱基）丙烯醯氧基 乙基磷酸酯等。 本發明之樹脂組成物(NR)中，其全固體成分之構成比 且為光自由基^^合性結合劑樹脂(A1).光聚合起始劑(b 1): 微粒子(C)=5〜80質量％ : 1〜40質量％ : 3〜35質量％。 本發明之樹脂組成物(NR)之全固體成分的構成比更宜 為光自由基聚合性結合劑樹脂(A1):光聚合起始劑(B1):微 粒子(C):著色劑(E):著色劑(E)以外之任意成分=5〜8〇質 量％: 1〜40質量％:3〜35質量％: 10〜50質量％:22〜5〇質量 %。 可使上述說明之各種必須成分與依需要而添加之任意 成分以符合上述摻合量之方式，利用一般方法均勻混合而 調製出本發明之樹脂組成物(NR)。 (2 )酸硬化型之樹脂組成物 從酸硬化型之負型感光性樹脂組成物去除有機溶劑(D) 而成之感光性組成物即為酸硬化性之感光性組成物。以下 37 201232178 將構成酸硬化性之感光性組成物的此一酸硬化型之負型残 光性樹脂組成物稱為樹脂組成物(να)。 本發明之感光性树脂組成物為樹脂組成物(Να)時，减 光性樹脂組成物含有下述必須成分：鹼可溶性樹脂(Α21)， 其係用作結合劑樹脂(A)，且具有羧基及/或酚性羥基；交聯 性樹脂(A22)，其係具有2個以上可與羧基及/或酚性羥基反 應之基的化合物；光酸產生劑(B2)，其係用作光活性劑（B) 者’微粒子(C) ’其係有機溶劑分散液令之微粒子(c)，且於 該分散液中，微粒子（C)以電泳光散射法測定之ξ電位為 -100〜-5mV ;及，有機溶劑(d)。 樹脂組成物(NA)於光蝕刻法等之曝光時，光照射部分 會由光酸產生劑(B2)產生酸，具有羧基及/或酚性羥基之鹼 可溶性樹脂（A21)會與交聯性樹脂（A22)(即具有2個以上可 與羧基及/或酚性羥基反應之基的化合物）進行交聯反應而 形成感光性組成物之硬化物。未受光照射之部分（未曝光部 分）宜對曝光後進行顯像時所使用之顯像液（通常為鹼性顯 像液）呈可溶性。 於此，就本發明之樹脂組成物(NA)所含有之必須成分 的上述微粒子(C)及有機溶劑（D)而言，其種類及摻合量等均 可與上述（1)樹脂組成物(nr)時完全相同。以下，依序說明 上述微粒子(C)與有機溶劑(D)以外之必須成分及任意成分。 (2-1)結合劑樹脂(Α):鹼可溶性樹脂(Α2丨）、交聯性樹脂(Α22) 本發明之感光性樹脂組成物為樹脂組成物(ΝΑ)時，結 合劑樹脂（Α)可列舉如下述鹼可溶性樹脂(Α2丨）與交聯性樹 38 201232178 脂（A22)之組合，即：鹼可溶性樹脂（A21)，其藉由用作光 活性劑(B)之光酸產生劑(B2)所產生之酸的作用而進行交聯 反應，且具有缓基及/或盼性經基；及，交聯性樹脂(A22)， 其係具有2個以上可與羧基及/或酚性羥基反應之基的化合 物。 (鹼可溶性樹脂(A21)) 鹼可溶性樹脂(A21)具有羧基及/或酚性羥基。因含有羧 基及/或酚性羥基而對鹼性溶液呈可溶性，且可與交聯性樹 脂(A22)進行交聯反應而形成感光性組成物之硬化物，該交 聯性樹脂(A22)係具有2個以上可與羧基及/或酚性羥基反應 之基的化合物。鹼可溶性樹脂(A21)只要是對鹼性溶液(構成 感光性組成物在光蝕刻等步驟中使用之顯像液）呈可溶性 之祕脂’即可無任何限制地予以使用’可列舉如：以具有 缓基與乙稀性雙鍵之單體及/或具有酚性羥基與乙烯性雙 鍵之單體為必要，使其進行聚合而獲得之樹脂(A21-1);及， 酚樹脂等。 以具有羧基與乙烯性雙鍵之單體及/或具有酚性羥基 與乙稀性雙鍵之單體為必要並使其聚合而得之樹脂 (A21-1)’可使具有綾基與乙烯性雙鍵之單體及/或具有酚性 罗二基與乙烯性雙鍵之單體依需要而與其他單體共聚合來製 于。此外’該驗可溶性樹脂(A21-1)中，以其他單體為主體 之單體單元的比例宜在3〇~95質 量％以下，更宜在50〜90質 里/〇以下。若在此範圍内，感光性組成物之鹼溶解性及顯 像性會變得良好。 * 39 201232178 此外，製作上述鹼可溶性樹脂（A2M)時使用之具有羧 基與乙烯性雙鍵之單體可列舉如丙稀酸、甲基丙烯酸、乙 稀基乙酸 '巴豆酸、依康酸、順丁稀二酸、反丁稀二酸、 桂皮酸或琪等之鹽。具有酚性羥基與乙烯性雙鍵之單體可 列舉如鄰m苯&烯、間經苯乙烯及對經苯乙稀等，以及其 等之苯環上的1個以上氫原子經曱基、乙基、正丁基等烷 基、甲氧基、乙氧基、正丁氧基等烷氧基、函素原子、烷 基之1個以上氫原子經_素原子取代之鹵烷基、硝基、氰基 及酿胺基取代的化合物等。 其他單體可列舉如烴系烯烴類、乙烯醚類、異丙烯醚 類、稀丙轉類、乙烯酯類 '烯丙酯類、（曱基）丙烯酸酯類、 (曱基）丙烯醯胺類、芳香族乙烯基化合物、氣化烯烴類及共 軛二烯類等’若考慮隔壁之耐熱性，則以（曱基）丙烯酸酯類 或（甲基）丙烯醯胺類為佳。此外，此等化合物亦可具有羰基 及烷氧基等之官能基。 酚樹脂係使酚類(選自酚、曱酚、二曱苯酚、間苯二酚 及氫酿等之芳香族羥基化合物以及該等之經烷基取代或經 鹵素取代的芳香族化合物中之至少1種）與甲醒_、乙酿、苯 甲酸專之輕化合物聚縮合而得者，可列舉如紛_甲酸樹脂、 甲酚-甲醛樹脂 '酚-甲酚_甲醛共縮合樹脂等。 上述鹼可溶性樹脂(A21)可使用市售品。就此種市售品 而言，作為使酚類與醛類在酸性催化劑存在下縮合而得之 酚酸清漆型酚樹脂之1種的甲酚系酚醛清漆型樹脂，可列舉 如EP4020G(商品名，旭有機材工業社製）及CRG_951(商品 201232178 名’昭和高分子社製）或是聚經苯乙稀等。 驗可溶性樹脂（A21)之酸價宜為1〇〜6〇〇nigK〇H/g，且 50〜300mgKOH/g更佳。若在該範圍内，感光性樹脂組成物 之顯像性會變得良好。 鹼可溶性樹脂(A21)之數平均分子量宜為2〇〇〜2〇,〇〇〇， 更宜為2,000〜15,000。若在該範圍内，則感光性樹脂組成物 之鹼溶解性及顯像性會變得良好。此外，驗可溶性樹脂(A21) 之①質S平均分子量宜為1.5><1〇3〜4〇xl〇3，更宜為 2_〇xl03〜2〇χ103。該質量平均分子量若小於丨5χ1〇3，會有 曝光時硬化不充分之情況，若超過4〇χ 1 〇3，則會有顯像性 降低之情況。 本發明之樹脂組成物(ΝΑ)中，鹼可溶性樹脂(Α2ΐ)之含 量相對於組成物之全固體成分宜為1 〇〜9〇質量％，更宜為 30〜80質量％。若在該範圍内，本發明之感光性樹脂組成物 之顯像性會變得良好。 (交聯性樹脂(Α22)) 交聯性樹脂(Α22)係具有2個以上可與羧基及/或酴性羥 基反應之基的化合物。藉由具有2個以上可與羧基及/或酚 性經基反應之基，可與驗可溶性樹脂(Α21)交聯而形成硬化 物。此外，下述撥墨劑具有羧基及/或羥基時，亦可與撥墨 劑交聯而形成硬化物。 交聯性樹脂(Α22)宜選自於由胺基樹脂、環氧化合物及 »夸唑啉化.合物所構成群組中之至少丨種。其等可單獨使用， 亦可併用2種以上。 41 201232178 胺基樹脂可列舉如三聚氰胺系化合物、胍胺系化合 物、尿素系化合物等之使一部分或全部胺基經羥曱基化的 化合物、或是使該業已羥甲基化之化合物之部分或全部羥 基以曱醇、乙醇、正丁醇、2-曱基-1-丙醇等而醚化的化合 物，例如六曱氧基曱基三聚氰胺等。 環氧化合物可列舉如、雙酚A型環氧樹脂、雙酚F型環 氧樹脂、酚系酚醛清漆型環氧樹脂、曱酚酚醛清漆型環氧 樹脂、三酚曱烷型環氧樹脂、溴化環氧樹脂等之環氧丙基 醚類、3, 4-環氧基環己基曱基-3, 4-環氧基環己烷羧酸酯、 雙(2, 3 -環氧基環戊基)醚等之脂環式環氧樹脂、二環氧丙基 六氫酞酸酯、二環氧丙基四氫酞酸酯、二環氧丙基酞酸酯 等之環氧丙基酯類類、四環氧丙基二胺基二苯基曱烷、三 環氧丙基對胺基酚等之環氧丙基胺類、三環氧丙基三聚異 氰酸酯等之雜環式環氧樹脂等。 哼唑啉化合物可列舉如2-乙烯基-2-。号唑啉、2-乙烯基 -4-曱基-2-噚唑啉、2-乙烯基-5-甲基-2-噚唑啉、2-異丙烯基 -2-。号唑啉及2-異丙烯基-4-曱基-2·-号唑啉等之聚合性單體 的共聚物。 本發明之樹脂組成物(NA)中，交聯性樹脂(A22)之含量 相對於組成物之全固體成分宜為1〜50質量％，且更宜為 5〜30質量％。若在該範圍内，感光性樹脂組成物之顯像性 會變得良好。 (2-2)光活性劑(B):光酸產生劑.(B2) ό 本發明之感光性樹脂組成物為樹脂組成物(ΝΑ)時，光 42 (3 201232178 =劑使时因光而產生酸之化合物，即光酸產 可列舉如二芳基物、三芳基-| ㈣化5物、顧基化合物及俩酿類等。 二絲铺鹽之陽離子部分的具體财列舉如 ==苯基苯細、雙(4_第三丁基苯心: 一方基破鎘鹽之陰離早邱八 根r 離子^的具體例可列舉如三氟甲確酸 广=Γ ::部”之1種與前述陰離子部分中之1種： 構成：三氣甲續酸雙(4-第三丁基笨基Μ鎖鹽。 疏、部分，例可列舉如三笨基 等。三土 1、—本基_2, 4, 6-三曱基笨基銃 = 之陰離子部分之具㈣可列舉如前述二芳 土碘鏘鹽讀離子部㈣具。 離子部分巾之丨―▲ -方錢鹽係由前述陽 点。偏一述陰離子部分中之1種的組合所構 1 σ，二氟甲磺酸三苯基鈑鹽。 ^ 丫井系化合物之具體例可列舉如2-甲基_4, 6_雙(三 :曱基)-1’ 3’ 5-二吖畊、2_(4_甲氧基笨基”,6，三氣甲 土)，，5·三啊、2必°夫喃基）乙職雙(三氣甲基Η 3 5_二口丫啡、2·(5_甲基钟南基)乙烯基_雙(三氯甲基)q 3 氧姆)罐你氣甲基⑴， 石尹、酿基化合物之具體例可列舉如雙（苯基續醯基）重氮 甲坑、雙(第三丁基續醯基)重氮甲院、雙(環己基續醯基)重 43 201232178 氮曱烷及雙（對甲苯磺醯基）重氮曱烷等。 石黃酸酿類之具體例可列舉如2-硝基苄基對曱苯磺酸 酯、α-(對甲苯磺醯氧基醯亞胺)_苯基乙腈等。 本發明之樹脂組成物(ΝΑ)中，光酸產生劑(Β2)之含量 相對於組成物之全固體成分宜為〇卜川質量％，且更宜為 1 20資量°/。。若在該範圍内，感光性樹脂組成物之顯像性 會變得良好。可列舉如摻合成下述比例者：相對於上述鹼 可溶性之結合劑樹脂，光酸產生劑宜為0.01〜30質量％，更 宜為0.1〜20質量。/。。若在此範圍内，感光性組成物之硬化性 及顯像性會變得良好。 (2_3)任意成分 本發明之樹脂組成物(N A)含有用作上述結合劑樹脂(A) 之驗可溶性樹脂（A21)與交聯性樹脂（A22)、用作光活性劑 (B)之光酸產生劑（B2)、上述微粒子(〇及有機溶劑（D)，但 在不損及本發明效果之範圍内，可以提升各種機能等為目 的而含有各種任意成分。 作為此種任意成分，在上述樹脂組成物(NR)中已作說 明之任意成分中，自由基交聯劑以外之所有成分亦可用於 樹脂組成物(NA)中。此外’該等任意成分之中，就除了撥 墨劑以外之任意成分而言，亦可使種類、摻合量及其等之 較佳態樣與上述樹脂組成物(NR)的情況相同。 在樹脂組成物(NA)之情況下，作為撥墨劑，與上述樹 脂組成物(NR)時相同地，可列舉如含氟化合物、含矽化合 物以及兼有氟原子與矽原子之化合物等。與上述者相同S 32 201232178 The type of the active agent varies, but the total solid content of the photosensitive resin composition is preferably 0.1 to 1% by mass, and more preferably 0 to 5 to 5 parts by mass. (Radical Crosslinking Agent) The resin composition (NR) of the present invention preferably contains a radical crosslinking agent (specifically, a radical crosslinking agent having two or more ethylenic double bonds) as a radical-hardening promoting agent. Any ingredient. Thereby, the hardenability of the binder resin (A1) at the time of exposure is improved, and the amount of exposure when the partition walls are formed can be reduced. Further, the radical crosslinking agent used in the present invention preferably has substantially no acidic group. The radical crosslinking agent having two or more ethylenic double bonds is not particularly limited, but may, for example, be diethylene glycol bis(indenyl) acrylate, tetraethylene glycol di(meth) acrylate, or tripropylene glycol. Di(indenyl)acrylate, neopentyl glycol di(meth)acrylate, 1,9-decanediol di(meth)acrylate, trimethylolpropane tris(decyl)acrylate, Pentaerythritol tri(meth)acrylate, neopentyltetrakis(mercapto)acrylic acid, ditrimethyl methacrylate tetra(methyl) acrylate, dipentaerythritol hexa(methyl) Acrylate, ethoxylated isocyanuric acid triacrylate and urethane acrylate. These may be used alone or in combination of two or more. In the present invention, a commercially available product can be used as the radical crosslinking agent having two or more ethylated double bonds. Such a commercially available product may, for example, be KAYARAD DPHA (a product name 'small mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate produced by Sakamoto Chemical Co., Ltd.), NKEster A-9300 (trade name, new) Nippon Chemical Industry Co., Ltd. 'Ethoxylated isocyanuric acid triacrylate>, NK Ester A-9300-lCL (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ε_caprolactone modified ginseng-(2- Propylene oxyethyl)trimeric isocyanate), ΒΑΝΙ_Μ (trade name, pill 33 201232178 manufactured by Shan Petrochemical Co., Ltd., double {4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxylated imine)phenyl}methane, BANI-X (trade name, 'N,N'-m-xylene-bis(allyl bicyclo[2.2.1]hept-5, manufactured by Maruzen Petrochemical Co., Ltd.) -ene-2,3-dicarboxylimenine)) and the like. Further, the amine phthalate acrylate may, for example, be KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific trade names may be exemplified by UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D. -P20 and so on. A-9300, BANI-M and BANI-X are preferred from the viewpoint of imparting hardness to the cured product and suppressing heat damage. From the viewpoint of imparting flexibility to the cured product, A-9300-1CL is preferred. Since the amine phthalate acrylate has a moderate development time and good imageability, it is ideal. In the resin composition (NR) of the present invention, the content of the above-mentioned radical crosslinking agent is preferably 丨 刈 刈 by mass relative to the total solid content of the composition. /. And more preferably 5 to 30% by mass. When it is 1 to 50% by mass, the developability of the photosensitive resin composition becomes good. (Thermal cross-linking agent) The thermal cross-linking agent is a compound having two or more groups reactive with a functional group of the binder resin (A1) contained in the photosensitive resin composition to be added; By the addition and subtraction (specifically, the addition and subtraction after development), the binder resin (4) is reacted to increase the crosslinking density of the cured product, thereby achieving an optional component having improved heat resistance. The thermal cross-linking agent varies depending on the type of the cross-linking reactive functional group of the cross-linking and curing binder resin (ai), and examples thereof include an amine-based resin and two or more epoxy groups. The compound has two or more of the 201232178 cultivating compound, the polycarbodiimide compound, and the compound having two or more oxazoline groups, and has two or more. Aziridine-based compounds, polyvalent metals, compounds having two or more mercapto groups, polyisocyanate compounds, and the like. These may be used alone or in combination of two or more. The thermal crosslinking agent added to the resin composition (NR) in the present invention is preferably an amine-based resin and a compound having one or more epoxy groups from the viewpoint of solvent resistance. Further, a compound having two or more epoxy groups is particularly preferable. σ Compound having two or more epoxy groups may specifically be exemplified by a bisphenol a type epoxy resin, a double hop F type epoxy resin, a viscous varnish type ring gas sapphire 匕 纷 纷 varnish type epoxy resin, three (4) Epoxy propyl _, 3, 4_epoxycyclohexylmethyl" 4 ^ cycline test, bis (2,3_epoxycyclopentyl) ) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Heterocyclic epoxides of amine-amino-glycidyl-glycidyl isocyanate = amides, triterpenes, and, in addition, the stupa of the above formula (1) (for example, 'NC -3〇〇0-H (trade name, 曰本化奸丨), the epoxy resin shown in the formula (2) of the oxygen tree and the commercial products of the general formula (3) and '), etc. The hydrazine resin used as the thermal amine-based resin may, for example, be a melamine-based compound, a urea-based compound or the like, or a guanidinium-based amine group which is thiolated. Knife or all, or make the industry A compound which is etherified by a part or all of a hydroxyl group of a compound of methylation 35 201232178 by decyl alcohol, ethanol, n-butanol, 2-mercapto-1-propanol or the like. Specifically, for example, hexahydroxyl Methyl melamine and alkylated hexamethylol melamine (hexamethoxymethyl melamine, etc.), hexabutylol melamine, 咅p divided by thiolated melamine and its alkylate, tetramethylbenzene And decylamine and alkylated tetrahydroindenyl benzoguanamine; and, partially hydroxylated benzoguanamine and alkylate thereof, etc. In the resin composition (NR) of the present invention, the above thermal crosslinking agent The blending ratio varies depending on the type and use of the optical element to be used, but is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass based on the total solid content of the composition. In the inside, the crosslinked density of the cured product constituting the partition wall is increased, and a partition wall having excellent heat resistance can be obtained. (Centane coupling agent) The resin composition (NR) of the present invention may further contain a decane coupling agent as an optional component. By blending a decane coupling agent, The adhesion of the obtained partition wall to the substrate is further improved, and the decane coupling agent may specifically be exemplified by tetraethoxy decane, 3-glycidoxypropyltrimethoxy decane, and methyltrimethoxy decane. , vinyl trimethoxy decane, 3-mercapto propylene methoxy propyl trimethoxy decane, 3-apropyl propyl trimethoxy decane, 3-mercaptopropyl trimethoxy decane, 3-aminopropyl Triethoxy decane, heptafluorooctylethyl trimethoxy decane, triethoxy decane containing a polyoxyalkylene chain, etc. These may be used alone or in combination of two or more. In the resin composition (NR), the ratio of the total solid content of the decane couple 36 201232178 mixture is preferably 0.1 to 20% by mass, more preferably 丨 to (7)% by mass. When the content is too small, the effect of improving the adhesion between the partition wall formed of the photosensitive resin composition and the substrate is low, and if the content is too large, the residue tends to be likely to be generated after development, which is not preferable. (Phosphate Compound) The resin composition (NR) may contain a phosphate compound as needed. The resin composition (NR) can improve the adhesion to the substrate by containing a phosphoric acid compound. Examples of the phosphoric acid compound (L) include mono(meth)acryloxyethyl phosphate, di(meth)acryloxyethyl phosphate, and decyl acryloxyethyl phosphate. . In the resin composition (NR) of the present invention, the composition ratio of the total solid content is a photo-radical bond resin (A1). Photopolymerization initiator (b 1): Microparticle (C) = 5 ~80% by mass: 1 to 40% by mass: 3 to 35% by mass. The composition ratio of the total solid content of the resin composition (NR) of the present invention is more preferably a photoradical polymerizable binder resin (A1): photopolymerization initiator (B1): fine particles (C): colorant (E) : Any component other than the coloring agent (E) = 5 to 8 % by mass: 1 to 40% by mass: 3 to 35% by mass: 10 to 50% by mass: 22 to 5 % by mass. The resin composition (NR) of the present invention can be prepared by uniformly mixing the various essential components described above and any optional components added as needed in a manner consistent with the above-mentioned blending amount by a general method. (2) Acid-hardening type resin composition The photosensitive composition obtained by removing the organic solvent (D) from the acid-curable negative photosensitive resin composition is an acid-curable photosensitive composition. In the following, the resin-cured negative-type residual resin composition constituting the acid-curable photosensitive composition is referred to as a resin composition (να). When the photosensitive resin composition of the present invention is a resin composition (Να), the light-reducing resin composition contains an essential component: an alkali-soluble resin (Α21) which is used as a binder resin (A) and has a carboxyl group. And/or a phenolic hydroxyl group; a crosslinkable resin (A22) which is a compound having two or more groups reactive with a carboxyl group and/or a phenolic hydroxyl group; and a photoacid generator (B2) which is used as a photoactive agent The agent (B) is a microparticle (C) which is an organic solvent dispersion (c), and in the dispersion, the zeta potential of the microparticle (C) measured by electrophoretic light scattering is -100 to -5 mV. ; and, organic solvent (d). When the resin composition (NA) is exposed by photolithography or the like, the light-irradiated portion generates an acid from the photo-acid generator (B2), and the alkali-soluble resin (A21) having a carboxyl group and/or a phenolic hydroxyl group is cross-linkable. The resin (A22) (that is, a compound having two or more groups reactive with a carboxyl group and/or a phenolic hydroxyl group) undergoes a crosslinking reaction to form a cured product of the photosensitive composition. The portion which is not exposed to light (unexposed portion) is preferably soluble in a developing liquid (usually an alkaline developing solution) used for development after exposure. Here, the fine particles (C) and the organic solvent (D), which are essential components contained in the resin composition (NA) of the present invention, may be the same as the above (1) resin composition. (nr) is exactly the same. Hereinafter, the essential components and optional components other than the fine particles (C) and the organic solvent (D) will be described in order. (2-1) Binder resin (Α): alkali-soluble resin (Α2丨), cross-linkable resin (Α22) When the photosensitive resin composition of the present invention is a resin composition (ΝΑ), a binder resin (Α) The combination of an alkali-soluble resin (Α2丨) and a crosslinkable tree 38 201232178 lipid (A22), that is, an alkali-soluble resin (A21) which is used as a photoacid generator of the photoactive agent (B), may be mentioned. (B2) performing a cross-linking reaction by the action of an acid generated, and having a slow-base and/or a transmissive base; and a crosslinkable resin (A22) having two or more carboxyl groups and/or phenols A compound based on a hydroxyl group. (Alkali-Soluble Resin (A21)) The alkali-soluble resin (A21) has a carboxyl group and/or a phenolic hydroxyl group. It is soluble in an alkaline solution by containing a carboxyl group and/or a phenolic hydroxyl group, and can be crosslinked with a crosslinkable resin (A22) to form a cured product of a photosensitive composition, and the crosslinkable resin (A22) is a cured product. A compound having two or more groups reactive with a carboxyl group and/or a phenolic hydroxyl group. The alkali-soluble resin (A21) can be used without any limitation as long as it is a lipid which is soluble in an alkaline solution (a developing liquid constituting a photosensitive composition in a step such as photolithography). A resin (A21-1) obtained by polymerizing a monomer having a slow group and an ethylene double bond and/or a monomer having a phenolic hydroxyl group and an ethylenic double bond; and a phenol resin. The resin (A21-1)' which has a monomer having a carboxyl group and an ethylenic double bond and/or a monomer having a phenolic hydroxyl group and an ethylene double bond is required to have a mercapto group and an ethyl group. The monomer of the double bond and/or the monomer having a phenolic ruthenyl group and an ethylenic double bond are prepared by copolymerizing with other monomers as needed. Further, in the soluble resin (A21-1), the proportion of the monomer unit mainly composed of other monomers is preferably from 3 to 95% by mass, more preferably from 50 to 90% by mass. Within this range, the alkali solubility and developability of the photosensitive composition become good. * 39 201232178 In addition, the monomer having a carboxyl group and an ethylenic double bond used in the preparation of the above alkali-soluble resin (A2M) may, for example, be acrylic acid, methacrylic acid, ethylideneacetic acid 'crotonic acid, isaconic acid, cis. Salts of succinic acid, antibutanic acid, cinnamic acid or qi. Examples of the monomer having a phenolic hydroxyl group and an ethylenic double bond include, for example, o-m benzene & olefin, styrene, p-benzoic acid, etc., and one or more hydrogen atoms on the benzene ring thereof. An alkoxy group such as an alkyl group such as an ethyl group or a n-butyl group, an alkoxy group such as a methoxy group, an ethoxy group or a n-butoxy group; a halogen atom group in which one or more hydrogen atoms of the alkyl group are substituted with a γ atom; Nitro, cyano and aryl-substituted compounds, and the like. Examples of the other monomer include hydrocarbon-based olefins, vinyl ethers, isopropylene ethers, dilute-propylene-transesters, vinyl esters, allyl esters, (mercapto) acrylates, and (fluorenyl) acrylamides. In the case of the aromatic vinyl compound, the vaporized olefin, the conjugated diene, etc., it is preferable to use (mercapto) acrylate or (meth) acrylamide as the heat resistance of the partition wall. Further, these compounds may have a functional group such as a carbonyl group or an alkoxy group. The phenol resin is a phenol (at least one selected from the group consisting of an aromatic hydroxy compound such as phenol, nonylphenol, dinonylphenol, resorcin, and hydrogen styrene, and at least one of the alkyl-substituted or halogen-substituted aromatic compounds). One type) is obtained by polycondensation with a light-weight compound of a ketone, a brewer or a benzoic acid, and examples thereof include a benzoic acid resin, a cresol-formaldehyde resin, a phenol-cresol-formaldehyde co-condensation resin, and the like. A commercially available product can be used for the above alkali-soluble resin (A21). In the case of the cresol novolac type resin which is one type of the phenolic varnish type phenol resin obtained by condensing the phenol and the aldehyde in the presence of an acidic catalyst, for example, EP4020G (trade name, Asahi Organic Materials Co., Ltd.) and CRG_951 (product 201232178 "Showa Polymer Co., Ltd.") or polystyrene. The acid value of the soluble resin (A21) is preferably from 1 〇 to 6 〇〇 nig K 〇 H / g, and more preferably from 50 to 300 mg KOH / g. When it is within this range, the developability of the photosensitive resin composition becomes good. The number average molecular weight of the alkali-soluble resin (A21) is preferably 2 Å to 2 Å, and more preferably 2,000 to 15,000. When it is in this range, the alkali solubility and developability of the photosensitive resin composition become good. Further, the average S molecular weight of the soluble resin (A21) is preferably 1.5 <1〇3~4〇xl〇3, more preferably 2_〇xl03~2〇χ103. If the mass average molecular weight is less than 丨5χ1〇3, the curing may be insufficient at the time of exposure, and if it exceeds 4 〇χ 1 〇3, the development property may be lowered. In the resin composition of the present invention, the content of the alkali-soluble resin (Α2ΐ) is preferably from 1 〇 to 9 〇 by mass, more preferably from 30 to 80% by mass, based on the total solid content of the composition. When it is within this range, the developability of the photosensitive resin composition of the present invention becomes good. (Crosslinkable Resin (Α22)) The crosslinkable resin (Α22) is a compound having two or more groups reactive with a carboxyl group and/or an anthracene hydroxyl group. By having two or more groups reactive with a carboxyl group and/or a phenolic group, a soluble resin (Α21) can be crosslinked to form a cured product. Further, when the following ink-repellent agent has a carboxyl group and/or a hydroxyl group, it may be crosslinked with an ink-repellent agent to form a cured product. The crosslinkable resin (Α22) is preferably selected from at least the group consisting of an amine resin, an epoxy compound, and a » oxazoline compound. These may be used alone or in combination of two or more. 41 201232178 The amine-based resin may, for example, be a compound obtained by hydroxyalkylation of a part or all of an amine group, such as a melamine-based compound, a guanamine-based compound or a urea-based compound, or a part of a compound which has been methylolated or A compound in which all of the hydroxyl groups are etherified with decyl alcohol, ethanol, n-butanol, 2-mercapto-1-propanol or the like, for example, hexamethoxy decyl melamine or the like. Examples of the epoxy compound include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a nonylphenol novolak type epoxy resin, and a trisphenol decane type epoxy resin. Epoxy propyl ethers such as brominated epoxy resins, 3,4-epoxycyclohexyldecyl-3,4-epoxycyclohexanecarboxylate, bis(2,3-epoxy ring) Epoxy propyl esters such as alicyclic epoxy resins such as pentyl)ether, diepoxypropyl hexahydrophthalate, diepoxypropyl tetrahydrofurfurate, and diepoxypropyl phthalate Heterocyclic epoxy such as tetrapropyloxypropyldiaminediphenylnonane, triepoxypropyl-aminophenol, etc., epoxypropylamine, triepoxypropyl trimer isocyanate Resin, etc. The oxazoline compound can be exemplified by 2-vinyl-2-. Oxazoline, 2-vinyl-4-mercapto-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-. A copolymer of a polymerizable monomer such as oxazoline or 2-isopropenyl-4-mercapto-2·-oxazoline. In the resin composition (NA) of the present invention, the content of the crosslinkable resin (A22) is preferably from 1 to 50% by mass, and more preferably from 5 to 30% by mass, based on the total solid content of the composition. When it is within this range, the developability of the photosensitive resin composition becomes good. (2-2) Photoactive agent (B): Photoacid generator. (B2) 时 When the photosensitive resin composition of the present invention is a resin composition (ΝΑ), light 42 (3 201232178 = agent causes light to be light Examples of the acid-producing compound, that is, the photoacid, may be exemplified by a diaryl group, a triaryl group, a tetrazide compound, a thiol compound, and a flavonoid. Benzene fine, bis (4_t-butyl phenyl core: a specific example of the cation of the cadmium salt of one side and the early eight argon ions of the cadmium salt can be exemplified by trifluoromethane acid = Γ :: part" And one of the foregoing anion moieties: Composition: tris-methyl benzoic acid bis(4-tert-butyl phenyl sulfonium salt. Sparse, part, for example, such as three stupid base, etc. The anion portion of the base 2, 4, 6-trisylphenyl group 铳 = (4) may be exemplified by the above-mentioned di-salt iodonium salt read ion portion (4). The ion portion of the towel 丨 ▲ - square money salt system The above-mentioned positive point: a combination of one of the anionic moieties, 1 σ, and triphenylsulfonium difluoromethanesulfonate. ^ Specific examples of the sputum compound can be exemplified by 2-methyl _4, 6 _ double (three: 曱基)-1' 3' 5-two吖耕, 2_(4_methoxy phenyl), 6, three gas sulphate, 5·3 ah, 2 must be 夫 喃 ))) B double (three gas methyl Η 3 5 _ 丫 丫Morphine, 2·(5-methyl-monanyl) vinyl-bis(trichloromethyl)q 3 oxol) can be your gas methyl (1), specific examples of stone Yin, brewing compounds can be cited as double (phenyl continued醯 base) diazonite pit, bis(t-butyl hydrazino) diazocarbazone, bis(cyclohexyl fluorenyl) weight 43 201232178 nitroxane and bis(p-toluenesulfonyl) diazonium Specific examples of the crude tonic acid include, for example, 2-nitrobenzyl p-toluenesulfonate, α-(p-toluenesulfonyloxyimide)-phenylacetonitrile, and the like. In the substance (ΝΑ), the content of the photoacid generator (Β2) is preferably 〇 川 质量 质量 质量 , , , , , , , , , 川 川 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The developing property of the resin composition may be good. For example, it may be a blending ratio of the above-mentioned alkali-soluble binder resin, and the photoacid generator is preferably 0.01 to 30% by mass, more preferably 0.1%. 20 quality. /. If within this range, sense (2_3) Arbitrary component The resin composition (NA) of the present invention contains the soluble resin (A21) used as the above binder resin (A) and crosslinkability Resin (A22), photoacid generator (B2) used as photoactive agent (B), and fine particles (〇 and organic solvent (D), but can improve various functions, etc., without damaging the effects of the present invention. Any optional component is contained in the resin composition (NR). Any component other than the radical crosslinking agent may be used in the resin composition (NA). . Further, among the optional components, any of the components other than the ink-repellent agent may be the same as the above-mentioned resin composition (NR). In the case of the resin composition (NA), as the ink repellent, a fluorine-containing compound, a ruthenium-containing compound, a compound having a fluorine atom and a ruthenium atom, and the like can be given as the resin composition (NR). Same as above

[S 44 201232178 地’撥墨劑宜使用側鏈具有氟烷基之聚合物，但為樹脂組 成物(NA)時’除了上述氟炫基之外，更宜使用側鏈具有羧 基及/或酚性羥基之聚合物。其理由與上述者相同，在後述 之利用光蝕刻法形成隔壁之後焙步驟中，上述撥墨劑會與 感光性組成物中之其他掺合成分反應，而在隔壁上部表面 固定化。此外’藉由具有上述酸性基而具有鹼可溶性者， 撥墨劑不易殘留在基板上已被隔壁區隔出之區域c點）内，以 噴墨法注入墨水時之墨水濕潤擴張性良好。 樹脂組成物(NA)中，撥墨劑之較佳態樣可更具體列舉 如：由側鏈具有至少丨個!；更宜全部）氫原子經氟原子取代且 碳數20以下之直鏈狀或分枝狀氟烷基(但，烷基包含具有醚 性氧者）且宜更具有羧基及/或酚性羥基的聚合物所構成之 撥墨劑。此外，從對上述隔壁之固定化及鹼可溶性(從點（d〇t) 中去除之性質）等之觀點來看，側鏈除了氟烷基以外還具有 竣基及/或紛性羥基之聚合物的酸價宜為5〜2〇〇mgK〇H/g， 且以10〜150mgKOH/g更佳。 上述聚合物更可於側鎖具有碎數200以下程度之聚石夕 氧鏈（直鏈）。樹脂組成物(NA)中，用作撥墨劑之聚合物之 氟含量與矽含量的較佳範圍與已敘述之樹脂組成物(NR)中 撥墨劑之聚合物的較佳範圍相同。 該等撥墨劑之製造方法可利用習用公知之方法。具體 來說，就側鏈具有氟烷基與羧基及/或酚性羥基的聚合物而 言，可利用日本特開2005-315984號公報等所記載之方法來 製造，而上述具有氟烷基之聚合物與具有聚矽氧鏈之聚合 45 201232178 物組合而成的撥墨劑，則可利用曰本特開2005_300759號公 報等所記載之方法來製造。 含有上述撥墨劑之樹脂組成物(NA)的固體成分中，撥 墨劑之含有比例與上述樹脂組成物(NR)時相同，相對於組 成物固體成分全量，宜在〇.〇1〜30質量％之範圍内。其理由 在於，所得隔壁之撥墨性良好，以噴墨法注入之墨水在點 内的濕潤擴張性良好，且注入之墨水層的均勻性良好。 此外’上述撥墨劑與界面活性劑之關係係與上述樹脂 組成物(NR)相同。因此，樹脂組成物(NA)(係以噴墨法以外 之方法形成像素’並形成光學元件用隔壁）宜添加界面活性 劑’且此種界面活性劑可列舉如與上述樹脂組成物(NR)時 相同之界面活性劑。此外’摻合量亦可與上述樹脂組成物 (NR)時相同。 本發明之樹脂組成物(NA)中，其全固體成分之構成比 宜為驗可溶性樹脂（A2):交聯性樹脂（A22):光酸產生劑 (B2).微粒子(C)=l〇〜90質量％ : 1〜50質量。/〇 : 0.1〜30質量 % : 3〜35質量％。 本發明之樹脂組成物(NA)中，其全固體成分之較佳構 成比宜為驗可溶性樹脂（A2):交聯性樹脂(A22):光酸產生 劑(B2).微粒子(C):著色劑(E):著色劑(E)以外之任意成 分—1〇〜80質量1〜50質量％ :〇.1〜30質量％: 3〜35質量％: 10〜50質量。/。： 1.21〜50質量％。 可使上述說明之各種必須成分與依需要而添加之任意 成刀以符合上述摻合量之方式，利用一般方法均勻混合而 46 201232178 調製出本發明之樹脂組成物(ΝΑ)。 (3) 3有鄰醌二疊氮化合物之正型感光性樹脂組成物 本發明之感光性樹脂組成物為含有鄰醌二疊氮化合物 之正型感光性樹脂組成物時，感光性樹脂組成物含有下述 必須成分：鹼可溶性樹脂（Α3),其係用作結合劑樹脂(Α) 者鄰醌一疊氮化合物(Β3)，其係用作光活性劑(β)者；微 才：子(c) ’其係有機溶劑分散液中之微粒子(C)，且該分散液 鉍粒子(C)以電泳光散射法測定之ξ電位為-100〜-5mV ; 及，有機溶劑(D)。以下，將含有鄰醌二疊氮化合物之正型 感光性樹脂組成物稱為樹脂組成物(p⑺。 已從樹脂組成物（PQ)去除有機溶劑（D)之感光性組成 物在光蝕刻等之曝光時，於光照射部分中，鄰醌二疊氮化 -物k藉由活性光線而使對驗水溶液之溶解性增加，於後 續進行之顯像時，會溶解於所用之顯像液(通常為鹼性顯像 液）而被去除。未受光照射之部分(未曝光部分)則成為隔壁。 此外’就本發明之樹脂組成物(PQ)所含有之必須成分 的上述微粒子(C)及有機溶劑(D)而言，其種類及摻合量等均 可與上述（1)樹脂組成物(NR)時完全相同。以下，依序說明 上述微粒子(C)與有機溶劑(D)以外之必須成分及任意成分。 (3-1)結合劑樹脂(A):鹼可溶性樹脂 作為結合劑樹脂(A)，可使用樹脂組成物(PQ)中供用以 形成光學兀件之隔壁的習用公知結合劑樹脂(八广鹼可溶性 樹脂。 此種鹼可溶性樹脂可列舉如酚甲醛樹脂、甲酚甲醛樹 47 201232178 脂、酚-曱酚-甲醛共縮合樹脂、酚改質二曱苯樹脂、聚羥苯 乙烯、聚鹵化羥基苯乙烯、N-(4-羥基苯基）曱基丙烯醯胺之 共聚物及氫醌單甲基丙烯酸酯共聚物。此外，亦可使用磺 醯基醯亞胺系聚合物、含羧基聚合物、含酚性羥基之丙烯 酸系樹脂、具有磺醯胺基之丙烯酸系樹脂及胺曱酸酯系樹 脂等各種鹼可溶性高分子化合物。 上述鹼可溶性樹脂可使用市售品。此種市售品以甲酚 系酚醛清漆樹脂而言，可列舉如EP4020G(商品名，旭有機 材工業社製）及CRG-951(商品名，昭和高分子社製）或是據 羥基苯乙烯等。 此等鹼可溶性樹脂以質量平均分子量為500〜60,000且 數平均分子量為200〜40,000者為宜。此外，鹼可溶性樹脂 可使用1種或組合2種以上使用。再者，樹脂組成物（PQ)中 用作結合劑樹脂（A)之驗可溶性樹脂含量相對於組成物脂 全固體成分宜為30〜85質量％，且更宜為50〜80質量％。 (3-2)光活性劑（B):鄰酿二疊氮化合物（o-quinonediazide compound) 鄰醌二疊氮化合物只要是具有至少1個鄰醌二疊氮化 物基之化合物且可藉活性光線而增加對鹼性水溶液之溶解 性者即不特別受限。此種鄰醌二疊氮化合物可具體列舉如 經基化合物與鄰苯并酿二疊氮化物或鄰萘酿二疊氮化物之 績酸®旨。 如上述般之鄰醌二疊氮化合物.可列舉如：1，2-萘醌-2- © 二疊氮-5-磺醯基氯化物與酚甲醛樹脂或曱酚曱醛樹脂之 48 201232178 酯、1，2-萘醌-2-二疊氮-5-磺醯基氣化物與五倍子酚丙酮樹 月曰之酯、1，2-奈醌-2-一疊氮_5_橫醯基氣化物與與間苯二齡 -苯曱醛樹脂之酯、1，2-萘醌_2-二疊氮-5-磺醯基氣化物與間 苯二酚-五倍子酚-丙酮共縮合樹脂之酯、使丨，2_萘醌_2_二 疊氮-5-磺醯基氯化物對末端具有羥基之聚酯作酯化而成之 物、使1，2-萘酿i-2-一疊氮_5_績醯基氣化物對义(4_經基苯基) 曱基丙烯醯胺之均聚物或與其他可共聚合之單體的共聚物 作酯化而成之物、1，2-萘醌_2_二疊氮_5_磺醯基氯化物與雙 酚甲醛樹脂之酯、使1，2-萘醌-2-二疊氮-5-磺醯基氯化物對 笨乙烯之均聚物或與其他可共聚合之單體的共聚物作酯 化而成之物、1,2-萘醌-2-二疊氮-5-磺醯基氯化物與聚羥基 二苯基酮之酯等。 樹脂組成物（pQ)中用作光活性劑（B)之鄰醌二疊氮化 合物（B3)之含量相對於組成物全固體成分宜為5〜6〇質量 % ’更宜為10〜40質量％。 (3-3)任意成分 雖然本發明之樹脂組成物(P Q)含有用作上述結合劑樹 月曰（A)之驗可洛性樹脂(A3)、用作光活性劑(b)之鄰覼二疊氮 化合物（B3)、上述微粒子（c)及有機溶劑(D)，但在不損及本 發明效果之範圍内’在提高各種機能等之目的下，可含有 各種任意成分。 作為此種任意成分，亦可將已在上述樹脂組成物(NR) 中作說明之任意成分中，除了自由基交聯劑以外之所有成 分用於樹脂組成物(PQ)。此外，該等任意成分之中，就撥 49 201232178 墨劑以外之任意成分而言，有關種類、摻合量及其等之較 佳態樣亦可與上述樹脂組成物(NR)之情況相同。 在樹脂組成物（PQ)之情況下，撥墨劑之較佳態樣可列 舉如具有氟烷基結構與酸性基之聚合物。其理由在於，具 有驗可溶性者較不易於點（dot)内殘留撥墨劑，以噴墨法注 入墨水時墨水之濕潤擴張性良好。上述酸性基可列舉如竣 基、酚性羥基、磷酸基、磺酸基等。此外’將成為此種撥 墨劑之聚合物中，氟炫基結構及酸性基可含在聚合物主鍵 中’亦可含在側鏈中，更可含在主鏈與側鍵兩者之中。 含有上述撥墨劑之樹脂組成物（PQ)的固體成分中，撥 墨劑之含有比例相對於組成物固體成分全量宜在〇.〇1〜3〇 質量％之範圍内。其理由在於，如此所得之隔壁的撥墨性 良好，藉噴墨法注入之墨水在點内之濕潤擴張性良好，且 所注入之墨水層的均勻性良好。 此外，上述撥墨劑與界面活性劑之關係與上述樹脂組 成物(NR)相同。因此，形成以噴墨法以外之方法進行像素 形成之光學元件用隔壁的樹脂組成物（PQ)宜添加界面活性 劑，且此種界面活性劑可列舉與上述樹脂組成物(nr)時相 同之界面活性劑。此外，就摻合量而Ί* ’亦可與上述樹脂 組成物(NR)之情況相同。 本發明之樹脂組成物(PQ)中，其食固體成分之構成比 宜為鹼可溶性樹脂（A3):光酸產生劑（03):微粒子（C) = 30~85質量％ : 5〜60質量°/〇 : 3〜35質量° 又，其全固體成分之較佳構成比為驗可溶性樹脂[S 44 201232178 It is preferable to use a polymer having a fluoroalkyl group in the side chain, but in the case of a resin composition (NA), it is more preferable to use a side chain having a carboxyl group and/or a phenol in addition to the above-mentioned fluoroheptyl group. a polymer of a hydroxyl group. The reason is the same as the above, and in the baking step in which the partition wall is formed by photolithography, which will be described later, the ink-repellent agent is reacted with the other blending component in the photosensitive composition, and is fixed on the upper surface of the partition wall. Further, the ink having the above-mentioned acidic group and having an alkali solubility is less likely to remain in the region c of the substrate which is partitioned by the partition wall, and the ink wettability is excellent when the ink is injected by the ink jet method. In the resin composition (NA), a preferred aspect of the ink-repellent agent may be more specifically listed as follows: a chain having at least one of the side chains; more preferably all of the hydrogen atoms substituted by a fluorine atom and having a carbon number of 20 or less Or an ink-repellent agent composed of a branched fluoroalkyl group (however, the alkyl group contains an ether oxygen) and preferably has a carboxyl group and/or a phenolic hydroxyl group. Further, from the viewpoints of immobilization of the partition walls and alkali solubility (the property of removal from a point (d〇t)), the side chain has a polymerization of a mercapto group and/or a divalent hydroxyl group in addition to the fluoroalkyl group. The acid value of the substance is preferably 5 to 2 〇〇 mg K 〇 H / g, and more preferably 10 to 150 mg KOH / g. The above polymer is more capable of side-locking with a poly-stone chain (straight chain) having a number of 200 or less. In the resin composition (NA), the preferred range of the fluorine content and the cerium content of the polymer used as the ink-repellent agent is the same as the preferred range of the polymer of the ink-repellent agent in the resin composition (NR) described. The method of producing such an ink-repellent agent can be carried out by a conventionally known method. Specifically, a polymer having a fluoroalkyl group and a carboxyl group and/or a phenolic hydroxyl group in the side chain can be produced by the method described in JP-A-2005-315984 or the like, and the above-mentioned fluoroalkyl group is used. The ink-repellent agent which is a combination of a polymer and a polymerization polymer having a polyoxygen chain of 45 201232178 can be produced by the method described in JP-A-2005-300759. In the solid content of the resin composition (NA) containing the above-mentioned ink repellent, the content of the ink repellent is the same as that of the above resin composition (NR), and is preferably in the range of 〇.〇1 to 30 with respect to the total solid content of the composition. Within the range of mass %. The reason for this is that the obtained partition walls have good ink repellency, and the ink which is injected by the ink jet method has good wet expandability in the dots, and the uniformity of the ink layer to be injected is good. Further, the relationship between the above-mentioned ink repellent and the surfactant is the same as that of the above resin composition (NR). Therefore, the resin composition (NA) (forming a pixel by a method other than the inkjet method and forming a partition for an optical element) is preferably a surfactant added, and such a surfactant may be exemplified by the above resin composition (NR). The same surfactant. Further, the blending amount may be the same as in the case of the above resin composition (NR). In the resin composition (NA) of the present invention, the composition ratio of the total solid content is preferably a soluble resin (A2): a crosslinkable resin (A22): a photoacid generator (B2). A microparticle (C) = l〇 ~ 90% by mass: 1 to 50 mass. /〇 : 0.1 to 30 mass % : 3 to 35 mass %. In the resin composition (NA) of the present invention, the preferred composition ratio of the total solid content is preferably the soluble resin (A2): crosslinkable resin (A22): photoacid generator (B2). Microparticles (C): Coloring agent (E): Any component other than the coloring agent (E) - 1 〇 to 80 mass 1 to 50% by mass: 〇.1 to 30% by mass: 3 to 35 mass%: 10 to 50 mass. /. : 1.21 to 50% by mass. The resin composition (ΝΑ) of the present invention can be prepared by uniformly mixing the various essential components described above with any of the necessary knives as needed in a manner consistent with the above-mentioned blending amount by a general method. (3) A positive photosensitive resin composition having an ortho-quinone diazide compound. The photosensitive resin composition of the present invention is a positive photosensitive resin composition containing an o-quinonediazide compound, and a photosensitive resin composition. Containing the following essential components: alkali-soluble resin (Α3), which is used as a binder resin (Α), an ortho-azide compound (Β3), which is used as a photoactive agent (β); (c) 'The fine particles (C) in the organic solvent dispersion, and the zeta potential of the dispersion ruthenium particles (C) measured by electrophoretic light scattering is -100 to -5 mV; and the organic solvent (D). Hereinafter, a positive photosensitive resin composition containing an o-quinonediazide compound is referred to as a resin composition (p(7). A photosensitive composition having been removed from the resin composition (PQ) as an organic solvent (D) is photoetched or the like. During exposure, in the irradiated portion of the light, the ortho-quinonediazide-k increases the solubility of the aqueous solution by the active light, and is dissolved in the developing solution used in the subsequent development (usually It is removed as an alkaline developing solution. The portion which is not exposed to light (unexposed portion) becomes a partition wall. Further, the above-mentioned fine particles (C) and organic components which are essential components contained in the resin composition (PQ) of the present invention. The solvent (D) may be completely the same as the above-mentioned (1) resin composition (NR), and the following description of the fine particles (C) and the organic solvent (D) will be sequentially described. (3-1) Binder resin (A): Alkali-soluble resin As the binder resin (A), a conventionally known binder for forming a partition wall of an optical element in a resin composition (PQ) can be used. Resin (Baguang alkali soluble resin. This alkali soluble resin Listed as phenol formaldehyde resin, cresol formaldehyde tree 47 201232178 lipid, phenol-nonanol-formaldehyde co-condensation resin, phenol-modified diterpene benzene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, N-(4-hydroxybenzene a copolymer of a mercapto acrylamide and a hydroquinone monomethacrylate copolymer. Further, a sulfonyl quinone imine polymer, a carboxyl group-containing polymer, or a phenolic hydroxyl group-containing acrylic resin may be used. Various alkali-soluble polymer compounds, such as an acrylamide-based acrylic resin and an amine phthalate-based resin. Commercially available products can be used as the alkali-soluble resin. Such a commercially available product may be a cresol-based novolak resin. For example, EP4020G (trade name, manufactured by Asahi Organic Materials Co., Ltd.) and CRG-951 (trade name, manufactured by Showa Polymer Co., Ltd.) or hydroxystyrene, etc. are used. These alkali-soluble resins have a mass average molecular weight of 500 to 60,000. The number average molecular weight is preferably from 200 to 40,000. Further, the alkali-soluble resin may be used alone or in combination of two or more. Further, the resin composition (PQ) is used as a binder resin (A) for the determination of the soluble resin content. phase The total solid content of the composition is preferably from 30 to 85% by mass, and more preferably from 50 to 80% by mass. (3-2) Photoactive agent (B): o-quinonediazide compound The quinonediazide compound is not particularly limited as long as it is a compound having at least one ortho-quinonediazide group and can be added to the alkaline aqueous solution by the active light. The ortho-quinonediazide compound can be used. Specifically, for example, a trans-base compound and an ortho-benzoic diazide or an o-naphtho-diazide acid acid acid. The ortho-quinonediazide compound as described above may be exemplified by 1,2-naphthoquinone. -2- © Diazide-5-sulfonyl chloride and phenol formaldehyde resin or indophenol furfural resin 48 201232178 Ester, 1,2-naphthoquinone-2-diazide-5-sulfonyl vapor Ester with gallnut phenol acetone, 1,2-naphtho-2-azide _5_cross fluorenyl vapor and ester with isophthalic acid-phenylfurfural resin, 1,2-naphthoquinone Ester of _2-diazide-5-sulfonyl vapor and resorcinol-glycoside-acetone co-condensation resin, 丨, 2_naphthoquinone-2_diazide-5-sulfonyl chloride Polymerization of hydroxyl groups at the ends Ester esterified as a homopolymer of 1,2-naphthalene i-2-monoazide _5_ 醯 气 气 气 ( (4_ phenylphenyl) decyl acrylamide Or esterified with a copolymer of other copolymerizable monomers, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and ester of bisphenol formaldehyde resin, 1 , 2-naphthoquinone-2-diazide-5-sulfonyl chloride is a mixture of a homopolymer of stupid ethylene or a copolymer with other copolymerizable monomers, 1,2- An ester of naphthoquinone-2-diazide-5-sulfonyl chloride and polyhydroxydiphenyl ketone. The content of the ortho-quinonediazide compound (B3) used as the photoactive agent (B) in the resin composition (pQ) is preferably 5 to 6 % by mass based on the total solid content of the composition, and more preferably 10 to 40% by mass. %. (3-3) Arbitrary component Although the resin composition (PQ) of the present invention contains the testable resin (A3) used as the above-mentioned binder (A), and is used as a neighboring agent of the photoactive agent (b) The diazide compound (B3), the fine particles (c), and the organic solvent (D) may contain various optional components for the purpose of improving various functions and the like without departing from the effects of the present invention. As such an optional component, all of the components other than the radical crosslinking agent which have been described in the above resin composition (NR) may be used for the resin composition (PQ). Further, among the optional components, the optimum type of the type, the blending amount, and the like may be the same as those of the above resin composition (NR) in terms of any component other than the ink of 201232178. In the case of the resin composition (PQ), preferred embodiments of the ink-repellent agent may be, for example, a polymer having a fluoroalkyl structure and an acidic group. The reason for this is that it is less likely to have a residual ink repellent in the dot, and the wet dilatability of the ink is good when the ink is injected by the ink jet method. Examples of the acidic group include a mercapto group, a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group. In addition, in the polymer which will become such an ink-repellent agent, the fluorophytic structure and the acidic group may be contained in the main bond of the polymer, which may be contained in the side chain, and may be contained in both the main chain and the side bond. . In the solid content of the resin composition (PQ) containing the above-mentioned ink repellent, the content of the ink repellent is preferably in the range of 〜1 to 3 〇 mass% based on the total solid content of the composition. The reason for this is that the ink absorbing property of the partition wall thus obtained is good, and the ink which is injected by the ink jet method has good wettability in the dots, and the uniformity of the ink layer to be injected is good. Further, the relationship between the above-mentioned ink repellent and the surfactant is the same as that of the above resin composition (NR). Therefore, it is preferable to add a surfactant to the resin composition (PQ) which forms the partition for optical elements which performs pixel formation by the method other than the inkjet method, and the surfactant is the same as the resin composition (nr) mentioned above. Surfactant. Further, the amount of Ί*' may be the same as in the case of the above resin composition (NR). In the resin composition (PQ) of the present invention, the composition ratio of the solid content of the food is preferably an alkali-soluble resin (A3): photoacid generator (03): fine particles (C) = 30 to 8 mass%: 5 to 60 mass °/〇: 3~35 mass °, and the preferred composition ratio of the whole solid component is the soluble resin

S 50 201232178 (A3):光酸產生劑(B3):微粒子(〇 :著色劑(E):著色劑(E) 以外之任思成分=30〜80質量。/〇 : 5〜60質量％ : 3-35質量％ : 10〜50質量％ : 1.21〜50質量％。 可配合上述摻合量，將上述說明之各種必須成分與依 需要來添加之任意成分以一般方法予以均勻混合，而調製 出本發明之樹脂組成物(PQ)。 (4)含有經封端化之酸性基的正型感光性樹脂組成物 本發明之感光性樹脂組成物係含有經封端化之酸性基 的正型感光性樹脂組成物時，感光性樹脂組成物含有下述 者作為必須成分：具有經封端化之酸性基的結合劑樹脂， 其係用作結合劑樹脂(A);用作光活性劑(B)之光酸產生劑； 微粒子(c)，其係有機溶劑分散液中之微粒子(c)，且該分散 液中微粒子（C)以電泳光散射法測定之ξ電位為 -100—5mV;及，有機溶劑（D)。以下，將含有經封端化之 酸性基的正型感光性樹脂組成物稱為樹脂組成物(PB)。 已自樹脂組成物（PB)去除有機溶劑之感光性組成 物在進行光蝕刻等之曝光時，光照射部分會自光酸產生劑 產生酸’藉由該酸之作用，具有經封端化之酸性基的結合 劑樹脂會成為鹼可溶性，在後續進行顯像時，會溶解於所 用顯像液(通常為鹼性顯像液）而被去除。未受光照射之部分 (未曝光部分）則成為隔壁。 於此，就本發明之樹脂組成物（PB)所含有之必須成分 的上述微粒子(C)及有機溶劑(d)而言，其種類及配合量等均 可與上述（1)樹脂組成物(NR)的情況完全相同。此外，光酸 51 201232178 產生劑之種類及配合量等，均可與上述(2)樹脂組成物(ΝΑ) 之光酸產生劑完全相同。 (4-1)、结合劑樹脂(Α广具有經封端化之酸性基的結合劑樹脂 具有經封端化之酸性基的結合劑樹脂可列舉習用公知 之驗可溶性樹脂的酸性基業經封端化而成之樹脂。 作為經封端化之酸性基中之酸性基，有羧酸基、磺酸 基、與已鍵結有2個全氟烧基或烧基之碳原子鍵結的羥基、 已鍵結芳基之羥基等。較佳之酸性基則是羧酸基、與已鍵 結有2個三氟曱基之碳原子鍵結的羥基、與鍵結有三氟曱基 與甲基之碳原子鍵結的羥基及已鍵結苯基之羥基。此外， 於上述者中’芳基及苯基亦可具有取代基，且該取代基以 i原子為宜，更宜氟原子。鍵結羥基之芳基以多氟羥笨基 為佳。 經封端化之酸性基的封端部分可列舉如下述結構：利 用烷基、烷氧羰基、三烷基矽基、醯基及環狀醚基等，將 醇類或齡類之烷性羥基或酚性羥基之氫原子或羧基之羥基 作取代而成者。適宜取代羥基之氫原子的烷基可列舉如： 可具有取代基（芳基 '烷氧基等）之碳數丨〜6的烷基。 該等烧基之具體例可列舉如碳數6以下之烧基（第三丁 基等）、全碳數7〜20之芳基取代烷基（苄基、三苯基曱基、對 甲氧基苄基基、3, 4-二甲氧基苄基、丨_苯氧基乙基等）及全 碳數8以下之烷氧基烷基（曱氧基曱基、丨_乙氧基乙基(2_曱 氧基乙氧基）甲基、苄氧基曱基等）。作為適宜取代經基之氩 原子的烷氧羰基’有全碳數8以下之烷氧羰基，且可列舉如S 50 201232178 (A3): Photoacid generator (B3): Fine particles (〇: Colorant (E): Coloring agent (E), other ingredients: 30 to 80 mass. /〇: 5 to 60% by mass: 3-35 mass%: 10 to 50 mass%: 1.21 to 50 mass%. The various essential components described above and the optional components added as needed may be uniformly mixed in a usual manner in accordance with the above blending amount, and prepared. The resin composition (PQ) of the present invention. (4) The positive photosensitive resin composition containing the blocked acidic group. The photosensitive resin composition of the present invention contains a positively-sensitive photosensitive group having a blocked acid group. In the case of the resin composition, the photosensitive resin composition contains, as an essential component, a binder resin having a blocked acid group, which is used as a binder resin (A); and as a photoactive agent (B) a photoacid generator; the microparticles (c), which are microparticles (c) in an organic solvent dispersion, and the microparticles (C) in the dispersion have a zeta potential of -100 to 5 mV as determined by electrophoretic light scattering; , organic solvent (D). Hereinafter, a positive photosensitive resin composition containing a blocked acidic group The resin composition (PB). The photosensitive composition which has been removed from the resin composition (PB) is subjected to photolithography or the like, and the light-irradiated portion generates an acid from the photo-acid generator. The binder resin having a blocked acidic group becomes alkali-soluble, and is dissolved in the developing solution (usually an alkaline developing solution) to be removed after subsequent development. The portion (unexposed portion) is a partition wall. Here, the type and amount of the fine particles (C) and the organic solvent (d) which are essential components contained in the resin composition (PB) of the present invention are It can be exactly the same as the case of the above-mentioned (1) resin composition (NR). Further, the kind and amount of the photoacid 51 201232178 generator can be the same as the photoacid generator of the above (2) resin composition (ΝΑ). (4-1), a binder resin (a binder resin having a blocked acid group-containing acid group), and a binder resin having a blocked acid group, may be exemplified by an acidic group of a known soluble resin. A resin that has been blocked. Is an acidic group in the blocked acidic group, having a carboxylic acid group, a sulfonic acid group, a hydroxyl group bonded to a carbon atom to which two perfluoroalkyl groups or an alkyl group have been bonded, and a bonded aryl group a hydroxyl group, etc. Preferably, the acidic group is a carboxylic acid group, a hydroxyl group bonded to a carbon atom to which two trifluorofluorenyl groups have been bonded, a hydroxyl group bonded to a carbon atom bonded to a trifluoromethyl group and a methyl group, and Further, in the above, the 'aryl group and the phenyl group may have a substituent, and the substituent is preferably an atom of an atom, more preferably a fluorine atom. The aryl group bonded to the hydroxyl group is polyfluorinated. Preferably, the blocked moiety of the blocked acidic group is exemplified by an alkyl group, an alkoxycarbonyl group, a trialkylsulfonyl group, a fluorenyl group and a cyclic ether group, etc., or an alcohol or The alkyl group of the aged or the hydrogen atom of the phenolic hydroxyl group or the hydroxyl group of the carboxyl group is substituted. The alkyl group which is preferably substituted with a hydrogen atom of a hydroxyl group may, for example, be an alkyl group having a carbon number of 丨6 or 6 which may have a substituent (aryl 'alkoxy group or the like). Specific examples of the calcining group include a calcining group having a carbon number of 6 or less (t-butyl group or the like), and an aryl-substituted alkyl group having a total carbon number of 7 to 20 (benzyl group, triphenylsulfonyl group, p-methoxy group). Alkoxyalkyl group (hydroxybenzyl group, 丨_ethoxy B) having a total carbon number of 8 or less and a carboxy group having a total carbon number of 8 or less A group of (2-methoxyethoxy)methyl, benzyloxyindenyl, and the like). The alkoxycarbonyl group which is a suitable substituted argon atom of the radical has an alkoxycarbonyl group having a total carbon number of 8 or less, and may be enumerated as

[S 52 201232178 第三丁氧羰基等。適宜取代羥基之氫原子的三烷基矽基可 列舉如全碳數10以下之三炫基矽基及三甲基矽基。適宜取 代羥基之氫原子的醯基有全碳數8以下之醯基’且可列舉如 二甲基乙SI基、苯甲醯基及乙醯基等。適宜取代經基之氫 原子的環狀醚基可列舉如四氫哌喃基等。 將酸性基封端化之方法可列舉如：因應酸性基之種 類’使醇類或叛酸或是該等之活性衍生体物發生反應之方 法。該等活性衍生物可列舉如烷基鹵化物、酸氣化物、酸 酐、氣化碳酸酯類及3, 4-二氫-2H-哌喃等。 具有該等經封端化之酸性基的結合劑樹脂以質量平均 分子量為500〜60,000且數平均分子量為2〇〇〜4〇,〇〇〇者為 宜。此外’結合劑樹脂可使用1種亦可組合2種以上作使用。 又’樹脂組成物（PB)中之結合劑樹脂含量相對於組成物之 全固體成分宜為30〜90質量％，更宜為50〜85質量％。 (4-2)任意成分 本發明之樹脂組成物(PB)雖含有用作上述結合劑樹脂 (A)之具有經封端化酸性基的結合劑樹脂、用作光活性劑(b) 之光酸產生劑、上述微粒子(C)及有機溶劑(D)，但在不損及 本發明效果之範圍内，在提升各種機能等之目的下，可含 有各種任意成分。 作為此種任意成分，已在上述樹脂組成物(NR)處作說 明之任意成分中，除了自由基交聯劑以外之全部成分亦可 於樹脂組成物(PB)中作使用。此外，該等任意成分之中， ό 就撥墨劑以外之任意成分而言，亦可使種類、配合量及其 53 201232178 等之較佳態樣與上述樹脂組成物(NR)之情況相同。 樹脂組成物(PB)時之撥墨劑的較佳態樣可列舉如：一 種具有氟烷基結構之聚合物，該聚合物之結構係至少在曝 光後具有酸性基者。此種撥墨劑具體可列舉如：在具有氟 院基結構之同時還具有經封端化之酸性基的聚合物；及’ 具有氟烷基結構與酸性基，且分子量與酸價已調整成可維 持耐鹼顯像性（顯像時不會輕易從未曝光部分溶出）之聚合 物等。舉例來說，其理由在於，一旦受曝光而生成酸性基， 點内不易殘留撥墨劑，以喷墨法注入墨水時墨水之濕潤擴 張性良好◎此外，經封端化之酸性基可列舉如與上述同樣 之物。 作為具有氟烷基結構之同時還具有經封端化酸性基之 聚合物’可列舉如揭示在國際公開第2004/042474號、國際 公開第2007/069703號及國際公開第2008/149776號等之具 有氟烷基之單體與2-四氫哌喃基甲基丙烯酸的共聚物等。 此外’該聚合物可在側鏈上具有矽數200以下程度之聚矽氣 鏈(直鏈）。 含有上述撥墨劑之樹脂組成物（PB)的固體成分中， ，梅 墨劑之含有比例相對於組成物固體成分全量宜在〇 ·υι 〜3〇 質量°/。之範圍内。其理由在於，如此所得隔壁之撥墨性^ 好’且以喷墨法注入之墨水在點内的濕潤擴張性良奸， 入之墨水層的均勻性良好。 此外’上述撥墨劑與界面活性劑之關係係與上迷樹月t 組成物(NR)相同。因此，形成以喷墨法以外之方法連 _ 像 54 201232178 素形成之光學元件用隔壁的樹脂組成物（PB)宜添加界面活 性劑，且此種界面活性劑可列舉與上述樹脂組成物(nr)時 同樣之界面活性劑。此外，配合量亦可與上述樹脂组成物 (NR)時相同。 本發明之樹脂組成物(PB)中，其全固體成分之構成比 宜為具有經封端化酸性基之結合劑樹脂(A4):光酸產生劑 (B4):微粒子(〇=30〜90質量％ : 〇·ΐ〜30質量％ : 3〜35質量 %。 又’其全固體成分之較佳構成比為鹼可溶性樹脂 (A3):光酸產生劑(B3):微粒子(c):著色劑(E):著色劑(E) 以外之任意成分=30〜90質量％ : 0.1-30質量。/〇 : 3〜35質量 °/〇: 10〜50質量％: 1.21〜50質量％。 可配合上述摻合量，將上述說明之各種必須成分與因 應需要而添加之任意成分以一般方法予以均勻混合而調製 出本發明之樹脂組成物(PB)。 [隔壁;| 本發明之隔壁係使用上述本發明之感光性樹脂組成物 並以光蝕刻法而將基板上區隔出用以形成像素之多數區塊 之形狀者，可適用在濾色器或有機EL元件之隔壁（以黑矩陣 為宜）等 (基板） 作為用以形成本發明之隔壁的上述基板’其材質並未 特別受限，但可列舉如一般可供用於光學元件之基板的材 質’例如：各種玻璃板；聚酯（聚對酞酸乙二酯等）、聚烯烴 55 201232178 (聚乙烯、聚丙烯等）' 聚碳酸酯、聚曱基丙烯酸甲酯、聚碾、 聚醯亞胺及聚（甲基）丙烯酸樹脂等之熱可塑性塑膠片；環氣 樹脂、不飽和聚酯等之熱硬化性塑膠片等。此外，可列舉 如預先使氮化矽或聚醯亞胺等之絕緣膜形成在上述基材而 形成之基板。從耐熱性之觀點來看，尤以玻璃板、聚醯亞 胺等之耐熱性塑膠為佳。 此外’於本發明中，上述基板使用具有下述表面特性 之基板時’可令使用本發明之感光性樹脂組成物之圖案的 顯像密著性效果更為顯著：即，隔壁形成面與光蝕刻法所 用驗性顯像液之親和性佳之表面特性。 於此’與鹼性顯像液之親和性佳係指，水之接觸角在 70。以下的情況。再者，水之接觸角在5〇。以下時(特別是水 之接觸角在30。以下時），可令使用本發明之感光性樹脂組 成物之圖案的顯像密著性效果更加顯著。此外，基板之種 類為基板表面具有如羥基等之親水性官能基且屬破螭基板 (例如無鹼玻璃、鹼玻璃等之玻璃基板)者時，可令使用本發 明之感光性樹脂組成物之圖案的顯像密著性效果更為顯 著。 又，本發明之隔壁形成部位只要是基板上即不特別受 限。亦即，於本說明書中，例如在基板形成有配線或其他 機能層時，「形成在基板上」一語意指形成在基板上之更上 方的配線上或機能層上。 /以下，作為製造本發明隔壁之方法的一例，針對使用 本發明之感光性樹脂組成物並以光蝕刻步驟來製造隔辟的[S 52 201232178 Third butoxycarbonyl and the like. The trialkylsulfonyl group which is suitable for substituting a hydrogen atom of a hydroxyl group may, for example, be a trisylfluorenyl group having a total carbon number of 10 or less and a trimethylsulfonyl group. The mercapto group which is suitable for the hydrogen atom of the hydroxyl group is a mercapto group having a total carbon number of 8 or less and may, for example, be a dimethylethyl SI group, a benzamidine group or an ethenyl group. The cyclic ether group which is suitable for substituting the hydrogen atom of the radical may, for example, be a tetrahydropyranyl group or the like. The method of blocking the acidic group may, for example, be a method of reacting an alcohol or a tickic acid or an active derivative thereof in response to the species of the acidic group. Examples of such reactive derivatives include alkyl halides, acid vapors, acid anhydrides, vaporized carbonates, and 3,4-dihydro-2H-pyran. The binder resin having such blocked acid groups has a mass average molecular weight of 500 to 60,000 and a number average molecular weight of 2 Å to 4 Å, which is preferred. Further, the binder resin may be used alone or in combination of two or more. Further, the content of the binder resin in the resin composition (PB) is preferably from 30 to 90% by mass, more preferably from 50 to 85% by mass, based on the total solid content of the composition. (4-2) Optional component The resin composition (PB) of the present invention contains a binder resin having a blocked acid group as the binder resin (A) and a light used as a photoactive agent (b) The acid generator, the fine particles (C), and the organic solvent (D) may contain various optional components for the purpose of improving various functions and the like without departing from the effects of the present invention. As the optional component, all of the components described in the above resin composition (NR), except for the radical crosslinking agent, may be used in the resin composition (PB). Further, among any of the optional components, the arbitrarily selected components other than the ink-repellent agent may be the same as the above-mentioned resin composition (NR). Preferred examples of the ink-repellent agent in the case of the resin composition (PB) include, for example, a polymer having a fluoroalkyl structure which has an acidic group at least after exposure. Specific examples of such an ink-repellent agent include a polymer having a fluorine-based structure and a blocked acid group; and 'having a fluoroalkyl structure and an acidic group, and the molecular weight and the acid value have been adjusted to A polymer which maintains alkali-resistant developability (it is not easily eluted from an unexposed portion when developing). For example, the reason is that when an acidic group is formed by exposure, the ink repellent is less likely to remain in the dots, and the wet dilatability of the ink is good when the ink is injected by the inkjet method. Further, the blocked acid group can be exemplified as The same thing as above. Examples of the polymer having a fluoroalkyl structure and having a blocked acid group are disclosed in, for example, International Publication No. 2004/042474, International Publication No. 2007/069703, and International Publication No. 2008/149776. A copolymer of a monomer having a fluoroalkyl group and 2-tetrahydropyranyl methacrylic acid. Further, the polymer may have a polyfluorene chain (straight chain) having a number of turns of 200 or less in the side chain. In the solid content of the resin composition (PB) containing the above-mentioned ink-repellent agent, the content ratio of the plum-based ink is preferably 〇·υι 3 to 3 〇 mass/% with respect to the total solid content of the composition. Within the scope. The reason for this is that the ink repellency of the partition wall thus obtained is good, and the ink which is injected by the ink jet method has a wet expansion property in the spot, and the uniformity of the ink layer is good. Further, the relationship between the above-mentioned ink-repellent agent and the surfactant is the same as that of the above-mentioned sapphire t composition (NR). Therefore, it is preferable to add a surfactant to the resin composition (PB) which is a partition for an optical element formed by a method other than the inkjet method, and the surfactant is exemplified by the above resin composition (nr). The same surfactant. Further, the compounding amount may be the same as in the case of the above resin composition (NR). In the resin composition (PB) of the present invention, the composition ratio of the total solid content is preferably a binder resin (A4) having a blocked acid group: a photoacid generator (B4): fine particles (〇=30 to 90) Mass % : 〇·ΐ~30% by mass: 3 to 35% by mass. Further, the preferred composition ratio of all solid components is alkali-soluble resin (A3): photoacid generator (B3): fine particles (c): coloring Agent (E): Any component other than the colorant (E) = 30 to 90% by mass: 0.1 to 30% by mass. / 〇: 3 to 35 mass % / 〇: 10 to 50% by mass: 1.21 to 50% by mass. The resin composition (PB) of the present invention is prepared by uniformly mixing the above-mentioned various essential components and any components added as needed in a usual manner in accordance with the above-mentioned blending amount. [Partition; | The photosensitive resin composition of the present invention can be applied to a partition of a color filter or an organic EL element by a photo-etching method to separate a substrate from a plurality of blocks for forming a pixel (in a black matrix) (Substrate) (the substrate) as the above-mentioned substrate for forming the partition wall of the present invention, the material thereof is not particularly limited. For example, a material generally available for a substrate for an optical element can be cited, for example, various glass sheets; polyester (polyethylene terephthalate or the like), polyolefin 55 201232178 (polyethylene, polypropylene, etc.), polycarbonate, Thermoplastic plastic sheets such as polymethyl methacrylate, poly-rolling, poly-imine, and poly(meth)acrylic resin; thermosetting plastic sheets such as cycloolefin resin and unsaturated polyester, etc. For example, a substrate formed by forming an insulating film such as tantalum nitride or polyimide on the substrate is preferably a heat-resistant plastic such as a glass plate or a polyimide. Further, in the present invention, when the substrate having the surface characteristics described above is used, the effect of the image-forming adhesion using the pattern of the photosensitive resin composition of the present invention can be made more remarkable: that is, the partition wall forming surface and light The surface characteristics of the inspectability developing solution used in the etching method are excellent. The affinity with the alkaline developing solution means that the contact angle of water is 70 or less. Furthermore, the contact angle of water is 5〇. The following (special When the contact angle of water is 30 or less, the effect of the image-forming adhesion of the pattern of the photosensitive resin composition of the present invention can be made more remarkable. Further, the type of the substrate is such that the surface of the substrate has a hydrophilic function such as a hydroxyl group. In the case of a ruthenium-based substrate (for example, a glass substrate such as an alkali-free glass or an alkali glass), the effect of the image-forming adhesion using the pattern of the photosensitive resin composition of the present invention can be made more remarkable. The partition forming portion is not particularly limited as long as it is on the substrate. That is, in the present specification, for example, when a wiring or other functional layer is formed on the substrate, the phrase "formed on the substrate" means formed above the substrate. On the wiring or on the functional layer. / Hereinafter, as an example of the method for producing the partition wall of the present invention, the photosensitive resin composition of the present invention is used and the photolithography step is used to fabricate the barrier.

is 56 201232178 方法’一邊參照（1)模式性顯示負型感光性樹脂組成物之隔 i九成方法的第l(al)至（cl)圖及（2)模式性顯示正型感光性 樹月曰組成物之隔壁形成方法的第1(a2)至（c2)圖，一邊進行 說明。 (朝基板上形成由感光性樹脂組成物所構成之濕潤膜=塗 佈步驟） 首先’為了在基板上形成感光性樹脂組成物之濕潤 膜於基板上之預定位置上塗佈感光性樹脂組成物（以下稱 塗佈v驟」）。塗佈方法可列舉如旋塗法(spin_c〇ating)、 喷務去、狹縫塗佈法、|昆塗法、旋轉塗佈法及棒塗法等習 用公知之方法。 θ於此’塗佈步驟所得感光性樹脂組成物之濕潤膜的膜 ^雖亦依使用之感光性樹脂種類及固體成分濃度以及下述 兒月之隔壁形成方法等而異，但會設定在所得之隔壁高度 成為所奴數值之厚度，例如前述所欲數值之2〜倍程度。 蚁j卩本發明之製造方法獲得之光學元件中，前述最 V之隔心度雖亦依光學元件之種類而異，但較宜為 二5 5〇_ ’更宜〇·2〜1〇_且以〇.5〜5μηι尤佳，因此，感光 一痒曰、且成物之塗佈係以最終所得隔壁之高度會成述 向度之方式進行。 (乾燥/預培步驟） 膜H著μ使已形成在基板上之感紐樹脂組成物的濕湖 黏著!^ 11由使該制膜乾燥，有機溶劑⑼會揮發而形戒 較少之感紐組成物層。感紐樹餘成物含有有 57 201232178 機溶劑（D)以外之低沸點化合物時，會連同有機溶劑（D)-起被去除。 進行感光性樹脂組成物所含有機溶劑（D)之揮發去除 時，宜進行真空乾燥或加熱乾燥。此外，為了不使感光性 組成物層發生外觀之不均且有效率地使其乾燥，更宜併用 真空乾燥與加熱乾燥。雖也會依各成分之種類及摻合比例 等而不同，但真空乾燥宜採用500〜10Pa、10〜300秒間程度， 加熱乾燥則可採用50〜120°C、10〜2,000秒間程度。 第l(al)、（a2)圖為基板1與感光性組成物層2之截面 圖，顯示於基板上分別塗佈負型感光性樹脂組成物及正型 感光性樹脂組成物並進行乾燥後之狀態（濕潤膜已成為感 光性組成物層之狀態）。 (曝光步驟） 接著，對一部分之感光性組成物層進行曝光。曝光宜 透過預定圖案之光罩進行。照射之光可列舉如可見光；紫 外線；遠紫外線；KrF準分子雷射、ArF準分子雷射、？2準 分子雷射、Kr2準分子雷射、KrAr準分子雷射及Ar2準分子 雷射等之準分子雷射；X射線；以及電子線等。以波長 100〜600nm之電磁波為宜，且更宜為在300〜500nm之範圍内 具有分布之光線，尤宜為i線(365nm)、h線(405nm)、g線 (436nm) ° 第l(bl)圖係一顯示曝光步驟之截面圖，該曝光步驟如 下：使光4透過預定圖案之光罩3而照射到基板1上之已依需 要而乾燥後的負型感光性組成物層2，光4僅穿透刻在上述 201232178 光罩3之預定圖案部分而到達基板丨上之負型感光性組成物 層2 ’而僅有曝光部分5感光而硬化。未受光照射之未曝光 部分6則處於上述負型感光性組成物之狀態，顯示出鹼可溶 性。 此外’第l(b2)圖係截面圖，顯示使用正型感光性樹脂 組成物時之曝光步驟。在此狀況下，光已到達正型感光性 組成物層2 ’曝光部分5藉光反應而成為鹼可溶性。未受照 射之未曝光部分6則呈上述正型感光性組成物之狀態，顯示 出耐鹼顯像性。 照射裝置可使用習知之超高壓水銀燈或深紫外線燈 (deep UV lamp)等。曝光量宜為hiooomj/cm2之範圍，更 宜為10~200mJ/cm2。若曝光量過低，在負型感光性組成物 的情況下’曝光部分5之硬化不充分，於其後之顯像過程中 有溶解或剝離之虞。另一方面，在正型感光性組成物之情 況下，則曝光部分之鹼溶解性不充分，有產生顯像殘渣之 虞。若曝光量過高，則不論是在負型感光性組成物或正型 感光性組成物的情況下，均有無法獲得高解像度之傾向。 在曝光後顯像前，特別是使用樹脂組成物(NA)或正型 感光性樹脂組成物時，為了促進反應，宜進行感光性組成 物層之加熱處理。加熱溫度則採用50〜140°C、10〜2,000秒 程度。此係一般稱為PEB(Post Exposure Bake)之處理。該 PEB係一種加熱處理，且係用以使曝光所產生之酸在樹脂 組成物(NA)或正型感光性樹脂組成物所形成之感光性組成 物層中擴散而施行的處理。 59 201232178 (顯像步驟） 曝光步驟後藉顯像液進行顯像，在使用負型感光性樹 脂組成物時，去除感光性組成物層之未曝光部分6,在使用 正型感光性樹脂組成物時，則是去除感光性組成物層之曝 光部分5。舉例來說，顯像液可使用含有氫氧化鉀等之鹼金 屬氫氧化物、碳酸鉀等之鹼金屬碳酸鹽、胺類、醇胺類以 及第4級敍鹽等之驗類的驗性水溶液。 顯像時間（與顯像液接觸之時間）宜為5〜180秒。此外， 顯像方法可為液態顯影法（liquid development)、浸潰法、喷 淋法等中之任一者，顯像後進行高壓水洗及流水洗淨，以 壓縮空氣或壓縮氮使其風乾，可藉此去除基材上之水分。 藉由如前述般於曝光步驟後使用顯像液進行顯像，在 使用負型感光性樹脂組成物時，第l(bl)圖所示基板〖上之感 光性組成物層的未曝光部分6被去除，可獲得如第i(ci)圖所 示截面圖般之結構，即基板丨與該基板上由曝光部分5所構 成之隔壁8的結構。此外，使用正型感光性樹脂組成物時， 第l(b2)圖所示基板丨上之感光性組成物層的曝光部分$被去 除，可獲得基板1與該基板上由未曝光部分6所構成之隔壁8 的結構。此外，隔壁8與基板1所包圍之部分係顯示藉由注 入墨水專而形成墨水層（即像素）之點（dot)7的部分。 於本發明之隔壁中，藉由使用上述本發明之負型感光 性樹脂組成物，在以顯像液去除感光性組成物層之上述未 曝光部分6之時，由於感光性組成物層之曝光部分5(隔壁8) 與基板1保持著充分之密著狀態，顯像液不會侵人兩者之界 201232178 面，因此隔壁8不會從基板1部分地剝離，結果可形成高解 像度之圖案。此外’在使用上述本發明之正型感光性樹脂 組成物的情況下，賴像液去除感紐組成物層之上述曝 光部分5時，由於感光性組成物層之未曝光部分6(隔壁8)與 基板1保持著充分之密著狀態’顯像液不會侵入兩者之界 面，因此隔壁8不會從基板1部分地制離，結果可形成高解 像度之圖案。 此外，用於形成隔壁之負型感光性樹脂組成物含有撥 墨劑時，第l(cl)圖所示隔壁8之上部表面層會形成撥墨劑不 均勻存在之層（未圖示）。隔壁形成所用之正型感光性樹脂組 成物含有撥墨劑時，第l(c2)圖所示隔壁8之上部表面層會形 成撥墨劑不均勻存在之層（未圖示）。該撥墨劑不均勻存在之 層係如下形成者：隔壁形成步驟剛開始時均勻溶解於感光 性樹脂組成物之撥墨劑因撥墨劑所具有之特性，在乾燥步 驟中隨著有機溶劑（D)從濕潤膜之揮發除去而往感光性組 成物層之上方遷移，因曝光而被固定在層上方之表面。 (後焙步驟） 接著’宜加熱基材1上之隔壁8。加熱方法可列舉如： 使隔壁8與基材1 一起以加熱板、烘箱等之加熱裝置進行加 熱處理（宜於15〇〜250°C下進行5〜90分鐘）之方法。藉由該加 熱處理，基材1上之隔壁8充分硬化’隔壁8與基材1所包圍 之點7的形狀亦會更為固定化。此外’該加熱處理之溫度更 宜在18(TC以上。若加熱溫度過低，因隔壁8之硬化不充分， 無法獲得充分之耐藥品性，之後，例如在喷墨塗佈步驟中 61 201232178 將墨水注入點7時，會有隔壁8因該墨水所含之溶劑而膨潤 或是墨水滲出之虞。另一方面，若加熱溫度過高，則會有 隔壁8發生熱分解之虞。 本發明之隔壁藉由使用上述本發明之感光性樹脂組成 物而改善隔壁之顯像密著性。同時，藉著調整該感光性樹 脂組成物中上述微粒子（C)之摻合量，於上述後焙步驟中， 亦可賦予隔壁8對熱之形狀安定性。藉此，只要在改善隔壁 之顯像密著性之同時一併抑制熱流(thermal flow)發生，結 果是可形成高解像度之圖案。 本發明之感光性樹脂組成物如前述般可形成高解像度 之圖案，可適宜用於形成隔壁之寬度平均在ΙΟΟμηι以下（更 宜50μηι以下）之圖案。特別是可形成15μηι以下之圖案。此 外，可適宜用於隣接之隔壁（黑矩陣）間的距離(點之寬度）平 均在1，000μηι以下（更宜500μιτι以下）之圖案。再者，可適宜 用於形成隔壁（黑矩陣）之高度平均在〇.〇5〜50μπι(更宜 0.2〜ΙΟμηι)的圖案。 1個開口部之體積宜為500〜3,000,ΟΟΟμηι3，更宜為 1,500〜1，500,000μηι3，且以3,000〜500,000μηι3 尤佳。若開口 部（點）之體積過小，則使用喷墨法時難以使墨水蚤充填至所 欲之點内。另一方面，若點之體積過大，則所充填之墨水 難以均勻填充於點内。 又，光學元件中隔壁與像素之尺寸會依光學元件之種 類而異。例如，4211寸電視之像素面積大致為75,000μηι2，32 0寸電視之像素面積大致為30,000μηι2。渡色器之膜厚大致上 62 201232178 為1〜3μηι，有機EL之膜厚大致上為0.1〜1 。若考慮到此等 事項，則開口部之體積範圍會成為上述之 500〜3,000,000μιη3 程度。 適用上述本發明之隔壁的光學元件，可具體列舉如濾 色器、有機EL元件等。以下，就此等光學元件中本發明之 隔壁的適用予以說明。 [濾色器] 本發明之濾色器係-種在基板上具有多數像素及位在 鄰接像素間之隔壁的濾、色器，其特徵在於前述隔壁係以上 述本發明之隔壁顧者。此外，於本發明H器中，隔 壁且為光學濃度為2〜7程度之黑矩陣。 如則述，本發明之濾'色器可於基板上形成隔壁(例如, ^ )後’藉由喷墨法或核等之—般方法，將墨水: 佈於隔壁之開口部而形成像素，藉此來進行製造。 三角2之配列並未特別受限，可列舉如條型、馬賽克型 t及4像素配置型等之習知Is 56 201232178 The method of '1' refers to (1) the first (al) to (cl) diagram of the method of displaying the negative photosensitive resin composition, and (2) the pattern display positive photosensitive tree The first (a2) to (c2) drawings of the method for forming the partition of the ruthenium composition will be described. (The wet film formed of the photosensitive resin composition is formed on the substrate = coating step) First, the photosensitive resin composition is applied to a predetermined position on the substrate in order to form a wet film of the photosensitive resin composition on the substrate. (hereinafter referred to as "coating v"). The coating method may be, for example, a conventionally known method such as a spin coating method, a spray coating method, a slit coating method, a kneading method, a spin coating method, or a bar coating method. The film of the wet film of the photosensitive resin composition obtained by the coating step is different depending on the type of photosensitive resin to be used, the solid content concentration, and the method of forming the partition wall in the following months, but it is set in the obtained The height of the partition wall becomes the thickness of the slave value, for example, 2 to 2 times the aforementioned desired value. In the optical element obtained by the manufacturing method of the present invention, the gap of the most V is different depending on the type of the optical element, but it is preferably 2 5 〇 _ 'more suitable 〇 2~1 〇 _ Further, it is preferable that 〇.5~5μηι is used, and therefore, the sensitization of the itch is carried out, and the coating of the finished product is carried out in such a manner that the height of the finally obtained partition wall is described. (Drying/Pre-Pipe Step) The film H is adhered to the wet lake of the sensory resin composition formed on the substrate. The film 11 is dried, the organic solvent (9) is volatilized, and the shape is less. Composition layer. When the residual material of the new tree contains a low boiling point compound other than the solvent (D), it will be removed together with the organic solvent (D). When volatilization of the organic solvent (D) contained in the photosensitive resin composition is carried out, it is preferred to carry out vacuum drying or heat drying. Further, in order to prevent the photosensitive composition layer from being uneven in appearance and to efficiently dry it, it is preferred to use vacuum drying and heat drying in combination. Although it varies depending on the type of each component and the blending ratio, vacuum drying is preferably carried out at a temperature of 500 to 10 Pa and 10 to 300 seconds, and heating and drying may be carried out at a temperature of 50 to 120 ° C for 10 to 2,000 seconds. The first (a) and (a2) are cross-sectional views of the substrate 1 and the photosensitive composition layer 2, and the negative photosensitive resin composition and the positive photosensitive resin composition are applied to the substrate and dried. The state (the state in which the wet film has become the photosensitive composition layer). (Exposure Step) Next, a part of the photosensitive composition layer is exposed. Exposure should be carried out through a reticle of a predetermined pattern. The light to be irradiated may be, for example, visible light; ultraviolet rays; far ultraviolet rays; KrF excimer laser, ArF excimer laser, ? 2 excimer lasers such as quasi-molecular lasers, Kr2 excimer lasers, KrAr excimer lasers, and Ar2 excimer lasers; X-rays; and electron lines. It is preferably an electromagnetic wave having a wavelength of 100 to 600 nm, and more preferably a light having a distribution in the range of 300 to 500 nm, particularly preferably i-line (365 nm), h-line (405 nm), g-line (436 nm) ° l ( Bl) shows a cross-sectional view of the exposure step, the exposure step is as follows: the light 4 is transmitted through the mask 3 of the predetermined pattern to the negative photosensitive composition layer 2 which has been dried as needed after the substrate 1 is dried. The light 4 penetrates only the predetermined pattern portion of the mask 32 of the above 201232178 to reach the negative photosensitive composition layer 2' on the substrate, and only the exposed portion 5 is photosensitive and hardened. The unexposed portion 6 which is not exposed to light is in the state of the above-mentioned negative photosensitive composition, and exhibits alkali solubility. Further, the 'l2' (b2) drawing is a cross-sectional view showing an exposure step when a positive photosensitive resin composition is used. In this case, the light has reached the positive photosensitive composition layer 2'. The exposed portion 5 is alkali-soluble by the light reaction. The unexposed portion 6 which is not irradiated is in the state of the above-mentioned positive photosensitive composition, and exhibits alkali-resistant developability. As the irradiation device, a conventional ultrahigh pressure mercury lamp or a deep ultraviolet lamp or the like can be used. The exposure amount is preferably in the range of hiooomj/cm2, more preferably 10 to 200 mJ/cm2. If the amount of exposure is too low, the hardening of the exposed portion 5 in the case of the negative photosensitive composition is insufficient, and there is dissolution or peeling during the subsequent development. On the other hand, in the case of the positive photosensitive composition, the alkali solubility of the exposed portion is insufficient, and there is a possibility that a developing residue is generated. When the amount of exposure is too high, there is a tendency that high resolution cannot be obtained in the case of a negative photosensitive composition or a positive photosensitive composition. Before the development after exposure, in particular, when a resin composition (NA) or a positive photosensitive resin composition is used, in order to promote the reaction, heat treatment of the photosensitive composition layer is preferably carried out. The heating temperature is 50 to 140 ° C for 10 to 2,000 seconds. This system is generally referred to as PEB (Post Exposure Bake) processing. The PEB is a heat treatment and is a treatment for diffusing an acid generated by exposure in a photosensitive composition layer formed of a resin composition (NA) or a positive photosensitive resin composition. 59 201232178 (development step) After the exposure step, development is performed by a developing solution, and when a negative photosensitive resin composition is used, the unexposed portion 6 of the photosensitive composition layer is removed, and a positive photosensitive resin composition is used. At this time, the exposed portion 5 of the photosensitive composition layer is removed. For example, an aqueous test solution containing an alkali metal hydroxide such as potassium hydroxide or an alkali metal carbonate such as potassium carbonate, an amine, an alcohol amine, or a fourth-order salt can be used as the developer. . The development time (time to contact with the developing solution) is preferably 5 to 180 seconds. In addition, the developing method may be any one of a liquid development method, a dipping method, a shower method, and the like, and after performing development, high-pressure water washing and running water washing are performed, and compressed air or compressed nitrogen is used to air dry. This can remove moisture from the substrate. By using the developing liquid after the exposure step as described above, when the negative photosensitive resin composition is used, the unexposed portion 6 of the photosensitive composition layer on the substrate shown in the first (bl) figure is used. After being removed, a structure like the cross-sectional view shown in the i-th (ci) figure, that is, the structure of the substrate 丨 and the partition wall 8 composed of the exposed portion 5 on the substrate can be obtained. Further, when a positive photosensitive resin composition is used, the exposed portion $ of the photosensitive composition layer on the substrate 第 shown in the first (b2) is removed, and the substrate 1 and the unexposed portion 6 on the substrate are obtained. The structure of the partition wall 8 is constructed. Further, a portion surrounded by the partition wall 8 and the substrate 1 is a portion showing a dot 7 of an ink layer (i.e., a pixel) by ink injection. In the partition wall of the present invention, by using the negative photosensitive resin composition of the present invention, when the unexposed portion 6 of the photosensitive composition layer is removed by the developing solution, the exposure of the photosensitive composition layer is caused. The portion 5 (the partition wall 8) is sufficiently adhered to the substrate 1, and the developing liquid does not invade the boundary of the two sides 201232178. Therefore, the partition wall 8 is not partially peeled off from the substrate 1, and as a result, a high resolution pattern can be formed. . Further, in the case where the above-mentioned positive photosensitive resin composition of the present invention is used, when the exposed portion 5 of the photosensitive composition layer is removed by the imaging liquid, the unexposed portion 6 of the photosensitive composition layer (partition 8) The substrate 1 is kept in a sufficiently close state. The developing solution does not intrude into the interface between the two. Therefore, the partition wall 8 is not partially separated from the substrate 1, and as a result, a high resolution pattern can be formed. Further, when the negative photosensitive resin composition for forming the partition wall contains the ink repellency agent, the upper surface layer of the partition wall 8 shown in Fig. 1(cl) forms a layer (not shown) in which the ink repellency is unevenly formed. When the positive photosensitive resin composition for forming the partition wall contains the ink-repellent agent, the upper surface layer of the partition wall 8 shown in the first (c2) diagram forms a layer (not shown) in which the ink-repellent agent is unevenly distributed. The layer in which the ink-repellent is unevenly formed is formed by the fact that the ink-repellent uniformly dissolved in the photosensitive resin composition at the beginning of the partition forming step is characterized by the ink-repellent agent, and the organic solvent is used in the drying step ( D) Removal from the volatilization of the wet film and migration to the upper side of the photosensitive composition layer, and fixation to the surface above the layer by exposure. (Post-baking step) Next, the partition wall 8 on the substrate 1 is preferably heated. The heating method may be a method in which the partition wall 8 and the substrate 1 are heat-treated by a heating means such as a hot plate or an oven (preferably at 15 to 250 ° C for 5 to 90 minutes). By this heat treatment, the partition wall 8 on the substrate 1 is sufficiently hardened. The shape of the point 7 surrounded by the partition wall 8 and the substrate 1 is also more fixed. Further, the temperature of the heat treatment is more preferably 18 (TC or more. If the heating temperature is too low, the hardening of the partition wall 8 is insufficient, and sufficient chemical resistance cannot be obtained, and thereafter, for example, in the inkjet coating step, 61 201232178 When the ink is injected into the dot 7, the partition wall 8 is swollen by the solvent contained in the ink or the ink is bleed out. On the other hand, if the heating temperature is too high, the partition wall 8 is thermally decomposed. The partition wall is improved in the image-forming adhesiveness of the partition wall by using the photosensitive resin composition of the present invention, and the amount of the fine particles (C) blended in the photosensitive resin composition is adjusted in the post-baking step. In addition, the shape of the heat of the partition wall 8 can be imparted to the partition wall 8. This improves the thermal conductivity of the partition wall while suppressing the occurrence of thermal flow, and as a result, a high resolution pattern can be formed. The photosensitive resin composition can form a high resolution pattern as described above, and can be suitably used to form a pattern in which the width of the partition walls is on the average of ΙΟΟμηι or less (more preferably 50 μm or less). In addition, it is suitable for the pattern of the distance between the adjacent partition walls (black matrix) (the width of the dots) on the average of 1,000 μm or less (more preferably 500 μm τι or less). Further, it can be suitably used for forming the partition wall. The height of the (black matrix) is an average of 〜. 5~50μπι (more preferably 0.2~ΙΟμηι). The volume of one opening is preferably 500~3,000, ΟΟΟμηι3, more preferably 1,500~1,500,000μηι3, and 3,000 to 500,000 μm 3 is particularly preferable. If the volume of the opening (dot) is too small, it is difficult to fill the ink cartridge to the desired point by using the ink jet method. On the other hand, if the volume of the dot is too large, the filled ink It is difficult to fill the dots evenly. Moreover, the size of the partitions and pixels in the optical component varies depending on the type of optical component. For example, the pixel area of a 4211-inch TV is approximately 75,000 μm 2 , and the pixel area of a 32-inch TV is approximately 30,000 μm 2 The film thickness of the color filter is approximately 62 to 32,32,322, and the film thickness of the organic EL is approximately 0.1 to 1. If these matters are considered, the volume of the opening will become the upper limit. The optical element of the partition wall of the present invention is specifically a color filter, an organic EL element, etc. Hereinafter, the application of the partition wall of the present invention to these optical elements will be described. The color filter of the present invention is a filter and a color filter having a plurality of pixels on a substrate and a partition wall between adjacent pixels, wherein the partition wall is a partition wall of the present invention. In the invention, in the H device, the partition wall is a black matrix having an optical density of about 2 to 7. As described above, the filter color filter of the present invention can form a partition wall (for example, ^) on the substrate by 'inkjet method or core In the usual method, the ink is formed by arranging the ink on the opening of the partition wall to form a pixel. The arrangement of the triangle 2 is not particularly limited, and examples such as a strip type, a mosaic type t, and a 4-pixel configuration type are exemplified.

合此像素形狀來進行。 列。上述隔壁之形成係J 基材上之3$;1"本發月之據色器時，上述隔壁形成後，1 水前，亦隔壁(例如黑矩陣)所區隔出的區域(點)内投入‘ 水化處理了以下::去對露出在點内之基材表面施行親‘ 臭==例如=溶液之洗淨處理、臟淨處理- 锻處理等Γ理；刀子切處理、電暈放電處理以及氧‘ (喷墨法之像素形成) 63 201232178 為了使像素以喷墨法形成在基材上以黑矩陣區隔出之 區域，首先，因應上述需要，以噴墨法對進行過親墨水化 處理步驟後之mR(紅）、b(藍）、g(綠)之3色墨水。墨水 之注入可使用—般祕喷墨狀墨裝置，錢常方法同 樣地進仃。此種‘5水注人洲n裝置並未特別受限， 但可❹利用下述方法之喷《置：使帶電之墨水連續喷 射並藉磁％予以控制之方法；使用壓電元件而間歇性地喷 射墨水之方法；m墨水加熱並·其發㈣間歇地 進行喷射之方法等之各種方法。 上此夕卜’於本說明書中，「墨水」係乾燥（或硬化）後具有 諸士光于電性機能之液體材料或固體材料(但固體材料時 為其溶液或分散液）的總稱，並不限於習知使用之著色材 料。此外，就注入上述墨水而形成之「像素」而言，亦同 樣地用於表示：隔賴區隔之各自具有光學、電性機能之 區段。 於此’用於形成慮色器之像素的墨水主要含有著色成 分、結合劑樹脂成分及溶#卜著色成分宜使用具優異财熱 性及耐光性等之顏料及染料。結合劑樹脂成分宜為透明且 具優異耐紐之樹脂，可列舉如叫酸細旨、三聚氮胺樹 脂及胺曱動旨樹料。水性墨水含有水及依需要而定之水 溶性有機料1作為溶劑，含有水溶‘_脂或水分散性樹脂 結合劑作為樹脂成分’且可依需要而含有各種助劑。此外， 油性墨水則含有有機溶劑作為溶劑，含有可溶於有機溶劑 之樹脂作為結合難脂成分，且依需要斜有各種助劑。This pixel shape is used in combination. Column. The partition wall is formed on the J substrate by 3$; 1" in the coloring device of the present month, after the partition is formed, in the area (dot) where the water is separated from the partition (for example, the black matrix) Invested in 'hydration treatment':: to perform the treatment of the surface of the substrate exposed in the point of the odor == for example = solution cleaning, dirty treatment - forging treatment; knife cutting, corona discharge Treatment and Oxygen' (Pixel Formation by Ink Jet Method) 63 201232178 In order to form a pixel on the substrate by an inkjet method in a region separated by a black matrix region, first, in order to meet the above requirements, the inkjet method is used to perform ink separation. Three color inks of mR (red), b (blue), and g (green) after the treatment step. Injecting ink can use the same inkjet ink device as usual, and the money is often used in the same way. This type of '5 water injection tank' is not particularly limited, but it can be sprayed by the following method: a method of continuously ejecting charged ink and controlling it by magnetic %; intermittent use of piezoelectric elements A method of ejecting ink, a method of heating m ink, and a method of ejecting (four) intermittently. In this specification, "ink" is a general term for a liquid material or a solid material (but a solution or dispersion thereof in the case of a solid material) which has a light energy after being dried (or hardened), and It is not limited to the colored materials conventionally used. Further, the "pixel" formed by injecting the above-described ink is similarly used to indicate a section in which each of the spacers has optical and electrical functions. Here, the ink for forming the pixel of the color filter mainly contains a coloring component, a binder resin component, and a coloring component, and a pigment and a dye having excellent heat and light resistance are preferably used. The binder resin component is preferably a resin which is transparent and excellent in resistance, and may be exemplified by an acid-based composition, a triazide resin, and an amine-based tree. The aqueous ink contains water and, if necessary, the water-soluble organic material 1 as a solvent, and contains a water-soluble fat or water-dispersible resin binder as a resin component, and may contain various auxiliary agents as needed. Further, the oil-based ink contains an organic solvent as a solvent, and contains a resin soluble in an organic solvent as a combination of a hard-to-lip component, and various additives are added as needed.

(S 64 201232178 —另外，於嘴墨法中，以上述喷墨裝置對點注入墨水後， 且依而要而進行乾燥、加熱硬化或紫外線硬化。 (光钮刻法之像素形成） 以光邮彳法使料形成於基材上 以黑矩陣區隔出之區 j時’與㈣黑料之製造方法同樣地，先依需要而洗淨 4』述基板後’將彩色墨水組成物塗佈於基板上。塗佈方法 2前述黑輯之製造方法中时佈方法相同 。之後，亦與 刖述同樣地_倾步驟、曝光步驟、顯像步驟、及後培 步驟’藉此於點内形成彩色層。使該步驟分別就R(紅）、 B(藍）、G(綠)之3色墨水分別進行(共3次），完成像素。 墨水主要含有著色成分、結合劑樹脂成分及溶劑，可 為水性墨水及油性墨水中之任一者。著色成分以具優異耐 熱性、耐光性等之顏料及/或染料為宜。結合劑樹脂成分以 透明且具優異耐熱性之樹脂為宜 ，可列舉如丙烯酸樹脂、 二聚氛胺樹脂及胺甲酸酯樹脂等。水性墨水含有水及依需 要而定之水溶性有機溶劑作為溶劑，且含有水溶性樹脂或 水分散性樹脂結合劑作為樹脂成分。此外，油性墨水則含 有有機溶劑作為溶劑，且含有可溶於有機溶劑之樹脂作為 結合劑樹脂成分。 如此以喷墨法、光蝕刻法等而使像素形成於基材上以 隔壁（例如黑矩陣）區隔出之領域後，依需要而形成保護膜 層。保護膜層宜在提升表面平坦性之目的與阻斷源自隔壁 或像素部分之墨水的溶出物到達液晶層的目的下形成。形 «1 成保護膜層時’宜於事前去除隔壁之撥墨性。若不去除撥 65 201232178 墨性，將會排拒面塗(over coat)用塗佈液，無法獲得均勻膜 厚而不理想。去除隔壁之撥墨性之方法可列舉如電漿灰化 處理或光灰化處理等。 為了使利用本發明之濾色器而製造出之液晶面板高品 位化，更可依需要而在隔壁（例如黑矩陣）上形成光間p = (photospacer) 〇 [有機EL元件] 本發明之有機EL元件係一種在基板上具有多數像素及 位在鄰接像素間之隔壁的有機EL元件，其特徵在於.二 隔壁係以上述本發明之隔壁形成者。 κ 奉發明之有機EL元件可如 , 彳衣13·。盲先，使 用賤鍍法等，在玻璃基板等之透明基板上形纽〇等之透明 電極，並依需要而將透明電極蝕刻成所欲之圖案。接著 與據色器之情況相同，在基板上形成隔壁(例如黑矩了 ’ ^隔壁(黑_)之開口部使时墨法，依序塗佈作為墨水之 電洞輪送材料溶液及發光材料溶液並予 扒〜冰’形成電涧 輸适層及發光層。更使用蒸鑛法等，形成㈣〇电/门 忐榇主 小成鋁專之電極而形 战像素，藉此製得有機EL元件。另，上述 / 限於嗔墨法，亦可以光㈣法進彳卜 ，、形成並不 [有機EL照明元件之製造] J興有機EL表示元件之製造相同地進行製造。“ 可使發出紅、、綠、藍等各色之發光體以喷墨方式來^層 將前述發光體分別塗佈在平面上。 實施例 66 201232178 以下，基於實施例來說明本發明，但本發明並不受其 等所侷限。另，只要無特別陳明，「份」、「％」分別指質量 份及質量％。 茲將以下各例中使用之化合物的縮寫顯示如下。 [1] 用於製造撥墨劑之化合物 (單體） C6FMA : CH2=C(CH3)COOCH2CH2(CF2)6F MAA :曱基丙烯酸 2-HEMA : 2-羥乙基甲基丙烯酸酯 PME400 : Blemmer PME-400(日本油月旨社製，CH2 = C(CH3)COO(CH2CH20)kCH3 :式中之k表示分子間之平均 值，k之值約為9。） GMA :曱基丙烯酸環氧丙酯 AOI : Karenz AOI(商品名，昭和電工社製，2-丙烯醯 氧基乙基異氰酸酯） (聚合起始劑、催化劑、聚合抑制劑） V-65 : V-65(和光純藥社製，2, 2’-偶氮雙(2, 4-二曱基 戊腈)） DBTDL :二丁基錫二月桂酸酯 TBQ 第三丁基對苯醌 (溶劑） MEK : 2-丁酮 [2] 感光性樹脂組成物成分 (結合劑樹脂(A)) 67 201232178 (樹脂組成物(NR)用）(S 64 201232178 - In addition, in the ink jet method, ink is injected into a dot by the above-described ink jet apparatus, and drying, heat curing, or ultraviolet curing is performed as desired. (Pixel formation by light button engraving) When the crucible is formed on the substrate and the region j separated by the black matrix region is the same as in the method for producing the black material, the substrate is washed as needed, and then the color ink composition is applied. On the substrate, the coating method is the same as in the manufacturing method of the black series. Then, similarly to the description, the tilting step, the exposing step, the developing step, and the post-culturing step are used to form a color in the dot. In this step, the three colors of R (red), B (blue), and G (green) are respectively carried out (three times in total) to complete the pixel. The ink mainly contains a coloring component, a binder resin component, and a solvent. It is preferably one of an aqueous ink and an oily ink. The coloring component is preferably a pigment and/or a dye having excellent heat resistance and light resistance, etc. The resin component of the binder is preferably a resin which is transparent and has excellent heat resistance, and is exemplified. Such as acrylic resin, diamine tree A lipid, a urethane resin, etc. The aqueous ink contains water and a water-soluble organic solvent as a solvent, and contains a water-soluble resin or a water-dispersible resin binder as a resin component. In addition, the oil-based ink contains an organic solvent. a solvent and a resin soluble in an organic solvent as a binder resin component. After the pixels are formed on the substrate by an inkjet method, a photolithography method, or the like, and are partitioned by a partition wall (for example, a black matrix), A protective film layer is formed as needed. The protective film layer is preferably formed for the purpose of improving surface flatness and blocking the elution of ink from the partition wall or the pixel portion to reach the liquid crystal layer. Remove the ink repellency of the next wall beforehand. If the ink is not removed, the coating liquid for overcoating will be rejected, and the uniform film thickness cannot be obtained. For example, plasma ashing treatment, light ashing treatment, etc. In order to make the liquid crystal panel manufactured by the color filter of the present invention high-grade, it is possible to be in the partition wall as needed ( For example, an organic EL element of the present invention is an organic EL element having a plurality of pixels on a substrate and a partition wall between adjacent pixels, and is characterized in that: The second partition wall is formed by the above-described partition wall of the present invention. κ The organic EL element of the invention can be, for example, 彳衣13·. Blind first, using a ruthenium plating method, etc., on a transparent substrate such as a glass substrate, a transparent shape such as a ruthenium or the like Electrode, and etching the transparent electrode into a desired pattern as needed. Then, as in the case of the color filter, a partition wall is formed on the substrate (for example, an opening portion of the black matrix '^ partition (black_) is used to make the ink method, The hole pumping material solution and the luminescent material solution as ink are sequentially coated and applied to form an electric transmission layer and a light-emitting layer. Further, using a steaming method or the like, an organic EL element is formed by forming a (four) 〇 electric/gate 小 main small aluminum electrode and forming a pixel. In addition, the above-mentioned / limited to the ink-jet method can also be carried out by the light (four) method, and the formation is not [manufacture of an organic EL illumination element]. "The illuminants of various colors such as red, green, and blue may be applied by an inkjet method to apply the illuminants to the plane. Embodiment 66 201232178 Hereinafter, the present invention will be described based on examples, but the present invention It is not subject to its limitations. In addition, as long as there is no special statement, "parts" and "%" refer to the mass and mass% respectively. The abbreviations of the compounds used in the following examples are shown below. [1] Compound for the production of ink-repellent (monomer) C6FMA : CH2=C(CH3)COOCH2CH2(CF2)6F MAA: 2-methacrylic acid 2-HEMA: 2-hydroxyethyl methacrylate PME400 : Blemmer PME -400 (manufactured by Nippon Oil Co., Ltd., CH2 = C(CH3)COO(CH2CH20)kCH3: where k represents the average value between molecules, and k has a value of about 9.) GMA: glycidyl methacrylate AOI : Karenz AOI (trade name, manufactured by Showa Denko, 2-propenyl methoxyethyl isocyanate) (polymerization initiator, catalyst, polymerization inhibitor) V-65 : V-65 (made by Wako Pure Chemical Industries, 2 , 2'-azobis(2,4-dimercapto valeronitrile)) DBTDL: dibutyltin dilaurate TBQ tert-butyl-p-benzoquinone (solvent) MEK : 2-butanone [2] photosensitive resin Composition component (binder resin (A)) 67 201232178 (for resin composition (NR))

EX1010 . EX-101 〇(商品名，Nagase ChemteXEX1010 . EX-101 〇 (trade name, Nagase ChemteX

Corporation製，於通式(2)所示環氧樹脂導入乙烯性雙鍵與 酸性基之樹脂溶液，固體成分：60質量。/〇，質量平均分子 量：3,020) ZCR1569H:KAYARAD ZCR-1569H(商品名，日本化 藥社製，於通式（1)所示具有聯苯骨架之環氧樹脂中導入乙 烯性雙鍵與酸性基之樹脂溶液；固體成分：7〇質量％，質 量平均分子量：4,710) ZCR1642H : ZCR-1642H(商品名，日本化藥社製，於 通式（1)所示具有聯笨骨架之環氧樹脂中導入乙烯性雙鍵與 酸性基之樹脂溶液；固體成分：60質量％，質量平均分子 量：7,900) ZAR2001H . ZAR-2001Η(商品名，於雙紛a型環氧樹月t 中導入乙烯性雙鍵與酸性基之樹脂溶液；固體成分：65質 量％，質量平均分子量：10,000) (樹脂組成物（N A)及正型感光性樹脂組成物用鹼可溶性樹 脂） EP4〇20G: EP4020G(旭有機材工業社製，甲齡齡搭清 漆樹脂；質量平均分子量：11，570) (樹脂組成物(NA)用交聯性樹脂） NW100LM : Nikalac NW-100LM(三和化學社製，六甲 氧基羥甲基三聚氰胺） (光活性劑(B)) 201232178 OXE02 : ΟΧΕ02(商品名，Ciba Specialty Chemicals社 製，乙酮l-[9-乙基-6-(2-曱基苯曱醯基）-9H-肼甲醯基-3-基乙醯肟）(通式（4)中，R21及R22為甲基，R23為乙 基，R24、R26及R27為氫原子且R25為2-甲基苯曱醯基之化 合物） NCI831 : ADEKAARKLS NCI-831(商品名，ADEKA社 製，肪酯類） TFE 三吖畊（TFE triazine) : TFE-三吖 >#(2-[2-(呋喃-2- 基）乙烯基]-4, 6-雙（三氣曱基)-3_三σ丫 π井） 4ΝΤ-250 : 4ΝΤ-250(東洋合成社製，2, 3, 4, 4，-四羥基 二苯基酮與6-二偶氮-5, 6-二氫-5-側氧-1-萘磺酸之酯化物） (微粒子（C)之分散液） NPCST:有機二氧化矽溶膠(商品名，曰產化學工業社 製，ξ電位：-15mV，平均粒徑：24nm，分散介質：乙二醇 單丙醚，固體成分：3〇質量％) IPAST :有機二氧化矽溶膠（商品名，曰產化學工業社 製’ ξ電位：-28mV，平均粒徑：45nm，分散介質：2_丙醇， 固體成分：30質量〇/0) ,PMAST:有機二氧化石夕溶膠（商品名，曰產化學工業社 ，ξ電位，平均粒徑：26nm，分散介質：pGMEA , 固體成分：30質量％) <ξ電位之測定〉 藉由各微粒子分散介質，將各分散液稀釋至50,000 °並以大塚電子社製ξ電位測定系統之ELSZseries來測定ξ 69 201232178 電位。使用以下各溶劑之物性值，依Huckel之數式計算出ξ 電位。此外，一併顯示各分散介質之SP值。 乙二醇單丙醚：折射率1.413、黏度2.04(mPa · s)、介 電率 10.92、SP 值 ll.l(cal/cm3)W2 2-丙醇：折射率1.378、黏度l.96(mPa . s)、介電率 18.30、 SP值 11.6(cal/cm3)l/2 PGMEA :折射率1.400、黏度l.i〇(mpa . s)、介電率 8.30、 SP值8.7(cal/cm3)l/2 (著色劑(E)) CB :碳黑分散液（平均2次粒徑120nm，分散介質： PGMEA ’碳黑：20質量％，胺價為18mgKOH/g之聚胺曱酸 酯系高分子分散劑：5質量％) 混合有機顏料：C.I.pigment blue 15 : 6、C.I.pigment red 254、C.I.pigment yellow 139與高分子分散劑之 10 : 5 : 5 : 5 的混合物，固體成分：25質量％，分散介質：PGMEA) (界面活性劑） BYK306 : BYK-306(商品名，BYK Japan KK製，聚醚 改質聚二甲基矽氧烷之12質量％溶液（二曱苯/單苯基二醇 (7/2)) (自由基交聯劑） BPEF : NK Ester A-BPEF(新中村化學工業社製，9, 9-雙[4-(2-丙烯醯氧基乙氧基）苯基第） UX5002D : KAYADAD UX-5002D(日本化藥社製，胺 甲酸酯丙烯酸酯）A resin solution of an ethylenic double bond and an acidic group is introduced into the epoxy resin of the formula (2), and the solid content is 60 mass. /〇, mass average molecular weight: 3,020) ZCR1569H: KAYARAD ZCR-1569H (trade name, manufactured by Nippon Kayaku Co., Ltd., introducing an ethylenic double bond and an acidic group into an epoxy resin having a biphenyl skeleton represented by the formula (1) Resin solution; solid content: 7〇 mass%, mass average molecular weight: 4,710) ZCR1642H: ZCR-1642H (trade name, manufactured by Nippon Kayaku Co., Ltd., in epoxy resin having a stupid skeleton represented by the general formula (1) A resin solution in which an ethylenic double bond and an acidic group are introduced; solid content: 60% by mass, mass average molecular weight: 7,900) ZAR2001H. ZAR-2001Η (trade name, introduction of an ethylenic double bond in a double-type epoxy tree t Resin solution with acidic group; solid content: 65 mass%, mass average molecular weight: 10,000) (resin composition (NA) and alkali-soluble resin for positive photosensitive resin composition) EP4〇20G: EP4020G (Asahi Organic Industry Manufactured, a aging varnish resin for ageing; mass average molecular weight: 11,570) (crosslinkable resin for resin composition (NA)) NW100LM : Nikalac NW-100LM (manufactured by Sanwa Chemical Co., Ltd., hexamethoxymethylol) Melamine) (photoactive Agent (B)) 201232178 OXE02 : ΟΧΕ02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd., ethyl ketone 1-[9-ethyl-6-(2-mercaptophenyl)-9H-indenyl-3 - hydrazide) (in the formula (4), R21 and R22 are a methyl group, R23 is an ethyl group, and R24, R26 and R27 are a hydrogen atom and R25 is a 2-methylphenylhydrazine group) NCI831: ADEKAARKLS NCI-831 (trade name, manufactured by ADEKA, fat esters) TFE triazine (TFE triazine) : TFE-三吖>#(2-[2-(furan-2-yl)vinyl]-4 , 6-double (three gas sulfhydryl)-3_three σ丫π well) 4ΝΤ-250 : 4ΝΤ-250 (made by Toyo Seisakusho Co., Ltd., 2, 3, 4, 4,-tetrahydroxydiphenyl ketone and 6- (Ester ester of diazo-5,6-dihydro-5-oxan-1-naphthalenesulfonic acid) (dispersion of fine particles (C)) NPCST: organic cerium oxide sol (trade name, 曰产化学工业社System, zeta potential: -15 mV, average particle diameter: 24 nm, dispersion medium: ethylene glycol monopropyl ether, solid content: 3 〇 mass%) IPAST: organic cerium oxide sol (trade name, manufactured by 化学Chemical Industry Co., Ltd.) Zeta potential: -28 mV, average particle size: 45 nm, dispersion medium: 2-propanol, solid content: 30 mass 〇/0) , PMAST: Organic sulphur dioxide sol (product name, 曰 化学 化学, ξ potential, average particle size: 26 nm, dispersion medium: pGMEA, solid content: 30% by mass) < Determination of zeta potential 〉 Each of the dispersions was diluted to 50,000 ° by each of the fine particle dispersion medium, and the potential of ξ 69 201232178 was measured by ELSZseries of a zeta potential measurement system manufactured by Otsuka Electronics Co., Ltd. The zeta potential was calculated according to the Huckel equation using the physical property values of the following solvents. Further, the SP value of each dispersion medium is shown together. Ethylene glycol monopropyl ether: refractive index 1.413, viscosity 2.04 (mPa · s), dielectric constant 10.92, SP value ll.l (cal/cm3) W2 2-propanol: refractive index 1.378, viscosity 1.96 (mPa s), dielectric ratio 18.30, SP value 11.6 (cal/cm3) l/2 PGMEA: refractive index 1.400, viscosity li〇 (mpa. s), dielectric constant 8.30, SP value 8.7 (cal/cm3) l/ 2 (colorant (E)) CB: carbon black dispersion (average secondary particle diameter 120 nm, dispersion medium: PGMEA 'carbon black: 20% by mass, amine valence 18 mg KOH/g of polyamine phthalate polymer dispersion Agent: 5% by mass) Mixed organic pigment: CIpigment blue 15 : 6, CIpigment red 254, CIpigment yellow 139 and polymer dispersant 10 : 5 : 5 : 5 mixture, solid content: 25% by mass, dispersed Medium: PGMEA) (surfactant) BYK306: BYK-306 (trade name, manufactured by BYK Japan KK, 12% by mass solution of polyether modified polydimethyl siloxane) (diphenylbenzene/monophenyl diol ( 7/2)) (free radical crosslinking agent) BPEF : NK Ester A-BPEF (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., 9, 9-bis[4-(2-acryloxyethoxy)phenyl) UX5002D : KAYADAD UX-5002D (manufactured by Nippon Kasei Co., Ltd., amine Formate acrylate)

70 201232178 (熱交聯劑） NC3000H : NC-3000-H(商品名，日本化藥社製，具有 通式（1)所示聯苯骨架之環氧樹脂） (矽烷偶合劑） KBM403 :商品名，信越化學社製，3-環氧丙氧基丙基 三甲氧基矽烷 (填酸化合物） PA :磷酸與單曱基丙烯醯氧基乙基磷酸酯、二曱基丙 烯醯氧基乙基磷酸酯之2: 1(質量比）混合物 (溶劑） PGMEA:丙二醇1-單曱醚2-乙酸酯 <撥墨劑之合成> [撥墨劑(E-1)之合成] 於設有攪拌機之内容積1L的高壓釜中饋入 MEK(420.0g) 、 C6FMA(99.0g) 、 MAA(9.0g) 、 PME400(63.0g)、GMA(9.0g)及聚合起始劑V-65(0.3g)，於氮 氣環境下一邊攪拌一邊於50°C下使其聚合24小時，合成出 粗共聚物。對所得粗共聚物之溶液加入己烧，進行再沉殿 純化後，真空乾燥而獲得撥墨劑(E-l)(162.3g)。 撥墨劑(E-1)之數平均分子量為64,700，質量平均分子 量為94,020，氟原子含量為31.4質量％，酸價為 32.6mgKOH/g。 [撥墨劑(E-2)之合成] · ό 於設有攪拌機之内容積1L的高壓釜中饋入 71 201232178 MEK(420.0g)、c6FMA(81.0g)、2-HEMA(36_0g)、 PME400(54.0g)、MAA(9.0g)及聚合起始劑V-65(l.lg)，於氮 氣環境下一邊攪拌一邊於50〇C下使其聚合24小時，獲得聚 合物之溶液。所得聚合物之數平均分子量為34,200，質量 平均分子量為63,900。 於設有攪拌機之内容積1L的高壓釜中饋入上述聚合物 之溶液（500.0g)、AOI(32.6g)、DBTDL(0.13g)、TBQ(1.6g) 及MEK(17.1g)，一邊進行攪拌一邊於4〇°c下使其反應24小 時。於該反應溶液中加入己烷進行再沉澱純化後，真空乾 燥而獲得撥墨劑(E-2)( 165.0g)。撥墨劑(E-2)之數平均分子 量為34,900,質量平均分子量為69,300,氟原子含量為21.1 質量％，乙稀性雙鍵含量為l_26xl〇-3mol/g，酸價為 26.8mgKOH/g。 此外，上述所得撥墨劑之各種物性係以下述方法測定 者。 <分子量> 數平均分子量（Μη)及質量平均分子量（Mw)係利用膠 透層析法，將聚苯乙烯用作標準物質來測定。 <氟原子含量> 聚合物中之氟原子含量係由聚合反應之饋入值算出。 <乙烯性雙鍵含量> 聚合物中之乙烯性雙鍵含量係以1，4-貳三氟曱基苯作 為標準物質，並以hNMR測定而算出。 · 201232178 酸價係由原料單體之摻合比例算出之理論值。 [實施例1] 結合劑樹脂(A)使用EX1010(以固體成分計係28 4%)， 光活性劑(B)使用〇XE02(以固體成分計係6 1〇/〇)，微粒子(c) 之分散液使用NPCST(以固體成分計係20.3%)，著色劑（e) 使用CB(以固體成分計係32_5。/〇，且固體成分亦包含聚胺甲 酸酯系高分子分散劑）’撥墨劑使用（E-2)(以固體成分計係 0.6%)，自由基交聯劑使用A-BPEF(以固體成分計係8.1 〇/〇)， 熱交聯劑使用NC3000(以固體成分計係4.1〇/〇)，混合PGMEA 使固體成分濃度成為15質量°/〇 ’而製出樹脂組成物(NR)。 作為玻璃基板，使用低壓水銀燈將AN100(旭硝子社製) 照射2分鐘紫外線。測定基板之水接觸角，結果為5。以下。 使用旋轉器’在上述玻璃基板上塗佈感光性樹脂組成 物後，於加熱板上以100°C使其乾燥2分鐘，形成膜厚2.0μηι 之感光性組成物層。接著’使用超高壓水銀燈，使曝光量 以i線(365nm)基準計係50mJ/cm2之光透過光罩而照射至感 光性組成物層，進行曝光。另，光罩係透光部與遮光部交 互排列成線狀之設計，透光部為5μπι、ΙΟμιη、15μηι，遮光 部為 ΙΟΟμιη。 接著’使用顯像機進行顯像。顯像液使用〇.4%ΤΜΑΗ (氫氧化四曱基錄）水溶液。之後，以水沖洗未曝光部分，使 其乾燥。接著’於烘箱中，於220°C下將玻璃板加熱(後焙)30 分鐘’藉此製得已形成隔壁之實施例丨的玻璃基板樣本（1)。 除了將光罩變更成遮光部為150μιη><400μηι且透光部為 73 201232178 20μηι之格子狀圖案者以外，與上述相同地製得已形成感光 性組成物硬化物之實施例1的玻璃基板樣本(2)。所形成之開 口部容積為120pL。再者，除了不使用光罩地進行曝光以 外’與上述者相同地製得實施例1的玻璃基板樣本(3)，其已 形成有感光性组成物之硬化物。 [實施例2〜4、6] 除了將各成分之摻合變更成如表2所示以外，與實施例 1相同地製造實施例2、實施例3、實施例6之樹脂組成物(NR) 以及實施例4之樹脂組成物(NA)。 使用所得之負型感光性樹脂組成物，將光蝕刻步驟及 製膜條件變更成如表2所示以外，與實施例1同樣地製得實 施例2〜4之玻璃基板樣本（1)，其等已形成有由感光性組成物 之硬化物所構成的隔壁。另外，PEB係指在曝光後且在顯 像前進行加熱之步驟。 此外，使用實施例3、實施例4及實施例6所得負型感光 性樹脂組成物，與實施例1同樣地製造出玻璃基板樣本(2)、 (3)。 [實施例5] 除了將各成分之掺合變更成如表2所示以外’與實施例 1同樣地製造出實施例5之樹脂組成物(PQ)。此外，使用所 得之正型感光性樹脂組成物，並使用採透光部與遮光部交 互排列成線狀之設計且遮光部為5μηι、1〇μηι、15μηι透光部 為ΙΟΟμπι之光·罩，將光蝕刻步驟及製膜條件變更成如表2所 示以外，與實施例1同樣地製出實施例5之玻璃基板樣本 201232178 (1)，其已形成有由感光性組成物之硬化物所構成的隔壁。 [比較例1、2] 除了將各成分之摻合變更成如表2所示以外’與貫施例 1同樣地製出比較例1及比較例2之樹脂組成物(NR) ° 使用所得之負型感光性樹脂組成物’除了將光触刻步 驟及製膜條件變更成如表2所示以外，與實施例1同樣地製 出比較例1、2之玻璃基板樣本（1)、（2)、（3) ’其等已形成有 由感光性組成物之硬化物所構成的隔壁。 [評估方法及評估結果] 以下述說明之方法，使用上述各實施例及比較例所製 出之玻璃基板樣本（1)，評估解像度與熱流。此外，使用上70 201232178 (Hot cross-linking agent) NC3000H : NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy resin having a biphenyl skeleton represented by the general formula (1)) (decane coupling agent) KBM403 : trade name , 3-Goxypropyloxypropyltrimethoxydecane (acid-filled compound), PA: Phosphoric acid with monomercaptopropenyloxyethyl phosphate, dimercaptopropenyloxyethyl phosphate Ester 2: 1 (mass ratio) mixture (solvent) PGMEA: propylene glycol 1-monodecyl ether 2-acetate <synthesis of ink-repellent> [Synthesis of ink-repellent (E-1)] The autoclave with a volume of 1 L of the blender was fed with MEK (420.0 g), C6FMA (99.0 g), MAA (9.0 g), PME400 (63.0 g), GMA (9.0 g) and polymerization initiator V-65 (0.3). g) The mixture was polymerized at 50 ° C for 24 hours while stirring under a nitrogen atmosphere to synthesize a crude copolymer. The solution of the obtained crude copolymer was added to a hexane, and after purification, it was vacuum-dried to obtain an ink-repellent (E-1) (162.3 g). The ink-repellent (E-1) had an average molecular weight of 64,700, a mass average molecular weight of 94,020, a fluorine atom content of 31.4% by mass, and an acid value of 32.6 mgKOH/g. [Synthesis of Ink Remover (E-2)] · 馈 In the autoclave with a 1L internal volume of the mixer, feed 71 201232178 MEK (420.0g), c6FMA (81.0g), 2-HEMA (36_0g), PME400 (54.0 g), MAA (9.0 g) and a polymerization initiator V-65 (1.gg) were polymerized at 50 ° C for 24 hours while stirring under a nitrogen atmosphere to obtain a polymer solution. The obtained polymer had a number average molecular weight of 34,200 and a mass average molecular weight of 63,900. The polymer solution (500.0 g), AOI (32.6 g), DBTDL (0.13 g), TBQ (1.6 g), and MEK (17.1 g) were fed to an autoclave having a 1 L internal volume of a stirrer. The mixture was reacted at 4 ° C for 24 hours while stirring. After hexane was added to the reaction solution for reprecipitation purification, it was vacuum dried to obtain an ink-repellent (E-2) (165.0 g). The ink-repellent (E-2) has an average molecular weight of 34,900, a mass average molecular weight of 69,300, a fluorine atom content of 21.1% by mass, a vinyl double bond content of l_26xl〇-3 mol/g, and an acid value of 26.8 mgKOH/g. . Further, various physical properties of the above-mentioned obtained ink repellent are measured by the following methods. <Molecular weight> The number average molecular weight (?n) and the mass average molecular weight (Mw) were measured by gel permeation chromatography using polystyrene as a standard substance. <Fluorine atom content> The fluorine atom content in the polymer is calculated from the feed value of the polymerization reaction. <Ethylene double bond content> The content of the ethylenic double bond in the polymer was calculated by NMR measurement using 1,4-fluorene trifluoromethane benzene as a standard material. · 201232178 Acid value is the theoretical value calculated from the blending ratio of raw material monomers. [Example 1] The binder resin (A) used EX1010 (28% by weight of the solid content), and the photoactive agent (B) used 〇XE02 (based on a solid content of 6 1 〇/〇), and the fine particles (c) The dispersion was NPCST (20.3% based on solid content), and the colorant (e) was CB (based on a solid content of 32_5./〇, and the solid component also contained a polyurethane-based polymer dispersant). The ink-repellent used (E-2) (0.6% based on solid content), the free radical crosslinking agent used A-BPEF (based on solid content 8.1 〇/〇), and the thermal crosslinking agent used NC3000 (solid content) In the case of 4.1 〇/〇), the PGMEA was mixed to have a solid content concentration of 15% by mass/〇' to prepare a resin composition (NR). As a glass substrate, AN100 (manufactured by Asahi Glass Co., Ltd.) was irradiated with ultraviolet rays for 2 minutes using a low-pressure mercury lamp. The water contact angle of the substrate was measured and found to be 5. the following. The photosensitive resin composition was applied onto the glass substrate by using a rotator, and then dried on a hot plate at 100 ° C for 2 minutes to form a photosensitive composition layer having a film thickness of 2.0 μm. Then, using an ultrahigh pressure mercury lamp, light having an exposure amount of 50 mJ/cm 2 on the basis of i line (365 nm) was passed through a photomask to be irradiated onto the photosensitive composition layer, and exposure was performed. Further, the reticle is designed such that the light-transmitting portion and the light-shielding portion are arranged in line shape, and the light-transmitting portion is 5 μm, ΙΟμιη, 15 μm, and the light-shielding portion is ΙΟΟμηη. Then 'developed using a video camera. For the developing solution, an aqueous solution of 4.4% 曱 (tetramethylene hydroxide) was used. Thereafter, the unexposed portion was rinsed with water to dry it. Then, the glass plate was heated (post-baked) at 220 ° C for 30 minutes in an oven to thereby prepare a glass substrate sample (1) of the example of which the partition walls were formed. The glass substrate of Example 1 in which the photosensitive composition cured product was formed was obtained in the same manner as described above except that the mask was changed to a lattice pattern in which the light-shielding portion was 150 μm><400 μm and the light-transmitting portion was 73 201232178 20 μηι. Sample (2). The opening volume formed was 120 pL. Further, the glass substrate sample (3) of Example 1 was produced in the same manner as the above except that the exposure was carried out without using a photomask, and a cured product of the photosensitive composition was formed. [Examples 2 to 4, 6] The resin compositions (NR) of Example 2, Example 3, and Example 6 were produced in the same manner as in Example 1 except that the blending of the respective components was changed to that shown in Table 2. And the resin composition (NA) of Example 4. The glass substrate sample (1) of Examples 2 to 4 was obtained in the same manner as in Example 1 except that the photo-etching step and the film forming conditions were changed to those shown in Table 2 using the obtained negative photosensitive resin composition. A partition wall composed of a cured product of the photosensitive composition has been formed. Further, PEB means a step of heating after exposure and before development. Further, using the negative photosensitive resin compositions obtained in Example 3, Example 4, and Example 6, glass substrate samples (2) and (3) were produced in the same manner as in Example 1. [Example 5] The resin composition (PQ) of Example 5 was produced in the same manner as in Example 1 except that the blending of the respective components was changed to that shown in Table 2. Further, the obtained positive-type photosensitive resin composition is used, and a design in which the light-transmitting portion and the light-shielding portion are alternately arranged in a line shape is used, and the light-shielding portion is a light-shielding portion of 5 μm, 1 〇μηι, and 15 μηι, and the light-transmitting portion is ΙΟΟμπι. The glass substrate sample 201232178 (1) of Example 5 was produced in the same manner as in Example 1 except that the photo-etching step and the film-forming conditions were changed as shown in Table 2. The cured product of the photosensitive composition was formed. The next door. [Comparative Examples 1 and 2] The resin composition (NR) of Comparative Example 1 and Comparative Example 2 was produced in the same manner as in Example 1 except that the blending of the respective components was changed to that shown in Table 2. In the negative photosensitive resin composition, the glass substrate samples (1) and (2) of Comparative Examples 1 and 2 were produced in the same manner as in Example 1 except that the photo-touching step and the film-forming conditions were changed as shown in Table 2. ), (3) 'The partition walls formed of the cured product of the photosensitive composition have been formed. [Evaluation method and evaluation result] The glass substrate sample (1) prepared in each of the above Examples and Comparative Examples was evaluated by the method described below to evaluate the resolution and heat flow. In addition, use

P 述實施例1、3、4、6及比較例1、2所製出之玻璃基板樣本 ‘ （2) ’以喷墨法注入墨水，進行墨水層均勻性之評估。又， 使用上述實施例1、3、4、6及比較例1、2所製出之玻璃基 板樣本(3)來評估撥墨性。茲將評估結果示於表2。 <顯像密著性> 於玻璃基板樣本（1)中’殘留有5μηι之線者評估為「〇」 (良好），5、10、Μμηι之全部的線剝離而未殘留者評估為「χ」 (不可）。 <熱流> 使用顯像後且在後焙前及後焙後之玻璃基板樣本G)， 以SEM觀察線之截面形狀並進行比較。隔壁在後培前後發 生熱流者評估為「X」（不可）’發生若干熱流者評估為「〇」 (良好），完全未發生熱流者評估為「◎」（優良）。 75 201232178 <撥液性> 透過測定玻璃基板樣本(3)之硬化物表面之PGME A接 觸角來評估撥液性。 接觸角係指在固體與液體接觸之點上，對液體表面之 接線與固體表面所構成的角，且以包含液體之側的角度來 予以定義。因此，接觸角越大，意指硬化物之撥液性越佳。 <噴墨後之墨水層均勻性> 使用攪拌器將液狀Epoxy ME-562(日本peln0x社 製）(6.25g)、硬化劑HV-562(日本Pelnox社製）(6.25g)及己二 酸二乙酯（12.5g)及丙二酸二乙酯（25.Og)攪拌混合1小時，製 出墨水。 使用喷墨法’以實施例1、4、6及比較例卜2為約120pL、 實施例3為約180pL之量將上述製出之墨水塗佈至玻璃基板 樣本(2)之隔壁間開口部。 [墨水層隔壁邊際膜厚（Mave)] 使用超深度形狀測定顯微鏡VK-8500(Keyence Corp0rati〇nN製）測定各試驗用光學元件3處之像素（即墨水 層）中之隔壁邊際部分的膜厚。測定處就各像素而言，如第 2(a)及(b)圖所示，在各邊之中央部隔壁邊際的4點，即第2(b) 圖所示之yl〜y4處’令其等之平均值為該像素中之墨水層隔 壁邊際之膜厚(M)，更令測得之3處像素平均值為墨水層隔 壁邊際膜厚(Mave)。 [墨水層中央膜厚(Nave)] 使用超》未度形狀測定顯微鏡VK-8500(Keyence 76 201232178P. The glass substrate samples prepared in Examples 1, 3, 4, and 6 and Comparative Examples 1 and 2 were injected with ink by an inkjet method to evaluate the uniformity of the ink layer. Further, the ink repellency was evaluated using the glass substrate samples (3) prepared in the above Examples 1, 3, 4, and 6 and Comparative Examples 1 and 2. The results of the evaluation are shown in Table 2. <Dynamic adhesion> In the glass substrate sample (1), the line of 5 μηι remained as "〇" (good), and the line of 5, 10, Μμηι was peeled off, and the remaining one was evaluated as " χ" (not available). <Heat Flow> Using the glass substrate sample G) after development and before and after the post-baking, the cross-sectional shape of the line was observed by SEM and compared. Those who developed heat flow in the next wall before and after the training were evaluated as "X" (not available). Those who experienced some heat flow were evaluated as "〇" (good), and those who did not have heat flow at all were evaluated as "◎" (good). 75 201232178 <liquid repellency> The liquid repellency was evaluated by measuring the PGME A contact angle of the surface of the cured product of the glass substrate sample (3). The contact angle is the angle formed by the connection of the liquid surface to the solid surface at the point where the solid is in contact with the liquid, and is defined by the angle of the side containing the liquid. Therefore, the larger the contact angle, the better the liquid repellency of the cured product. <Ink Layer Uniformity After Inkjet> Liquid Epoxy ME-562 (manufactured by Nippon Pelox Co., Ltd.) (6.25 g) and hardener HV-562 (manufactured by Pelnox, Japan) (6.25 g) and Diethyl diacrylate (12.5 g) and diethyl malonate (25.Og) were stirred and mixed for 1 hour to prepare an ink. The ink produced by the inkjet method was applied to the opening between the partition walls of the glass substrate sample (2) in an amount of about 120 pL in Examples 1, 4, and 6 and Comparative Example 2, and about 180 pL in Example 3. . [Ink layer barrier film thickness (Mave)] The film thickness of the partition wall portion in the pixel (i.e., ink layer) of each test optical element 3 was measured using an ultra-depth shape measuring microscope VK-8500 (manufactured by Keyence Corp.). . For each pixel, as shown in Fig. 2(a) and (b), at the 4th point of the partition wall at the center of each side, that is, at the yl~y4 shown in the second (b) diagram. The average value of the film is the film thickness (M) of the edge of the ink layer in the pixel, and the average value of the three pixels measured is the edge film thickness (Mave) of the ink layer. [Ink Layer Central Film Thickness (Nave)] Using Ultra" Unshaped Shape Measuring Microscope VK-8500 (Keyence 76 201232178

Corp0rati〇nN製）測定各試纖 層）中之中央膜厚。測定處就1學元件3處之像素（即墨水 所示，令制定值為該像^像素而言，如第2(a)及(b)圖 位置之膜厚(N)。更令测得K層中央即第2(b)圖所示x 邊際膜厚(Nave)。 ~像素之平均值為墨水層隔壁 [墨水層均勻性] 以下述計算式算出上述所得之Mave及勤e值。 Mave/Navex 100 將]\^”心&”><1〇〇為8〇以上 、 上者砰估為「◎」（優良），60 以上且小於80者評估為Γ〇 μ 」（良好），小於60者評估為Γχ (不可）。 」 77 201232178 表2 資旆例 比較例 1 2 3 4 5 6 1 2 光 性 m 成 物 固 體 成 分 摻 比 率 質 量 % 结合劑樹脂 ㈧ ΕΧ1 010 28.4 47.9 31.0 ZCR1569H 21.5 ZCR1642H 21.7 ZAR2001 Η 21.5 EP4020G 49.3 70.8 NW1 OOLM 21.1 光活性劑 (Β) ΟΧΕ02 6.1 4.6 3.7 10.3 6.6 NCI831 3.5 TF£ triazine 7.0 4NT-250 17.7 微®子 (C) NPCST 20.3 1 8.6 IPAST 1 8.4 21.1 10.6 19.1 PMAST 22.1 著色劑 {〇) C巳 32.5 46.0 46.0 34.2 35.4 混合有梅顔科 46.4 撥墨劑 (E-1) 1.4 (E-2) 0.6 0.3 0.5 0.7 0.4 界面活性劑 BYK306 0.3 0.9 交聯劑 (自由基/熱） A-BPEF 8.1 UX5002D 6.1 6.2 6.1 NC3000H 4.1 3.1 3.1 6.8 4.4 偶合劑 KBM403 3.0 磷駿化合物 PA 0.3 合計（貢量％) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 感光性樹脂绍成物固體成分灌度 (質量％) 15.0 1 5.0 1 5.0 15.0 15.0 15.0 15.0 15.0 先蛀刻 腸光量（mJ/cm2) 50 50 50 100 200 20 50 50 PEB 無 無 無 100Ό (2分） 無 無 無 無 製膜 條件 技璃基板樣本 (1)〜（3)膜厚（Km) 2 1 3 2 2 2 2 2 玻璃基板橒本（2〉 容《(ρϋ 120 180 120 120 120 120 評估 解像度 Ο Ο Ο Ο Ο Ο X X 熱流 © 〇 X Ο PGMEA接觸角Γ ) 48 45 50 46 47 46 犋墨後之墨水層均勻性 @ @ @ X 〇 78 201232178 從表2可知’微粒子(C)使用ξ電位在_5mV以下之NPCST 或IPAST之實施例卜6在顯像後殘留有5μπι之線，解像力良 好另方面，未使用微粒子（C)之比較例1及微粒子（〇)使 用ξ電位超過-5mV之較大PMAST的比較例2在顯像後連 15μπι之線亦剝離，隔壁之顯像密著性不佳，解像力不良。 再者，微粒子（c)使用ξ電位在_5mV以下iNpcsT或 IPAST，且微粒子(〇在感光性樹脂組成物固體成分中之比 率佔13%以上之實施例1〜4、6則是熱流獲得抑制。因此， 更摻合撥墨劑之實施例1、3、4、6在喷墨後之墨水層均勻 性。另一方面，未使用微粒子（C)之比較例丨在噴墨後之墨 水層均勻性不佳。此外’微粒子(c)使用ξ電位超過_5mV之 PM AST的比較例2即使微粒子(C)之摻合量高達22丨％，仍發 生右干之熱流，相較於貫施例1、3、4、6，噴墨後之墨水 層平坦性較差。 產業上之可利用性 本發明之隔壁形成用感光性樹脂組成物因隔壁之顯像 密著性獲得改善’可藉由使用該組成物來形成高解像度之 圖案。藉由此種隔壁，可提供高解像度之濾色器及有機EL 元件。 此外，於此援引已在2010年12月20日提申之日本專利 申請案第2010-283376號之說明書、申請專利範圍、摘要及 圖式之全部内容，並作為本發明說明書之揭示内容予以納 入0 79 201232178 I：圖式簡單說明3 第1 (a 1)至（c 2)圖係模式性地顯示使用本發明之感光性 樹脂組成物來形成隔壁之步驟者。 第2(a)、（b)圖係顯示墨水層厚度之測定位置者，該墨 水層厚度係用於評估：使用本發明之感光性樹脂組成物所 形成之喷墨用隔壁來形成像素時的墨水層均勻性。 【主要元件符號說明】 1...基板 7.··點(dot) 2...感光性組成物層 8...隔壁 3...光罩 11...墨水層 4...光 X...墨水層厚測定處(中央） 5...曝光部分 y 1〜y4...墨水層厚測定處(隔 6...未曝光部分 壁邊際） * 80The central film thickness in each of the test fiber layers was measured by Corp0rati〇nN. The measurement is performed on the pixel of the 3 element of the element (that is, the ink indicates that the value is the pixel of the image, such as the film thickness (N) of the position of the second (a) and (b). The center of the K layer is the x-thickness film thickness (Nave) shown in Fig. 2(b). The average value of the pixels is the ink layer partition [ink layer uniformity]. The Mave and the e-values obtained above are calculated by the following calculation formula. /Navex 100 will be \\""heart&"><1〇〇 is 8〇 or higher, the upper one is estimated to be “◎” (excellent), and those above 60 and less than 80 are evaluated as Γ〇μ” (good) ), less than 60 is evaluated as Γχ (not). ” 77 201232178 Table 2 旆 Example Comparative Example 1 2 3 4 5 6 1 2 Photoelectric m Solid Content Increasing Ratio Mass % Binding Resin (8) ΕΧ1 010 28.4 47.9 31.0 ZCR1569H 21.5 ZCR1642H 21.7 ZAR2001 Η 21.5 EP4020G 49.3 70.8 NW1 OOLM 21.1 Photoactive agent (Β) ΟΧΕ02 6.1 4.6 3.7 10.3 6.6 NCI831 3.5 TF£ triazine 7.0 4NT-250 17.7 Micro® sub (C) NPCST 20.3 1 8.6 IPAST 1 8.4 21.1 10.6 19.1 PMAST 22.1 Colorant {〇) C巳32.5 46.0 46.0 34.2 35.4 Mixed meyanaceae 46.4 Toner (E-1) 1.4 (E-2) 0.6 0.3 0.5 0.7 0.4 Surfactant BYK306 0.3 0.9 Crosslinker (free radical /Heat) A-BPEF 8.1 UX5002D 6.1 6.2 6.1 NC3000H 4.1 3.1 3.1 6.8 4.4 Coupling agent KBM403 3.0 Phosphorus compound PA 0.3 Total (% by weight) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Photosensitive resin (% by mass) 15.0 1 5.0 1 5.0 15.0 15.0 15.0 15.0 15.0 First engraving light amount (mJ/cm2) 50 50 50 100 200 20 50 50 PEB No or no 100 Ό (2 points) No or no film-forming conditions Substrate sample (1)~(3) Film thickness (Km) 2 1 3 2 2 2 2 2 Glass substrate 橒 (2> 容"(ρϋ 120 180 120 120 120 120 Evaluation of resolution Ο Ο Ο Ο Ο XX XX heat flow © 〇X Ο PGMEA contact angle Γ ) 48 45 50 46 47 46 Uniformity of ink layer after @ ink @ @ @ X 〇78 201232178 It can be seen from Table 2 that 'microparticles (C) use NPCST or IPAST with a zeta potential below _5mV In Example 6, after the development, a line of 5 μm was left, and the resolution was good. On the other hand, Comparative Example 1 in which the fine particles (C) and the fine particles (〇) were used in Comparative Example 2 in which the larger PMAST having a zeta potential of more than -5 mV was used. The line of 15μπι is also peeled off, and the image adhesion of the next wall is poor, and the resolution is poor. Further, the fine particles (c) use iNpcsT or IPAST having a zeta potential of _5 mV or less, and the fine particles (the ratio of 〇 in the solid content of the photosensitive resin composition accounts for 13% or more, and Examples 1 to 4 and 6 are heat flow suppression). Therefore, the ink layer uniformity of the inkjet inks of Examples 1, 3, 4, and 6 which are more blended with the ink-repellent agent. On the other hand, the comparative example of the fine particles (C) is not used, and the ink layer after the inkjet is used. In addition, the 'microparticles (c) use the PM AST with a zeta potential exceeding _5 mV. Even if the amount of the fine particles (C) is as high as 22%, the right-hand heat flow still occurs, compared to the continuous application. In the first, third, fourth, and sixth embodiments, the ink layer after inkjet is inferior in flatness. INDUSTRIAL APPLICABILITY The photosensitive resin composition for forming a partition wall of the present invention is improved in image display adhesion by the partition wall. The composition is used to form a high-resolution pattern. This partition wall provides a high-resolution color filter and an organic EL element. Further, the Japanese patent application filed on December 20, 2010 is hereby incorporated by reference. The specification, patent application scope, abstract and schema of No. 2010-283376 The entire contents are incorporated in the disclosure of the present specification. 0 79 201232178 I: BRIEF DESCRIPTION OF THE DRAWINGS 3 The first (a 1) to (c 2) diagrams schematically show the use of the photosensitive resin composition of the present invention. The steps of forming the partition walls are shown in Fig. 2(a) and (b) showing the measurement position of the thickness of the ink layer for evaluating the ink jet formed by using the photosensitive resin composition of the present invention. The ink layer uniformity when forming a pixel by the partition wall. [Description of main component symbols] 1...substrate 7.·dot 2...photosensitive composition layer 8...partition wall 3...light Cover 11... Ink layer 4... Light X... Ink layer thickness measurement (center) 5... Exposure part y 1 to y4... Ink layer thickness measurement (separation 6...not exposed Partial wall margin) * 80

Claims (1)

201232178 七、申請專利範園： L —種感光性樹脂組成物，係用於以光蝕刻法形成隔壁 者’該隔壁係配設成使基板上區隔出用以形成像素之多 數區塊的形狀；且，該感光性樹脂組成物含有： 結合劑樹脂(A); 光活性劑（B); 微粒子(C)，其係以有機溶劑作為分散介質之分散 液中的微粒子（C) ’且該分散液中之微粒子(C)以電泳光 散射法所測定之ξ電位為-100〜-5mV ;及 龜 % 有機溶劑(D)’其至少一部分為前述分散液之有機 溶齊|J。 如申凊專利範圍第i項之感光性樹脂組成物，其中前述 微粒子(C)之平均粒徑為5〜1〇〇nm。 .如：睛專利範圍第丨或2項之感光性樹脂組成物，其中前 W微粒子(C)之分散液中的分散介質係具有至少)個羥 基且SP值為9〜20(cal/cmy2之有機溶劑。 = 至3項# —項之感練樹脂組成 5. ’其中前賴粒子(〇為二氧切微粒子。 二請專利範圍第4項之感紐樹脂組成物 ，其中前述 —虱化矽微粒子為膠體二氧化矽。 如申請專利範圍第！至5項中 物，甘丄 $ 項之感光性樹脂組成 ^中前述微粒子(C)之含量相對於組成物之總固體 3 s為3〜35質量0/〇 〇 如申請專利範圍第1至6項中 只—項之感光性樹脂組成 6 201232178 物，其更含有著色劑(E)。 8. 如申請專利範圍第7項之感光性樹脂組成物，其中前述 著色劑（E)係選自於由碳黑、鈦黑、黑色金屬氧化物顏 料、銀錫合金及有機顏料所構成群組中之至少1種物質。 9. 如申請專利範圍第1至8項中任一項之感光性樹脂組成 物，其中前述基板之隔壁形成面具有下述表面特性：其 與用於前述光蝕刻法之鹼性顯影液的親和性良好。 10. —種隔壁，係形成為使基板上區隔出用以形成像素之多 數區塊的形狀者，其特徵在於：該隔壁係使用如申請專 利範圍第1至9項中任一項之感光性樹脂組成物並以光 蝕刻法形成者。 11. 一種濾色器，係在基板上具有多數像素及位在鄰接像素 間之隔壁者，且該隔壁係如申請專利範圍第10項之隔 壁。 12. —種有機EL元件，係在基板上具有多數像素及位在鄰接 像素間之隔壁者，且該隔壁係如申請專利範圍第10項之 隔壁。 β 82201232178 VII. Application for Patent Park: L. A photosensitive resin composition for forming a partition by photolithography. The partition is arranged such that the substrate is partitioned to form a plurality of blocks of pixels. Further, the photosensitive resin composition contains: a binder resin (A); a photoactive agent (B); and a microparticle (C) which is a microparticle (C) in a dispersion of an organic solvent as a dispersion medium and The zeta potential of the fine particles (C) in the dispersion is -100 to -5 mV as measured by electrophoretic light scattering; and at least a part of the organic solvent (D) of the turtle is the organic solvent of the dispersion. The photosensitive resin composition of claim i, wherein the fine particles (C) have an average particle diameter of 5 to 1 〇〇 nm. For example, the photosensitive resin composition of the second or second aspect of the invention, wherein the dispersion medium in the dispersion of the front W fine particles (C) has at least one hydroxyl group and an SP value of 9 to 20 (cal/cmy2) Organic solvent. = to 3 items #--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- The microparticles are colloidal cerium oxide. The content of the above-mentioned microparticles (C) in the photosensitive resin composition of the kanji$ item is in the range of 3 to 35 of the total solids of the composition. Quality 0 / For example, the photosensitive resin composition of the first to sixth items of claims 1 to 6 is 201232178, which further contains a coloring agent (E). 8. The photosensitive resin composition of claim 7 And the coloring agent (E) is at least one selected from the group consisting of carbon black, titanium black, ferrous metal oxide pigment, silver tin alloy, and organic pigment. a photosensitive resin composition according to any one of items 1 to 8, wherein The partition wall forming surface of the substrate has surface characteristics which are excellent in affinity with the alkaline developing solution used in the photolithography method. 10. A partition wall is formed so as to partition the substrate to form a pixel. The shape of a plurality of blocks is characterized in that the partition wall is formed by photolithography using a photosensitive resin composition according to any one of claims 1 to 9. 11. A color filter There are a plurality of pixels on the substrate and a spacer between the adjacent pixels, and the partition wall is a partition wall of the tenth item of the patent application. 12. An organic EL element having a plurality of pixels on the substrate and adjacent pixels The next door is the next door, and the partition is next door to the 10th article of the patent application.
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