TW583506B - Preserving method for color resist - Google Patents

Preserving method for color resist Download PDF

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Publication number
TW583506B
TW583506B TW091119214A TW91119214A TW583506B TW 583506 B TW583506 B TW 583506B TW 091119214 A TW091119214 A TW 091119214A TW 91119214 A TW91119214 A TW 91119214A TW 583506 B TW583506 B TW 583506B
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Taiwan
Prior art keywords
acid
resin composition
photosensitive resin
colored photosensitive
pigment
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TW091119214A
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Chinese (zh)
Inventor
Koji Ichikawa
Koji Baba
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Sumitomo Chemical Co
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Priority claimed from JP2001297063A external-priority patent/JP2003107727A/en
Priority claimed from JP2001336141A external-priority patent/JP4139910B2/en
Application filed by Sumitomo Chemical Co filed Critical Sumitomo Chemical Co
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Publication of TW583506B publication Critical patent/TW583506B/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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • 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
    • G03F7/027—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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)

Abstract

A preserving method for color resist, preserving the color resist with (A) colorant, (B) binder polymer, (C) photopolymerization compound,(D) photopolymerization imitator, and (E) solvent over -6 DEG C and under 15 DEG C, or over -10 DEG C and under 30 DEG C with continuing shake the color resist. According to the preserving method, because of the quality of the preserved color resist has no change, and the gelatinization matters will not be formed. Therefore, the pattern forming condition the same as using the color resist after fabricating to form the coloration pattern is used, and then the same coloration pattern is formed.

Description

9927 pif 1 玖、發明說明： 發明領域 本發明係有關於著色感光樹脂組成物之保存方法。’ 習知枝術 著色感光樹脂組成物(color resist)係爲含有著色劑的感光 性樹脂組成物(resist)，並適於形成構成彩色瀘光片(c〇l〇r filter) 著色圖案的材料。此處彩色瀘光片1係爲用以將液晶顯示裝置 的顯示影像彩色化，並用以將固態攝像元件所攝像的影像彩色 化的光學元件(請參照第ΙΑ、1B圖）。著色圖案2例如是色像 素2R、2G、2B與黑色矩陣(black matrix)2BM等，且其構成爲 條紋狀（請參照第1A圖）或是馬賽克(mosaic)狀（請參照第1B 圖）。已知在著色感光性組成物係含有(A)著色劑、（B)高分子結 合劑、（C)光聚合性化合物、（D)光聚合引發劑與(E)溶劑，並已 知含有作爲(A)著色劑的顏料。於感光樹脂組成物中，（A)顏料 係在組成物中呈分散狀態，並且通常(B)高分子結合劑、（C)光 聚合性化合物與(D)光聚合引發劑係溶解於(E)溶劑中。著色感 光樹脂係塗佈於基板3上，除去(E)溶劑所得的著色感光層4係 可溶於鹼性水溶液中（第2A圖），藉由照射光線6(第2B圖）， 由（D)光聚合引發劑產生活性自由基或是酸，並由此活性自由基 或是酸使(C)光聚合性化合物聚合。由於此著色感光層在水溶液 中成爲不溶性，故此著色感光樹脂組成物係作爲負型光阻而作 爲形成著色圖案的材料(第2C圖）。由於在著色感光樹脂組成物 中含有(C)光聚合性化合物與(D)光聚合引發劑，長時間保存的 話則會由於光聚合性化合物的聚合而導致品質產生變化。因 此，彩色濾光片之製造法，係採用在每一次製造彩色濾光片時 9927 pif 1 製造必要量的著色感光樹脂組成物。 但是，如在每一次製造彩色濾光片時才製造著色感光樹脂 組成物，則必須配合彩色濾光片的製造計畫以製造著色感光樹 脂組成物，而且，由於一次之必要用量的製造量少，因而不利 於著色感光樹脂的生產性。 而且，爲了避免著色感光樹脂組成物的品質變化，在製造 後至彩色濾光片的製造的期間爲止，需儘可能的將之靜置，並 以乾冰等例如是冷卻至攝氏零下25度以保存。 但是，靜置並以乾冰等保存於冷卻狀態的著色感光樹脂組 成物，係具有溶液在短時間內產生膠化物的情形。 此處本發明者們經銳意檢討的結果，係硏究出含有(A)著 色劑、（B)高分子結合劑、（C)光聚合性化合物、（D)光聚合引發 劑與(E)溶劑的著色感光樹脂組成物如果保持在攝氏零下6度 以上攝氏15度以下的話，於長時間其相互間的品質不會導致 大的變化，並不會生成膠化物而能夠進行保存，然後能夠一次 大量的著色感光樹脂，進而能夠提升此著色感光樹脂組成物的 生產性，從而完成本發明。 而且，本發明者們係硏究出將(A)著色劑、（B)高分子結合 劑、（C)光聚合性化合物、（D)光聚合引發劑與(E)溶劑的著色感 光樹脂組成物，使其震動的保存在攝氏零下10度以上攝氏30 度以下的話，能夠抑制膠化物的生成，從而完成本發明。 發明槪要 本發明的目的係提供一種著色感光樹脂組成物的保存方 法，其特徵爲將含有(A)著色劑、（B)高分子結合劑、（C)光聚合 性化合物、（D)光聚合引發劑與(E)溶劑的著色感光樹脂組成物 9927 pif 1 保存在攝氏零下6度以上攝氏15度以下(下述之本發明第一實 施例）。 本發明的另一目的係提供一種著色感光樹脂組成物的保 存方法，其特徵爲將含有（A)著色劑、（B，)高分子結合劑、（C)光 聚合性化合物、（D)光聚合引發劑與（E)溶劑的著色感光樹脂組 成物使其震動的保存在攝氏零下度以上攝氏30度以下（下述 之本發明第二實施例）° 圖式之簡單說明 第1A圖至第1B圖所繪示爲彩色濾光片之一例的示意圖； 第2A圖至第2C圖所繪示爲著色圖案的製造步驟的示意 圖， 第3A圖至第3C圖所繪示爲著色圖案的製造步驟的示意 圖，以及 第4A圖至第4C圖所繪示爲著色圖案的製造步驟的示意 圖。 圖式之標示說明 1 :彩色濾光片 2、2,、2” ：著色圖案 3 :基板 4、4,、4” ：著色感光層 5 :光罩 6 :光線 41 :未照射區域 42 :照射區域 9927 pif 1 51 :玻璃板 52 :遮光層 53 :透光部 2B :藍色圖案 2BM :黑色矩陣 2G :綠色圖案 2R :紅色圖案 發明的實施例 以本發明之方法保存的著色感光樹脂組成物係包含(A)著 色劑、（B)高分子結合劑、（C)光聚合性化合物、（D)光聚合引發 劑與(E)溶劑。 (A)著色劑可以是有機物的有機著色劑，亦可以無機物的 無機著色劑，有機著色劑可以是顏料，亦可以是染料。而且， 著色劑亦可以是天然色素或是合成色素。無機著色劑亦可以是 金屬氧化物、金屬錯鹽、硫酸鋇的無機鹽(體質顏料)等的無機 顏。且在著色劑中，較佳爲採用有機著色劑，更佳爲使用有機 顏料。 具體的有機顏料以及無機顏料，例如是所舉的於彩色索引 (Color Index，The Society of Dyers and Colourists 出版）以顏料 (pigment)所分類的顏料。具體而言例如是所舉的c.I·顏料黃1、 C.I.顏料黃3、C.I·顏料黃12、C.I.顏料黃13、C.I·顏料黃14、 C.I.顏料黃15、C.I·顏料黃16、c·;[•顏料黃17、Cl顏料黃20、 C.I.顏料黃24、C.I.顏料黃31、C.I.顏料黃53、C.I·顏料黃83、 C.I·顔料黃86、C.I·顏料黃93、C.I.顏料黃109、C.I.顏料黃110、 C.I.顏料黃117、C.I.顏料黃125、C.I.顏料黃128、C.I.顏料黃 9927 pif 1 137、0·Ι·顏料黃 138、C.I·顏料黃 139、c.I·顏料黃 147、c.I.顏 料黃150、C.I·顏料黃153、C.I·顏料黃154、C.I·顏料黃166、 C.I·顏料黃173等黃色顏料， C.I·顏料橘13、C.I·顏料橘31、C.I.顏料橘36、C.I·顏料橘 38、C.I.顏料橘40、C.I.顏料橘42、C.I.顏料橘43、（：丄顏料橘 51、C.I.顏料橘55、C.I.顏料橘59、c.I·顏料橘6丨、c.I.顏料橘 64、C.I.顏料橘65、C.I.顏料橘71、·顏料橘等的橘色顏料， C.I.顏料紅9、C.I·顏料紅97、C.I·顏料紅1〇5、c.I·顏料紅 122、C.I.顏料紅 123、C.I·顏料紅 144、C_I·顏料紅 149、C_I·顏 料紅166、C.I.顏料紅168、C.I·顏料紅176、C.I.顏料紅177、 C.I·顏料紅180、C.I.顏料紅192、C.I·顏料紅215、C.I.顏料紅 216、C.I·顏料紅 224、C.I·顔料紅 242、C.I·顏料紅 254、C.I.顏 料紅264、C.I·顏料紅265等的紅色顏料， C.I·顏料藍 15、C_I·顔料藍 15 : 3、C.I·顏料藍 15 : 6、C.I. 顏料藍15 ·· 4、C.I·顏料藍15 : 6、C.I.顏料藍60等的藍色燃料， C.I·顏料紫1、C.I_顏料紫19、C.I.顏料紫23、C.I·顏料紫 29、C.I·顏料紫32、C.I·顏料紫36、C.I.顏料紫38等的紫色顏 料， C.I·顏料綠7、C.I·顏料綠36等的綠色顏料， C.I·顏料棕23、C.I·顏料棕25等的棕色顏料， C.I·顏料黑1、C.I·顏料黑7等的黑色顏料。此些有機顏料 以及無機顏料係可以個別單獨使用，亦可以兩種以上混合使 用。 有機顏料亦可以因應需要施加例如是松香處理、使用導入 酸性基或是鹼性基之顏料衍生物的表面處理、藉由高分子化合 物對顏料表面的嫁接(grafting)處理、藉由硫酸微粒化法等的微 9927 pifl 粒化處理、或是藉由用以除去不純物的有機溶劑或水或水的洗 淨處理。有機顏料的粒徑槪略爲10奈米以上150奈米以下。 著色劑的含有量，著色感光樹脂組成物包含的揮發成分 (溶劑），相對於揮發後之固體成份其質量分率爲5%以上’在考 慮到形成充分著色之著色圖案的話則爲10%以上，再者爲20 %以上特別是30%以上，通常爲60%以下，較佳爲50%以下 的範圍。而且，著色劑係使用有機顏料的場合，此有機顏料的 使用量相對於全體量的質量分率爲50%以上，較佳爲55%以 上，著色劑的全體量（100%)亦可以是有機顏料。 (B)高分子結合劑係可以使用丙烯醯系共聚物，例如所舉 的是含有羧基的單體以及能夠與其共聚合之其他單體的共聚 合物等。 含有羧基的單體例如是所舉的不飽和單羧酸、不飽和雙羧 酸或不飽和三羧酸等的不飽和多價羧酸等的分子中，至少具有 一個羧基的不飽和羧酸。此處不飽和單羧酸例如是所舉的丙烯 醯酸、甲基丙烯醯酸、丁烯酸、2-氯丙醯酸、2-苯基丙烯酸等。 不飽和雙羧酸例如是所舉的順丁烯二酸、反式丁烯二酸、甲叉 丁二酸、順式甲基丁烯二酸與甲基反式丁烯二酸等。不飽和多 價羧酸係爲其酸酐，具體而言亦可以是所舉的順丁烯二酸酐、 反式丁烯二酸酐與順式甲基丁烯二酸酐。而且不飽和多價羧酸 亦可以爲其單(2-甲基丙烯醯基氧基烷基）酯，具體而言例如是 丁二酸單(2_丙烯醯基氧基乙基）、鄰苯二甲酸單(2_丙烯醯基氧 基乙基）、鄰苯二甲酸單(2-甲基丙烯醯基氧基乙基)等。不飽和 多價羧酸亦可以爲兩端末爲羧基高分子的單（甲基）丙烯醯酯， 具體而言例如是0 -聚己內酯單丙烯酸酯與〇_聚己內酯單甲基 丙烯酸酯。含有羧基的單體例如是可以單獨個別使用或是兩種 583506 9927 pif 1 以上分別使用。 能夠與含有羧基的單體共聚合的其他單體，例如是所舉的 苯乙烯、α-甲基苯乙烯、0-乙烯基甲苯、m-乙烯基甲苯、P-乙烯基甲苯、p-氯苯乙烯、〇-甲氧基苯乙，嫌、m-甲氧基苯乙烯、 p-甲氧基苯乙烯、〇-乙烯基苄基甲基醚、m-乙烯基苄基甲基醚、 P-乙烯基苄基甲基醚、〇-乙烯基苄基環氧丙基醚、m-乙烯基苄 基環氧丙基醚、P-乙烯基T基環氧丙基醚、茚等芳香族乙烯基 化合物， 甲基丙烯酸酯、甲基甲基丙烯酸酯、乙基丙烯酸酯、乙基 # 甲基丙烯酸酯、η-丙基丙烯酸酯、η-丙基甲基丙烯酸酯、i-丙基 丙烯酸酯、i-丙基甲基丙烯酸酯、η-丁基丙烯酸酯、η-丁基甲基 丙烯酸酯、i-丁基丙烯酸酯、i-丁基甲基丙烯酸酯、sec-丁基丙 烯酸酯、sec-丁基甲基丙烯酸酯、t-丁基丙烯酸酯、t-丁基甲基 丙烯酸酯、2-羥乙基丙烯酸酯、2-羥乙基甲基丙烯酸酯、2-羥 丙基丙烯酸酯、2-羥丙基甲基丙烯酸酯、3-羥丙基丙烯酸酯、 3-羥丙基甲基丙烯酸酯、2-羥丁基丙烯酸酯、2-羥丁基甲基丙 烯酸酯、3-羥丁基丙烯酸酯、3-羥丁基甲基丙烯酸酯、4-羥丁 基丙烯酸酯、4-羥丁基甲基丙烯酸酯、烯丙基丙烯酸酯、烯丙 _ 基甲基丙烯酸酯、苄基丙烯酸酯、苄基甲基丙烯酸酯、環己基 丙烯酸酯、環己基甲基丙烯酸酯、酚基丙烯酸酯、酚基甲基丙 烯酸酯、2-甲基乙基丙烯酸酯、苯氧基乙基丙烯酸酯、甲氧基 二乙二醇丙烯酸酯、甲氧基二乙二醇甲基丙烯酸酯、甲氧基三 乙二醇丙烯酸酯、甲氧基三乙二醇甲基丙烯酸酯、甲氧基丙二 醇丙烯酸酯、甲氧基丙二醇甲基丙烯酸酯、甲氧基二丙二醇丙 烯酸酯、甲氧基二丙二醇甲基丙烯酸酯、異冰片丙烯酸酯、異 冰片甲基丙烯酸酯、環戊二烯基丙烯酸酯、環戊二烯基甲基丙 11 583506 9927 pif 1 烯酸酯、2-羥基-3-苯氧基丙基丙烯酸酯、2-羥基-3-苯氧基丙基 甲基丙烯酸酯、丙三醇單丙烯酸酯、丙三醇單甲基丙烯酸酯等 的不飽和睃酸酯類， ^ 2-氨基乙基丙烯酸酯、2-氨基乙基甲基丙烯酸酯、2-二甲 基氨基乙基丙烯酸酯、2-二甲基氨基乙基甲基丙烯酸酯、2-氨 基丙基丙烯酸酯、2-氨基丙基甲基丙烯酸酯、2-二甲基氨基丙 基丙烯酸酯、2-二甲基氨基丙基甲基丙烯酸酯、3-氨基丙基丙 烯酸酯、3-氨基丙基甲基丙烯酸酯、3-二甲基氨基丙基丙烯酸 酯、3-二甲基氨基丙基甲基丙烯酸酯等的不飽和羧酸氨基烷基 酯類， 環氧丙基丙烯酸酯、環氧丙基甲基丙烯酸酯等的不飽和羧 酸氨基環氧丙基酯類， 醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、安息香酸乙烯酯 等的不飽和羧酸氨基乙烯基酯類， 乙烯基甲基醚、乙烯基乙基醚、丙烯基環氧丙基醚等的不 飽和醚類，丙烯腈、甲基丙烯腈、α -氯丙烯腈、醯胺化亞乙烯 基等的醯胺化乙烯基化合物， 丙烯醯胺、甲基丙烯醯胺、α -氯丙烯醯胺、Ν-2-氧乙基 < 丙烯醯胺、Ν-2-氧乙基甲基丙烯醯胺等不飽和胺類， 順丁烯二醯亞胺、Ν-苯基順丁烯二醯亞胺、Ν-環己基順丁 烯二醯亞胺等的不飽和亞胺類， 1，3-丁二烯、異戊二烯、氯丁二烯等二烯酯類， 聚苯乙烯、聚甲基丙烯酸酯、聚甲基甲基丙烯酸酯、聚-η-丁基丙烯酸酯、聚-η-丁基甲基丙烯酸酯、聚矽氧烷之聚合分子 練的末端具有單丙烯醯基或是單甲基丙烯醯基的巨單體類。此 些單體係可以個別單獨使用或是兩種以上混合使用。 12 583506 9927 pif 1 於共聚物中含有羧基的單體單位的含有量，其質量分率通 常是10〜50%左右、較佳爲15〜40%左右、更佳爲25〜40% 左右。 丙烯醯系共聚合物例如是所舉的（甲基)丙烯酸/甲基（甲基) 丙烯酸酯共聚合物、（甲基）丙烯酸/苄基（甲基）丙烯酸酯共聚合 物、（甲基）丙烯酸/2-羥乙基（甲基）丙烯酸酯/苄基（曱基）丙烯酸 酯共聚合物、（甲基)丙烯酸/甲基（甲基)丙烯酸酯/聚苯乙烯巨單 體共聚合物、（甲基)丙烯酸/甲基（甲基）丙烯酸酯/甲基（甲基)丙 烯酸酯巨單體共聚合物、（甲基)丙烯酸/苄基（甲基)丙烯酸酯/聚 苯乙烯巨單體共聚合物、（甲基)丙烯酸/苄基（甲基)丙烯酸酯/甲 基（甲基)丙烯酸酯巨單體共聚物、（甲基)丙烯酸/2-羥乙基（甲基） 丙烯酸酯/苄基（甲基)丙烯酸酯/聚苯乙烯巨單體共聚合物、（甲 基）丙烯酸/2-羥乙基（甲基）丙烯酸酯/苄基（甲基)丙烯酸酯/甲基 (甲基）丙烯酸酯巨單體共聚合物、甲基丙烯酸/聚苯乙烯/苄基 (甲基)丙烯酸酯/N_苯基順丁烯二醯亞胺、（甲基)丙烯酸/丁二酸 單（2-丙烯醯基氧基乙基)/聚苯乙烯/丙基（甲基）丙烯酸/N-苯基 順丁烯二醯亞胺共聚合物、（甲基)丙烯酸/苄基（甲基)丙烯酸酯 /N-苯基順丁烯二醯亞胺/聚苯乙烯/丙三醇單甲基丙烯酸酯共聚 合物等。而且，丙烯酸酯以及甲基丙烯酸酯係表示爲（甲基)丙 烯酸酯。其中較佳爲使用（甲基)丙烯酸/苄基（甲基)丙烯酸酯共 聚合物、（甲基）丙烯酸/苄基（甲基）丙烯酸酯/聚苯乙烯共聚合 物、甲基（甲基)丙烯酸酯/(甲基)丙烯酸/聚苯乙烯共聚合物，更 佳爲使用（甲基)丙烯酸/苄基（甲基)丙烯酸酯共聚合物。 丙烯醯系共聚合物之聚苯乙烯換算重量平均分子量較佳 爲3000〜4000000,更佳爲5000〜1000000、特佳爲20000〜 40000。重量平均分子量(Mw)係爲以聚苯乙烯爲基準，藉由凝 13 9927 pif 1 膠滲透層析(gel permeation chromatography，GPC)測定所得的 値。 丙烯醯系共聚合物之酸價較佳爲30〜250、更佳爲60〜 180、特佳爲90〜160。此處酸價係爲測定中和1克丙烯醯系共 聚合物所需氫氧化鈉量(mg)的値，通常係能夠將1克的高分子 結合劑溶解於10立方公分的水與40立方公分的丙酮的混合溶 劑，一邊測量pH値並一邊加入氫氧化鈉滴定以求得。 結合樹脂係使用對著色感光樹脂組成物的質量分率通常 爲5%以上，較佳爲10%以上，更佳爲20%以上，通常爲90 %以下，較佳爲80%以下，更佳爲70%以下左右的範圍。 (C) 光聚合性化合物係藉由照光並藉由光聚合引發劑所產 生的活性自由基、酸等聚合的化合物，例如是具有聚合性的碳 -碳不飽和結合的化合物等。 光聚合性化合物較佳爲4官能基以上的多官能基光聚合 性化合物。4官能基以上的多官能基光聚合性化合物例如是所 舉的季戊四醇四丙烯酸酯、季戊四醇四（甲基)丙烯酸酯、二季 戊四醇五丙烯酸酯、二季戊四醇五（甲基)丙烯酸酯、二季戊四 醇六丙烯酸酯、二季戊四醇六（甲基)丙烯酸酯。 著色感光樹脂組成物的光聚合性化合物含量係爲對著色 感光樹脂組成物的質量分率通常1%以上60%以下，較佳爲3 %以上50%以下。 (D) 光聚合引發劑例如是所舉的藉由照光產生活性自由基 的活性自由基產生劑，產生酸的酸產生劑。活性自由基產生劑 例如是所舉的乙醯苯系光聚合引發劑、三氮雜苯系光聚合引發 劑、二苯乙醇酮系光聚合引發劑、二苯甲酮系光聚合引發劑、 噻噸酮系光聚合引發劑。 583506 9927 pif 1 乙醯苯系光聚合引發劑例如是所舉的二乙氧基乙醯苯、2-經基-2-甲基_1_苯基丙烷酮、苄基二甲基縮酮、2_羥基_2_甲 基-W4-(2-羥基乙氧基）苯基]丙烷小酮、卜羥基環己基苯基酮、 2-甲基-2-嗎啉代4-(4-甲硫基苯基）丙烷_；μ嗣、羥基_2_甲基 甲基乙烯基)苯基]丙烷酮的寡聚物等。 二苯乙醇酮系光聚合引發劑例如是所舉的二苯乙醇酮、二 苯乙醇酮甲基醚、二苯乙醇酮乙基醚、二苯乙醇酮異丙基醚、 二苯乙醇酮異丁基醚等。 三氮雜苯系光聚合引發劑例如是所舉的2,4-雙（三氯甲 基）-6-(4-甲氧基苯基)-13,5_三氮雜苯、2,4·雙（三氯甲基)-6-(4-甲氧基萘基）-1，3,5·三氮雜苯、2,4-雙（三氯甲基）-6-胡椒基 -1，3,5-三氮雜苯、2,4·雙（三氯甲基）-6-(4-甲氧基苯乙烯 基）-1，3,5_三氮雜苯、2,4-雙（三氯甲基）-6-[2-(5-甲基呋喃-2-基） 乙烯基]-1，3,5-三氮雜苯、2,4-雙（三氯甲基)-6-[2-(呋喃-2-基）乙 烯基]-1，3,5-三氮雜苯、2,4-雙（三氯甲基）-6-[2-(4-乙基氨基-2_ 甲基苯基）乙稀基]-1，3,5-三氮雜苯、2,4-雙(三氯甲基)-6-[2_(3,4-二甲氧基苯基）乙烯基]-1,3,5-三氮雜苯等。 二苯甲酮系光聚合引發劑例如是所舉的二苯甲酮、〇-二苯 甲酮安息香酸甲酯、4-苯基二苯甲酮、4-苯醯基-4’-甲基二苯基 硫化物、3,3’，4,4，-四（t·丁基過氧羰基）二苯甲酮、2,4,6-三甲基 二苯甲酮等。 噻噸酮系光聚合引發劑例如是所舉的2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、1-氯-4-丙氧基噻噸酮等。 活性自由基產生劑例如是所舉的2,4,6-三甲苯基二苯基氧 化膦、2,2，-雙（〇-氯苯基)-4,4，，5,5，-四苯基連二咪唑、10· 15 9927 pifl 丁基-2-氯卩丫卩定酮、2-乙基蔥醌、卞基、9,1〇-菲醌、茨醒、苯基 乙醛酸甲酯、二茂鈦化合物等。 酸產生劑例如是可以使用4-羥基苯基二甲基鎏p_甲苯磺 醯酯、4-羥基苯基二甲基鎏六氟銻酸酯、4_乙酸基苯基二甲基 鎏P-甲苯磺醯I旨、4·乙酸基雜•甲基· |麵六氟鍊酸醋、 三苯基鎏P-甲苯磺醯酯、三苯基鎏六氟銻酸酯、二苯基碘氫基 p-甲本漏醯酉日、一本基碘氫基六氟銻酸酯等的鐵鹽類或硝基节 對甲苯磺酯'二苯乙醇酮對甲苯磺酯等。 / 而且，上述作爲活性自由基產生劑的化合物中，亦有同時 產生活性自由基與酸的化合物，例如是三連氮系光聚合引發劑 等的活性自由基產生劑，亦可以作爲酸產生劑使用。 此些光聚合引發劑係能夠個別單獨使用或是兩種以上組 合使用。於光聚合引發劑中，乙醯苯系光聚合引發劑較佳爲使 用2-甲基-2-嗎啉代-1-(4-甲硫基苯基)丙烷酮，三氮雜苯系光 聚合引發劑較佳爲使用2,4·雙（二氯甲基)胡椒基-丨，〗，％三氮 雜苯。 著色感光樹脂組成物的光聚合引發劑的含量係爲對著色 感光樹脂組成物的質量分率通常1%以上25%以下，較佳爲3 %以上20%以下。 本發明的著色感光樹脂組成物亦可以含有光聚合引發助 劑。光聚合引發助劑係與光聚合引發劑組合使用，用以促進光 聚合性化合物聚合。光聚合引發助劑例如是所舉的胺系光聚合 引發助劑、烷氧基蔥系光聚合引發助劑等。 胺系光聚合引發助劑例如是所舉的三乙醇胺、甲基二乙醇 胺、三異丙醇胺、4-二甲醇胺安息香酸甲酯、4-二甲醇胺安息 香酸乙酯、4-二甲醇胺安息香酸乙酯異戊酯、安息香酸2-二甲 583506 9927 pif 1 醇胺乙酯、4-二甲醇胺安息香酸2-乙基己酯。N，N-二甲基對甲 苯胺、4,4’-雙（二甲胺）二苯甲酮（通稱米希勒酮）、4,4’-雙（二乙 胺）二苯甲酮、4,4’-雙（乙基甲胺）二苯甲酮等。 烷氧基蔥系光聚合引發助劑例如是，所舉的9,10-二甲氧基 蔥、2-乙基-9，10_二甲氧基蔥、9，10-二乙氧基甲氧基蔥、2-乙基 _9，10_二乙氧基甲氧基蔥等。 於使用光聚合引發助劑的場合，其使用量爲對1莫耳的光 聚合引發劑爲1〇莫耳以下，較佳爲〇.〇1莫耳以上5莫耳以下。 於使用光聚合引發劑與光聚合引發助劑的場合，其合計量 對高分子結合劑與光聚合性化合物之合計量的莫耳分率，通常 爲3%以上48%以下，較佳爲5%以上36%以下。 (E)溶劑係與通常著色感光樹脂組成物所使用的溶劑相 同，例如是所舉的醚類、芳香族碳化氫類、酮類、醇類、酯類 與醯胺類。 醚類例如是所舉的四氫呋喃、四氫吡喃、1,4-二氧雜環己 烷、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單 丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、 二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丙醚、二乙二 醇單丁醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二 醇單丙醚乙酸酯、甲基乙二醇乙醚乙酸酯、乙基乙二醇乙醚乙 酸酯、乙基乙氧乙氧基乙醇乙酸酯、丁基乙氧乙氧基乙醇乙酸 酯、丙二醇甲醚乙酸酯、甲氧基丁基乙酸酯、甲氧基戊基乙酸 酯、苯甲醚、苯乙醚、甲基苯甲醚等。 芳香族碳化氫類例如是所舉的苯、甲苯、二甲苯、三甲苯 等。 酮類例如是所舉的甲基乙酮、丙酮、甲基戊酮、甲基異丁 17 9927 pif 1 酮、2-丁酮、2_庚酮、4-甲基-2-戊酮、環己酮等。 醇類例如是所舉的甲醇、乙醇、丙醇、丁醇、己醇、環己 醇、乙二醇、丙二醇等。 酯類例如是所舉的乙酸乙酯、乙酸:n-丁酯、乙酸異丁酯、 甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、 丁酸乙酯、丁酸丁酯、烷酯類、丙醇酸甲酯、丙醇酸乙酯、羥 基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、氧甲基乙酸甲酯、 氧甲基乙酸乙酯、氧甲基乙酸丁酯、氧乙基乙酸甲酯、氧乙基 乙酸乙酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-甲氧基丙酸 甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸 乙酯、2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基丙酸丙酯、 2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、 2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-羥基-2-甲基丙酸甲 酯、2-羥基-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙 氧基-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、 乙醯乙酸甲酯、乙醯乙酸乙酯、2-羧基丁酸甲酯、3-甲氧基丁 基乙酯、3-甲基-3-甲氧基丁基乙酯，丁內醯胺等。 醯胺類例如是所舉的N，N’-2-二甲基甲醯胺、N，N’-二甲基 乙醯胺等。 其他的溶劑例如是所舉的N-甲基吡咯烷酮、二甲亞砜等。 於上述溶劑中較佳爲使用3-甲基丙酸甲酯、3-乙氧基丙酸 甲酯、3-乙氧基丙酸乙酯、乙基乙二醇乙醚乙酸酯、丙醇酸乙 酯、二乙二醇二甲醚、乙酸丁酯、乙基乙氧乙氧基乙醇乙酸酯、 丁基乙氧乙氧基乙醇乙酸酯、丙二醇單甲醚乙酸酯、2-庚酮等。 此些溶劑係能夠個別單獨使用或是兩種以上組合使用。其 使用量係對溶劑稀釋狀態之著色感光樹脂組成物含量的質量 9927 pif 1 分率通常爲50%以上90%以下，較佳爲60%以上85%以下。 著色感光樹脂組成物含有作爲著色劑之原料的場合亦可 以含有顏料分散劑。藉由含有顏料分散劑，所含顏料能夠具有 均勻的分散狀態，而能夠得到均勻著色的著色圖案。顏料分散 劑例如是所舉的聚酯系高分子分散劑、丙烯醯系高分子分散 劑、聚氨基甲酸乙酯系高分子分散劑等的分散劑，陽離子系界 面活性劑、陰離子系界面活性劑、非離子系界面活性劑等的界 面活性劑。含有顏料分散劑的場合，其含有量係對1質量份的 著色劑通常爲0.01質量份以上，較佳爲0·05質量份以上，通 常爲1質量份以下、較佳爲0.5質量份以下。 著色感光樹脂物亦可以含有塡充劑、高分子結合劑(Β)以 外的化合物、密著促進劑、抗氧化劑、紫外線吸收劑、抗凝集 劑、有機酸、有機氨化合物、硬化劑等添加劑。 塡充劑例如是所舉的玻璃、鋁等的微粒子。 高分子化合物例如是所舉的聚乙烯醇、聚丙烯酸' 乙二醇 單烷醚、聚氯烷基丙烯醯酯等。 密著促進劑例如是所舉的乙烯基三甲氧矽烷、乙烯基三乙 氧矽烷、乙烯基三（2-甲氧基乙氧基）矽烷、Ν-(2-氨基乙基)-3-氨基丙基三甲氧矽烷、3-氨基丙基三乙氧矽烷、3-環氧丙氧基 丙基三甲氧矽烷、3-環氧丙氧基甲基二甲氧矽烷、2-(3,4_環氧 環己基）乙基三甲氧矽烷、3-氯丙基甲基二甲氧矽烷、3-氯丙基 三甲氧矽烷、3-甲基丙烯醯基丙基三甲氧矽烷、3-氫硫基丙基 三甲氧矽烷等。 抗氧化劑例如是所舉的2.2-硫代雙(4-甲基丁基酣）、 2,6-二-t-丁基酚等。 紫外線吸收劑例如是所舉的2-(2-羥基-3-t-丁基甲基苯 583506 9927 pif 1 基）-5-苯并三唑等的苯并三唑系，2-羥基-4-辛基羥基二苯甲酮 等的二苯甲酮系，2,4-二-t-丁基苯基-3,5-二-t-丁基-4-羥基苯甲 酸酯等的苯甲酸酯類。 抗凝集劑例如是所舉的聚丙烯酸鈉，鹽等。 有機酸例如是所舉的甲酸、乙酸、丙酸、丁酸、戊酸、三 甲基乙酸、己酸、二乙基乙酸、庚酸、辛酸等的脂肪族單羧酸 類， 乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛 二酸、壬二酸、癸二酸、巴西二酸、甲基丙二酸、乙基丙二酸、籲 二甲基丙二酸、甲基丁二酸、四甲基丁二酸、環己烷羧酸、甲 叉丁二酸、順式甲基丁烯二酸、順丁烯二酸、反式丁烯二酸、 甲基反式丁烯二酸等的脂肪族雙羧酸類， 均丙三甲酸、丙烯-1，2,3-羧酸、樟腦三酸等的脂肪族三羧 酸類， 安息香酸、甲苯酸、對異丙基苯甲酸、連苯三酸、均三甲 苯等的芳香族單羧酸類， 苯二甲酸、異苯二甲酸、對苯二甲酸等的芳香族雙羧酸類， 偏苯三酸、均苯三甲酸、偏苯四甲酸、均苯四甲酸等的芳 籲 香族聚羧酸類。 有機胺化合物例如是所舉的η-丙胺、i-丙胺、η-丁胺、i-丁胺、sec_丁胺、t-丁胺、η-戊胺、η-己胺、η-庚胺、η-辛胺、 η-壬胺、η-癸胺、η_~[--胺、η-十二胺等的單院胺類， 環己胺、2-甲基環己胺、3-甲基環己胺、4-甲基環己胺等 的單環烷胺類， 甲基乙胺、二甲胺、甲基η-丙胺、乙基η-丙胺、二η-丙 胺、二 i_丙胺、二 η_丁胺、二 i_丁胺、二 sec-丁胺、二 t-丁胺、 20 583506 9927 pif 1 二n_戊胺、二n-己胺等的雙烷胺類， 甲基環己胺、乙基環己胺等的單烷基單環烷胺類， 二環己胺等的雙環烷胺類， 二甲基乙胺、甲基二乙胺、三乙胺，、二甲基η-丙胺、二乙 基η-丙胺、甲基二η-丙胺、乙基二η-丙胺、三η-丙胺、三i-丙胺、三η-丁胺、三i-丁胺、三sec-丁胺、三t-丁胺、三η-戊 胺、三η-己胺等的三烷胺類， 二甲基環己胺、二乙基環己胺等的二烷基單環烷胺類， 甲基二環己胺、乙基二環乙胺等的單烷基雙環烷胺類， 0 三環己胺等的三環烷胺類， 2- 氣基乙醇、3-氛基-1-丙醇、1-氨基-2-丙醇、4_氣基-1- 丁醇、5-氨基-1-戊醇、6-氨基-1-己醇等的單烷醇胺類， 4-氨基-1-環己醇等的單環烷醇胺類， 二乙醇胺、二η-丙醇胺、二i-丙醇胺、二η-丁醇胺、二 i-丁醇胺、二η-戊醇胺、二η-己醇胺等的二烷醇胺類， 二(4_環己醇)胺等的二環烷醇類， 三乙醇胺、三η-丙醇胺、三i-丙醇胺、三η-丁醇胺、三 i-丁醇胺、三n_戊醇胺、三η-己醇胺等的三烷醇胺類， 籲 三（4-環己醇）胺等的三環烷醇類， 3- 氨基-1，2-丙二醇、2-氨基-1，3-丙二醇、4-氨基-1，2-丁二 醇、4-氨基-1，3-丁二醇、3-二甲胺-1，2-丙二醇、2-二甲胺-1，3-丙二醇、3-二乙胺-1，2-丙二醇、2-二乙胺-1，3-丙二醇等的氨基 烷二醇類， 4_氨基-1，2-環己二醇、4-氨基-1，3-環己二醇等的氨基環烷 二醇類， 1-氨基環戊酮甲醇、4-氨基環戊酮甲醇等的含氨基環烷酮 21 583506 9927 pif 1 甲醇類， 1-氨基環己酮甲醇、4-氨基環己酮甲醇、4-二甲基環戊烷 甲醇、4-二乙基環戊烷甲醇、4-二甲基環己烷甲醇、4-二乙基 環己烷甲醇等的含氨基環鏈烷酮甲醇類，， β-丙氨酸、2-氨基丁酸、3-氨基丁酸、4-氨基丁酸、2-氨 基異乙酸、3-氨基異乙酸、2-氨基戊酸、5-氨基戊酸、6-氨基庚 酸、1-氨基環丙烷羧酸、1-氨基環己烷羧酸、4-氨基環己烷羧 酸等的氨基羧酸類， 苯胺、〇-甲基苯胺、m-甲基苯胺、ρ-甲基苯胺、ρ-乙基苯 0 胺、p-n-丙基苯胺、p-i-丙基苯胺、ρ-η-丁基苯胺、p-t-丁基苯 胺、1-萘胺、2-萘胺、N，N-二甲基苯胺、N，N-二乙基苯胺、p- 甲基-二甲基苯胺等的芳香族胺類， 〇-氨基苄基乙醇、m-氨基苄基乙醇、p-氨基苄基乙醇、p-二甲基氨基苄基乙醇、P-二乙基氨基苄基乙醇等的氨基苄基乙 醇類， 〇-氨基酚、m-氨基酚、p-氨基酚、p-二甲基氨基酚、p-二 乙基氨基酚等的氨基酚類， m-氨基安息香酸、p-氨基安息香酸、p-二甲基氨基安息香 籲 酸、P-二乙基氨基安息香酸等的氨基安息香酸類。 硬化劑例如是所舉的能夠藉由加熱與高分子結合劑(B)中 的羧基反應以將高分子結合劑架橋的化合物。而且亦舉出此些 單獨聚合以將著色圖案硬化的化合物。此些化合物例如是所舉 的環氧化合物、氧雜環丁烷化合物。 環氧化合物例如是所舉的雙酚A系環氧樹脂、氫化雙酚A 系環氧樹脂、雙酚F系環氧樹脂、氫化雙酚F系環氧樹脂、酚 醛型環氧樹脂、其他的芳香族系環氧樹脂、脂環族系環氧樹 22 583506 9927 pif 1 脂、複素環式環氧樹脂、縮水甘油酸酯系樹脂、縮水甘油胺系 樹脂、環氧化油等的環氧樹脂，或是此些環氧樹脂的溴化衍生 物，環氧樹脂以及其溴化衍生物之外的脂肪族、脂環族或是芳 香族的環氧化合物，丁二烯之（共）聚合物的環氧化物、異戊二 烯之（共）聚合物的環氧化物、環氧丙基（甲基)丙烯酸酯的（共)聚 合物、三環氧丙基異醯胺酯等。 氧雜環丁烷化合物例如是所舉的碳酸酯雙氧雜環丁烷、二 甲苯雙氧雜環丁烷、己二酸酯雙氧雜環丁烷、對苯二甲酯雙氧 雜環丁烷、環己烷二羧酸雙氧雜環丁烷等。 本發明的著色感光組成物以環氧化合物、氧雜環丁烷化合 物作爲硬化劑的場合’亦可以包含環氧化合物的環氧基、氧雜 環丁烷化合物的骨架開環聚合所得的化合物。此些化合物例如 是多價羧酸類、多價羧酸酐類、酸產生劑等。 多價羧酸類例如是所舉的苯二甲酸、3,4_二曱基苯二甲 酸、異苯一甲酸、對苯二甲酸、均苯四甲酸、偏苯三酸、 萘四羧酸、3,3’，4,4’-二苯甲酮四羧酸等的芳香族多價羧酸類， 丁一酸、戊一酸、己二酸、丨，2,3,4_丁烷四羧酸、順丁烯 一酸、反式丁烯二酸、甲叉丁二酸等的脂肪族多價羧酸， 六氫苯二甲酸、3,4-二甲基四氫苯二甲酸、六氫異苯二甲 酸、六氫對苯二甲酸、I，2,4-環戊烷三羧酸、丨,2,4_環己烷三羧 酸、環戊烷四羧酸、I，2,4,5-環己烷四羧酸等脂環族多價羧酸類。 多價竣酸酐例如是所舉的苯二甲酸酐、均苯四甲酸酐、偏 本二酸酐、3,3’，4,4’-二苯甲酮四羧酸二酐等的芳香族多價羧酸 酐類， 甲叉丁二酸酐、丁二酸酐、順式甲基丁烯二酸酐、十二碳 烯琥珀酸酐、丙三羧酸酐、順丁烯二酸酐、丁烷四羧酸 23 583506 9927 pifl 二酐等的脂肪族多價羧酸酐類， 六氫苯二甲酸酐、3,4-二甲基四氫苯二甲酸酐、1，2,4-環戊 烷三羧酸酐、1，2,4-環己烷三羧酸酐、環戊烷四羧酸二酐、 1，2,4,5-環己烷四羧酸等脂環族多價羧酸，二酐、雙環庚烯二甲酸 酐、草淨津酸酐等的脂環族多價羧酸無水物類， 乙二醇雙偏苯三酸、丙三醇雙偏苯三酸酐等含有酯基的羧 酸酐類。 羧酸酐類例如是可以使用市售的環氧樹脂硬化劑。環氧樹 脂硬化劑例如是所舉的商品名「ADEKA HARDENER-EH-700」 ^ (旭電化工業(株)）、商品名「力卡西得（!；力シy H')HH」（新日 本理化(株)）、商品名「MH-700」（新日本理化(株))等。 硬化劑係能夠個別單獨使用或是使用兩種以上混合者。 於著色感光樹脂組成物中，（A)著色劑係使用顏料的場 合，顏料通常係分散於組成物中。而且，（A)著色劑係使用染料 的場合，染料係可以分散於組成物中，亦可以溶解於溶劑中。 (B)高分子結合劑、（C)光聚合性化合物、（D)光聚合引發劑係溶 解於(E)溶劑中。 本發明第一實施例的保存方法係將著色感光樹脂組成物 _ 保持在攝氏零下6度以上攝氏15度以下。著色感光樹脂組成 物不邊震動保存的場合，超過攝氏15度的話則於長時間保存 期間的黏度容易產生變化，並且在攝氏8度以下，而且未滿攝 氏零下6度則容易產生膠化物。 本發明第一實施例的保存方法係將著色感光樹脂組成物 塡充保存於容器中，並且保存於由此容器內容積減去著色感光 樹脂組成物所佔體積所得的空隙部，且空隙部與內容積的比率 (空隙率，％)與此空隙部環境氣體之氧分壓（hPa)的乘積爲 24 583506 9927 pif 1 2000(% · hPa)以上，較佳爲4000(% · hPa)以上的環境氣體中。 與空隙部環境氣體之氧分壓的乘積小於2000(%· hPa)的話則易 產生膠化物。 本發明第二實施例的保存方法係爲使著色感光樹脂組成 物震動的保存。 使著色感光樹脂組成物震動的方法，例如是將著色感光樹 脂組成物塡充入容器中並震動此容器。 於本發明的第二實施例中，著色感光樹脂組成物係能夠塡 充對容器內容積50%以上100%以下的塡充率。亦可以爲50 # %以下，然而由於塡充的效率低落之故而較爲不佳。塡充率未 滿100%則在容器內產生空隙，此空隙亦可以塡入氮氣、氬氣 等惰性氣體，亦可以塡入空氣。 容器的振動例如是亦可以使用搖動器，以水平方向或是垂 直方向震動容器。而且亦可以密閉塡充有著色感光樹脂組成物 的容器，重複的上下反轉。容器係可以連續的震動，亦可以以 30分鐘內的間隔重複操作震動與靜置。 於本發明的第二實施例中，保存溫度爲攝氏零下1〇度以 上，較佳爲攝氏零下7度以上，攝氏30度以下，較佳爲攝氏 _ 零下10度以上。 於本發明的第一實施例與第二實施例中，容器係爲無色透 明之可見光可透過材質，例如是無機玻璃製的容器，具體而言 可使用無色透明的玻璃容器等，然而較佳爲保存在光的透過率 在250奈米〜440奈米的波長範圍爲〇%以上8%以下、較佳爲 5%以下的容器，例如是藉由保存於著色的玻璃瓶等之中而能 夠抑制膠化物的產生。亦可以在光透過率於250奈米〜440奈 米的波長範圍超過8%的容器，例如是無色透明的玻璃瓶內裝 25 583506 9927 pifl 入著色感光樹脂組成物，再將此容器置入光透過率在250奈米 〜440奈米的波長範圍爲8%以下、較佳爲5%以下的容器’例 如是硬紙箱、黑色的塑膠袋、著色之塑膠製保管容器、金屬製 保管容器等之中以保存。 ， 超過440奈米波長範圍之光透過率可以超過8% ’然而較 佳爲8%以下，更佳爲5%以下。亦可以使用將250奈米〜440 奈米波長範圍的光完全遮斷的容器(透過率爲〇%) ° 由保存後的著色感光樹脂組成物形成著色圖案’例如是亦 可以圖案化與通常相同之保存後的著色感光樹脂組成物。具體 而言，係將保存後的著色感光樹脂組成物塗佈於基板3上’除 去(E)溶劑以形成著色感光層4(第2A圖），再藉由曝光此著色感 光層(第2B圖）並顯影的方法以形成。 基板3例如是所舉的玻璃基板、矽基板、聚碳酸酯基板、 聚乙酯基板、芳香族聚醯胺樹脂基板、聚醯胺醯亞胺基板、聚 醯亞胺樹脂基板等的表面平坦的基板。此些基板亦可以進行矽 烷偶合劑等的藥品處理、電漿處理、離子電鍍、濺鍍、化學氣 相沈積法、真空蒸鍍等前處理。基板係使用矽基板的場合，亦 可以在矽基板等的表面形成電荷耦合元件(CCD)、薄膜電晶體 (thin film transistor，TFT)等0 著色感光樹脂組成物的塗佈，例如是採用將著色感光樹脂 組成物均勻厚度的塗佈在基板上的方法，例如是旋轉塗佈(spin coat)法、流延塗佈法、滾筒塗佈(roll c〇at)法以及狹縫與旋轉塗 佈法等通常的塗佈方法進行。塗佈後(E)溶劑的去除例如是可以 進行加熱。其後形成的著色感光層4係爲由著色感光樹脂組成 物除去(E)溶劑等揮發成分之固體成份所形成的層。 其次對著色感光層4曝光(第2B圖）。曝光可以是例如藉 26 583506 9927 pifl 由光罩5照射光線6,光線6通常係採用稱爲g線(波長436奈 米）、i線(波長365奈米)的紫外線。光線係間隔光罩照射，此 處光罩5例如是在玻璃基板51的表面形成遮蔽光線的遮光層 52。玻璃基板Η未設置遮光部52的部位爲光線透過的透光部 53 ’依照此透光部的圖案將圖案曝光於著色感光層4，以形成 光線未照射的未照射區域41與光線照射的照射區域42。照射 區域42的光線照射量，係能夠依照所使用的(A)著色劑的種類 或含量、（B)高分子結合劑重量平均分子量、含量、單體單位組 成、（C)光聚合性化合物的種類、含量、（D)光聚合引發劑的種 類、含量等作適當選擇。 曝光後係加以顯影(第2C圖）。顯影例如是使曝光後的著 色感光層4與顯影液接觸，具體而言係將表面上形成有著色感 光層4的基板3浸入顯影液。顯影液通常係使用鹼性水溶液。 鹼性水溶液例如是所舉的碳酸鈉、碳酸鉀、氫氧化鈉、氫氧化 鉀、四甲基銨氫氧化物等鹼性化合物的水溶液。藉由顯影以將 光線未照射的未照射區域41除去。另一方面，殘留的光線照 射區域42構成著色圖案2。 顯影後，通常係藉由水洗乾燥而能夠的到所需之著色圖案鲁 2。乾燥後亦可以加熱。藉由加熱著色圖案增加硬度可以增強 其機械強度，著色感光樹脂組成物含有硬化劑的場合，則能夠 更提升機械強度。加熱溫度通常爲攝氏180度以上，較佳爲攝 氏200度以上。通常爲攝氏250度以下。 在形成著色圖案2的基板3上，再塗佈含有不同色著色劑 的著色感光樹脂組成物，除去溶劑則形成著色感光層4’，藉 由曝光(第3B圖）並顯影(第3C圖）著色感光層4’，而能再形成 著色圖案2’。再者，使用含有不同色著色劑的著色感光樹脂組 27 583506 9927 pifl 成物並重複上述的操作，而能夠依序形成著色圖案2”（第4A 圖至第4C圖），進而能夠製造具有著色圖案2,2’，2”的彩色濾光 片1(第1A圖至第1B圖）。用於製造上述彩色濾光片1的著色 感光樹脂組成物，係可以使用製造後直接使用者’亦可以使用 短期保存者，亦可以使用以本發明的方法保存者。 依照本發明第一實施例的保存方法，保存期間即使爲12 個月，著色感光樹脂組成物的品質不會產生變化。而且’亦不 會產生膠狀物。因此，能夠與使用製造後著色感光樹脂組成物 形成著色圖案，以相同的條件形成著色圖案。而且，由於著色 _ 感光樹脂組成物能夠長期間的保存且品質不產生大的變化’而 能夠一次大量的製造，進而能夠提升著色感光樹脂組成物的生 產性。提升著色感光樹脂組成物之生產性的效果’係隨著保存 期間3月、6月、12月的增加而增大。 依照本發明第一實施例的保存方法’由於保存中的著色感 光樹脂組成物幾乎不會產生膠化物，而能夠與使用製造後著色 感光樹脂組成物形成著色圖案相同的條件’以形成同樣的著色 圖案。 以下係藉由實驗例以更詳細說明本發明’然而本發明並非 馨 限定於下述實驗例。 尙且，於下述實驗例與比較例中’係評價著色感光樹脂組 成物的品質、黏度變化率以及膠化物的有無。黏度變化率係由 測定保存開始前的黏度U Q)與測定保存後的黏度U )所得的式 (1)計算出。 黏度變化率=¥ (!) 著色感光樹脂組成物之膠化物的有無係由目視觀察評價。 28 583506 9927 pif 1 第一實驗例[綠色著色感光樹脂組成物] 將含有： (A)顏料[c丄顏料綠36，粒徑爲3〇〜8〇奈米左右]〇 74〇質 量份， (A) 顏料[C.I·顏料黃150，粒徑爲30〜80奈米左右]0.340 質量份， (B) 甲基丙烯酸與苄基甲基丙烯酸酯的共聚合物[甲基丙 嫌酸單位與苄基甲基丙烯酸酯單位的組成比爲質量比(莫耳比）0 並爲35 : 65，重量平均分子量(Mw)爲35000，酸價爲135]0.787 質量份， (C) 二季戊四醇六丙烯酸酯0.472質量份， (D) 光聚合引發劑[2-甲基-2-嗎啉代小(4-甲硫基苯基)丙烷 -1-酮]0.189質量份， 光聚合引發助劑[4,4’_雙（二乙胺)二苯甲酮]0.063質量份， (E) 丙二醇單甲醚乙酸酯11·8質量份左右、環氧化合物[正 甲酚酣醒型環氧樹脂、「Sumiepoxy ESCN_195_XL-80」（住友 化學工業(株)製)]0.315質量份以及非離子系界面活性劑0.318 · 質量份 的著色感光樹脂組成物(綠色)置入保存容器[25〇奈米〜440奈 米的光透過率在5%以下的遮光]，並將容器密封’個別靜置保 存在攝氏零下5度與攝氏1〇度。經過6個月後以及經過12個 月後，著色感光樹脂組成物的黏度變化率如表1所示。尙且’ 經過6個月或是經過12個月保存後的著色感光樹脂組成物’ 無論是在何溫度保存者皆未生成膠狀物。 上述經12個月保存後的著色感光樹脂組成物’將之塗佈 29 9927 pif 1 於基板3上，將溶劑揮發以形成著色感光層4(第2A圖)，藉由 對此著色感光層4進行曝光(第2B圖），再進行顯影(第2C圖）， 而能夠得到與使用保存開始前之著色感光樹脂組成物所形成 之著色圖案相同的綠色透明著色圖案。， 第一比較例[綠色著色感光樹脂組成物] 將與第一實驗例相同之著色感光樹脂組成物置入與第一 實驗例相同之保存容器，個別靜置保存在攝氏零下8度、攝氏 20度與攝氏30度。於攝氏零下8度保存者在1週後產生膠化 物。經過3個月、經過6個月與經過12個月的黏度變化如表1 所示。尙且，於攝氏20度保存者在經6個月保存後亦不會產 生膠狀物，於攝氏30度保存者，經過1個月保存以及經3個 月保存亦不會產生膠狀物。 第二實驗例[紅色著色感光樹脂組成物的長期保存] 將含有： (A)顏料[C.I·顏料紅254，粒徑爲30〜40奈米左右]0.794 質量份， (A) 顏料[C.I_顏料黃139，粒徑爲30〜80奈米左右]0.211 質量份， (B) 甲基丙烯酸與苄基甲基丙烯酸酯的共聚合物[甲基丙 嫌酸單位與苄基甲基丙烯酸酯單位的組成比爲質量比（莫耳比) 並爲27 : 73，重量平均分子量(Mw)爲30000，酸價爲102]0·860 質量份’ (C) 二季戊四醇六丙烯酸酯0.546質量份， (D) 光聚合引發劑[2-甲基-2-嗎啉代-1-(4-甲硫基苯基)丙烷 583506 9927 pif 1 -1-_]〇·〇82 質量份， (D)光聚合引發劑[2,4_雙（三氯甲基)-6-胡椒基-1，3,5-三氮 雜苯]0.082質量份， 光聚合引發助劑[2,4-二乙基噻噸酮，]〇·〇82質量份， (Ε)丙二醇單甲醚乙酸酯12.0質量份左右以及非離子系界 面活性劑0.352質量份 的著色感光樹脂組成物（紅色）置入與第一實驗例相同的保存容 器並將容器密封，個別靜置保存在攝氏零下5度、攝氏5度與 攝氏10度。經過6個月後以及經過12個月後，著色感光樹脂 組成物的黏度變化率如表1所示。尙且，經過6個月或是經過 12個月保存後的著色感光樹脂組成物，無論是在何溫度保存者 皆未生成膠狀物。 上述經12個月保存後的著色感光樹脂組成物，將之塗佈 於基板3上，將溶劑揮發以形成著色感光層4(第2Α圖），藉由 對此著色感光層4進行曝光(第2Β圖），再進行顯影(第2C圖）， 而能夠得到與使用保存開始前之著色感光樹脂組成物所形成 之著色圖案相同的紅色透明著色圖案。 第二比較例[紅色著色感光樹脂組成物] 將與第二實驗例相同之著色感光樹脂組成物置入與第一 實驗例相同之保存容器，個別靜置保存在攝氏20度與攝氏30 度。經過3個月、經過6個月與經過12個月的黏度變化如表1 所示。尙且，於攝氏20度保存者在經6個月保存後亦不會產 生膠狀物，於攝氏30度保存者，經過1個月保存以及經3個 月保存亦不會產生膠狀物。 31 583506 9927 pif 1 = [藍色著色感光樹脂組成物] 將含有： (A)顏料⑴丄顏料藍15: 6,粒徑爲30〜90奈米左右]1.303 質量份， (A)顔料[C.I·顏料紫23，粒徑爲2〇〜6〇奈米左右]0·016質 量份， (Β)甲基丙烯酸與苄基甲基丙烯酸酯的共聚合物[甲基丙 稀酸單位與苄基甲基丙烯酸酯單位的組成比爲質量比（莫耳比） 並爲30 : 70，重量平均分子量(皿…爲25000，酸價爲113]0.756 質量份， 1 (C) 二季戊四醇六丙烯酸酯0.887質量份， (D) 光聚合引發劑[2-甲基-2-嗎琳代-1-(4-甲硫基苯基)丙烷 -1-酮]0.197質量份， 光聚合引發助劑[2,4-二乙基噻噸酮]0.099質量份， (E) 丙二醇單甲醚乙酸酯11_7質量份左右以及非離子系界 面活性劑0.314質量份 的著色感光樹脂組成物置入與第一實驗例相同的保存容器並 將容器密封，個別靜置保存在攝氏零下5度、攝氏5度與攝氏 毎 10度。經過6個月後以及經過12個月後，著色感光樹脂組成 物的黏度變化率如表1所示。尙且’經過6個月或是經過I2 個月保存後的著色感光樹脂組成物’無論是在何溫度保存者皆 未生成膠狀物。 上述經12個月保存後的著色感光樹脂組成物，將之塗佈 於基板3上，將溶劑揮發以形成著色感光層4(第2A圖），藉由 對此著色感光層4進行曝光(第2B圖），再進行顯影(第2C圖）， 而能夠得到與使用保存開始前之著色感光樹脂組成物所形成 32 "27pifl "27pifl 之箸色《案相 同的藍色透明著色圖案。 第四實驗例[綠 將含有：9927 pif 1 (ii) Description of the invention: FIELD OF THE INVENTION The present invention relates to a method for preserving a colored photosensitive resin composition. ”Conventional branch technique The color resist composition is a photosensitive resin composition containing a colorant and is suitable for forming a color pattern of a color filter. Here, the color phosphor film 1 is an optical element for colorizing a display image of a liquid crystal display device and for coloring an image captured by a solid-state imaging element (refer to FIGS. 1A and 1B). The colored pattern 2 is, for example, color pixels 2R, 2G, 2B, and a black matrix 2BM, and is configured in a stripe shape (see FIG. 1A) or a mosaic shape (see FIG. 1B). It is known that the colored photosensitive composition system contains (A) a colorant, (B) a polymer binder, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, and is known to contain as (A) Pigment of a colorant. In the photosensitive resin composition, (A) a pigment is dispersed in the composition, and (B) a polymer binder, (C) a photopolymerizable compound, and (D) a photopolymerization initiator are usually dissolved in (E) ) In a solvent. The colored photosensitive resin is coated on the substrate 3, and the colored photosensitive layer 4 obtained by removing the (E) solvent is soluble in an alkaline aqueous solution (Figure 2A), and is irradiated with light 6 (Figure 2B). The photopolymerization initiator generates a living radical or an acid, and polymerizes the (C) photopolymerizable compound from the living radical or the acid. Since the colored photosensitive layer becomes insoluble in an aqueous solution, the colored photosensitive resin composition is used as a negative photoresist as a material for forming a colored pattern (Fig. 2C). Since the (C) photopolymerizable compound and (D) photopolymerization initiator are contained in the colored photosensitive resin composition, the quality changes due to the polymerization of the photopolymerizable compound when stored for a long time. Therefore, the color filter manufacturing method uses 9927 pif 1 to produce a necessary amount of coloring photosensitive resin composition each time the color filter is manufactured. However, if the colored photosensitive resin composition is manufactured every time the color filter is manufactured, it is necessary to cooperate with the manufacturing plan of the color filter to manufacture the colored photosensitive resin composition. Moreover, the amount of manufacturing required due to the one-time use is small. Therefore, it is not conducive to the productivity of the colored photosensitive resin. In addition, in order to avoid the quality change of the colored photosensitive resin composition, it is necessary to leave it as far as possible from the time of manufacture to the manufacture of the color filter, and cool it with dry ice, for example, to a temperature of minus 25 degrees Celsius for storage. . However, the colored photosensitive resin composition that has been left standing and stored in a cooled state with dry ice or the like may have a solution that generates a gel in a short time. As a result of intensive review by the present inventors, they have found out that (A) a coloring agent, (B) a polymer binder, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) If the solvent-colored photosensitive resin composition is maintained at -6 ° C or higher and 15 ° C or lower, its mutual quality will not cause a large change over a long period of time, and it will not be gelled and can be stored. A large number of colored photosensitive resins can further improve the productivity of the colored photosensitive resin composition, thereby completing the present invention. In addition, the inventors have studied the coloring photosensitive resin composition of (A) a colorant, (B) a polymer binder, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. If the object is stored at a temperature of minus 10 degrees Celsius or more and 30 degrees Celsius or less, the formation of colloids can be suppressed, thereby completing the present invention. SUMMARY OF THE INVENTION The object of the present invention is to provide a method for preserving a colored photosensitive resin composition, comprising: (A) a coloring agent, (B) a polymer binder, (C) a photopolymerizable compound, and (D) light The coloring photosensitive resin composition 9927 pif 1 of the polymerization initiator and the (E) solvent is stored at a temperature of -6 ° C to 15 ° C (the first embodiment of the present invention described below). Another object of the present invention is to provide a method for preserving a colored photosensitive resin composition, comprising: (A) a coloring agent, (B,) a polymer binder, (C) a photopolymerizable compound, and (D) light. The coloring photosensitive resin composition of the polymerization initiator and the (E) solvent is stored under shaking at a temperature of minus zero degrees Celsius or more and 30 degrees Celsius or less (the second embodiment of the present invention described below). Figure 1B is a schematic diagram of an example of a color filter; Figures 2A to 2C are schematic diagrams showing the manufacturing steps of a colored pattern, and Figures 3A to 3C are the manufacturing steps of a colored pattern. And FIG. 4A to FIG. 4C show the manufacturing steps of the colored pattern. Description of the drawing 1: color filter 2, 2, 2, 2 ": colored pattern 3: substrate 4, 4, 4, 4": colored photosensitive layer 5: photomask 6: light 41: unirradiated area 42: illuminated Area 9927 pif 1 51: glass plate 52: light-shielding layer 53: light transmitting portion 2B: blue pattern 2BM: black matrix 2G: green pattern 2R: red pattern Example of the invention The colored photosensitive resin composition preserved by the method of the present invention The system contains (A) a colorant, (B) a polymer binder, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. (A) The colorant may be an organic colorant or an inorganic colorant, and the organic colorant may be a pigment or a dye. Moreover, the colorant may be a natural pigment or a synthetic pigment. The inorganic colorant may be an inorganic color such as a metal oxide, a metal salt, an inorganic salt of barium sulfate (complex pigment), or the like. Among the colorants, an organic colorant is preferably used, and an organic pigment is more preferably used. Specific organic pigments and inorganic pigments are, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). Specific examples are cI · Pigment Yellow 1, CI Pigment Yellow 3, CI · Pigment Yellow 12, CI Pigment Yellow 13, CI · Pigment Yellow 14, CI Pigment Yellow 15, CI · Pigment Yellow 16, c ·; [• Pigment Yellow 17, Cl Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment yellow 110, CI pigment yellow 117, CI pigment yellow 125, CI pigment yellow 128, CI pigment yellow 9927 pif 1 137, 0.1 pigment yellow 138, CI pigment yellow 139, cI pigment yellow 147, cI pigment yellow 150, CI · Pigment Yellow 153, CI · Pigment Yellow 154, CI · Pigment Yellow 166, CI · Pigment Yellow 173 and other yellow pigments, CI · Pigment Orange 13, CI · Pigment Orange 31, CI Pigment Orange 36, CI · Pigment Orange 38. CI Pigment Orange 40, CI Pigment Orange 42, CI Pigment Orange 43, (: Black Pigment Orange 51, CI Pigment Orange 55, CI Pigment Orange 59, cI Pigment Orange 6 丨, CI Pigment Orange 64, CI Pigment Orange 65 , CI Pigment Orange 71, · Pigment Orange and other orange pigments, CI Pigment Red 9, CI · Pigment Red 97, CI · Pigment Red 105, cI · Pigment Red 122, C. I. Pigment Red 123, CI Pigment Red 144, C_I Pigment Red 149, C_I Pigment Red 166, CI Pigment Red 168, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192 , CI · Pigment Red 215, CI · Pigment Red 216, CI · Pigment Red 224, CI · Pigment Red 242, CI · Pigment Red 254, CI · Pigment Red 264, CI · Pigment Red 265, etc., CI · Pigment Blue 15 C_I · Pigment Blue 15: 3, CI · Pigment Blue 15: 6, CI Pigment Blue 15 ·· 4, CI · Pigment Blue 15: 6, CI Pigment Blue 60 and other blue fuels, CI · Pigment Blue 1, C .I_Pigment Violet 19, CI Pigment Violet 23, CI · Pigment Violet 29, CI · Pigment Violet 32, CI · Pigment Violet 36, CI Pigment Violet 38 and other purple pigments, CI · Pigment Green 7, CI · Pigment Green 36 Green pigments such as CI · Pigment Brown 23, CI · Pigment Brown 25 and other brown pigments, CI · Pigment Black 1, CI · Pigment Black 7 and other black pigments. These organic pigments and inorganic pigments can be used individually, They can also be used in combination of two or more. The organic pigment may be applied with a rosin treatment, a surface treatment using a pigment derivative that introduces an acidic group or a basic group, a grafting treatment of the pigment surface by a polymer compound, or a sulfuric acid micronization method according to need. Etc. Micro 9927 pifl granulation treatment, or an organic solvent or water or water washing treatment to remove impurities. The particle size of the organic pigment is approximately 10 nm to 150 nm. The content of the colorant, and the volatile component (solvent) contained in the colored photosensitive resin composition, have a mass fraction of 5% or more with respect to the solid content after volatilization, which is 10% or more in consideration of the formation of a sufficiently colored colored pattern. Furthermore, it is 20% or more, especially 30% or more, usually 60% or less, and preferably 50% or less. Moreover, when the colorant is an organic pigment, the mass fraction of the amount of the organic pigment used relative to the total amount is 50% or more, preferably 55% or more. The entire amount of the colorant (100%) may be organic. pigment. (B) As the polymer binder, a propylene fluorene-based copolymer can be used. For example, a copolymer containing a carboxyl group-containing monomer and other monomers copolymerizable therewith can be used. The carboxyl group-containing monomer is, for example, an unsaturated polycarboxylic acid such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, and the like, and an unsaturated carboxylic acid having at least one carboxyl group. Here, the unsaturated monocarboxylic acid is, for example, acrylic acid, methacrylic acid, butenoic acid, 2-chloropropionic acid, 2-phenylacrylic acid, or the like. The unsaturated dicarboxylic acid is exemplified by maleic acid, trans-butenedioic acid, methylene succinic acid, cis-methyl butenedioic acid and methyl trans-butenedioic acid, and the like. The unsaturated polyvalent carboxylic acid is an anhydride thereof, and specifically, maleic anhydride, transbutanedioic anhydride, and maleic butanedioic anhydride may be mentioned. Moreover, the unsaturated polyvalent carboxylic acid may also be its mono (2-methacrylfluorenyloxyalkyl) ester, specifically, for example, succinic acid mono (2-propenylfluorenyloxyethyl), o-benzene Dicarboxylic acid mono (2-propenylfluorenyloxyethyl), phthalic acid mono (2-methacrylfluorenyloxyethyl), and the like. The unsaturated polyvalent carboxylic acid may be a mono (meth) acrylic acid ester having a carboxyl polymer at both ends, and specifically, for example, 0-polycaprolactone monoacrylate and 0-polycaprolactone monomethacrylic acid ester. The carboxyl group-containing monomers can be used singly or in combination of 583506 9927 pif 1 or more. Other monomers that can be copolymerized with carboxyl-containing monomers are, for example, styrene, α-methylstyrene, 0-vinyltoluene, m-vinyltoluene, P-vinyltoluene, p-chloro Styrene, 0-methoxyphenylethyl, m-methoxystyrene, p-methoxystyrene, 0-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, P -Vinyl benzyl methyl ether, 0-vinyl benzyl epoxy propyl ether, m-vinyl benzyl epoxy propyl ether, P-vinyl T-based epoxy propyl ether, indene and other aromatic ethylene Base compound, methacrylate, methmethacrylate, ethacrylate, ethyl # methacrylate, η-propyl acrylate, η-propyl methacrylate, i-propyl acrylate , I-propyl methacrylate, η-butyl acrylate, η-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate Ester, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate , 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl Acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methyl Acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenol acrylate, phenol methacrylate, 2-methylethyl acrylate, phenoxyethyl acrylate, methoxydiethyl Glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol Methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclopentadienyl acrylate, cyclopentadienyl methyl Prop 11 583506 9927 pif 1 enoate, 2-hydroxy- 3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. ^ 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate , 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropylmethyl Unsaturated carboxylic acid amino alkyl esters such as acrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc. Unsaturated carboxylic acid amino glycidyl esters such as methacrylate, unsaturated vinyl amino esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc. Unsaturated ethers such as methyl ether, vinyl ethyl ether, propenyl glycidyl ether, acrylonitrile, methacrylic acid , Α - chloro acrylonitrile, vinylidene group of Amides Amides such as vinyl compounds, acrylamide, methyl acrylamide, α - chloro acrylamide, Ν-2- oxoethyl < Unsaturated amines such as acrylamide, N-2-oxoethylmethacrylamide, maleic acid, N-phenyl maleimide, N-cyclohexyl maleimide Unsaturated imines such as enediimine, diene esters such as 1,3-butadiene, isoprene, chloroprene, polystyrene, polymethacrylate, polymethylformamide Polymer monomers based on polyacrylic acid esters, poly-η-butyl acrylates, poly-η-butyl methacrylates, and polysiloxanes have monoacrylfluorene groups or monomethacrylfluorene groups at the ends. . These single systems can be used individually or in combination of two or more. 12 583506 9927 pif 1 The content of the monomer unit containing a carboxyl group in the copolymer is usually about 10 to 50%, preferably about 15 to 40%, and more preferably about 25 to 40%. The acrylic fluorene-based copolymer is, for example, a (meth) acrylic acid / meth (meth) acrylate copolymer, a (meth) acrylic acid / benzyl (meth) acrylate copolymer, or (meth) ) Acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (fluorenyl) acrylate copolymer, (meth) acrylic acid / meth (meth) acrylate / polystyrene macromonomer copolymerization Polymer, (meth) acrylic acid / meth (meth) acrylate / meth (meth) acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene Macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / meth (meth) acrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (methyl ) Acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / Meth (meth) acrylate macromonomer copolymer, methacrylic acid / polystyrene / benzyl (meth) acrylate / N_phenylcis butylene difluorene , (Meth) acrylic acid / succinic acid mono (2-propenyloxyethyl) / polystyrene / propyl (meth) acrylic acid / N-phenylcis butylene diimide copolymer, (Meth) acrylic acid / benzyl (meth) acrylate / N-phenylcis butylene diimide / polystyrene / glycerol monomethacrylate copolymer and the like. In addition, acrylates and methacrylates are represented as (meth) acrylates. Among them, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene copolymer, and methyl (methyl) ) Acrylate / (meth) acrylic acid / polystyrene copolymer, more preferably a (meth) acrylic acid / benzyl (meth) acrylate copolymer. The polystyrene-equivalent weight average molecular weight of the propylene-based copolymer is preferably 3000 to 4,000,000, more preferably 5,000 to 1,000,000, and particularly preferably 20,000 to 40,000. The weight-average molecular weight (Mw) is based on polystyrene, and the fluorene measured by GPC 13 9927 pif 1 gel permeation chromatography (GPC). The acid value of the propylene-based copolymer is preferably 30 to 250, more preferably 60 to 180, and particularly preferably 90 to 160. Here, the acid value is determined by measuring the amount of sodium hydroxide (mg) required to neutralize 1 gram of propylene fluorene-based copolymer. Generally, 1 gram of polymer binder can be dissolved in 10 cubic centimeters of water and 40 cubic meters. A mixed solvent of acetone in cm was determined by measuring pH 一边 and titrating with sodium hydroxide. The mass fraction of the colored photosensitive resin composition used in combination with the resin system is usually 5% or more, preferably 10% or more, more preferably 20% or more, usually 90% or less, preferably 80% or less, and more preferably A range of about 70% or less. (C) The photopolymerizable compound is a compound polymerized by living radicals, acids, and the like generated by irradiation with light and a photopolymerization initiator, and is, for example, a compound having a polymerizable carbon-carbon unsaturated bond. The photopolymerizable compound is preferably a polyfunctional photopolymerizable compound having four or more functional groups. The polyfunctional photopolymerizable compound having four or more functional groups is, for example, pentaerythritol tetraacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Acrylate, dipentaerythritol hexa (meth) acrylate. The content of the photopolymerizable compound in the colored photosensitive resin composition is such that the mass fraction of the colored photosensitive resin composition is usually 1% or more and 60% or less, and preferably 3% or more and 50% or less. (D) The photopolymerization initiator is, for example, an active radical generator that generates an active radical by irradiation with light, and an acid generator that generates an acid. The living radical generator is, for example, the acetophenone-based photopolymerization initiator, the triazabenzene-based photopolymerization initiator, the benzophenone-based photopolymerization initiator, the benzophenone-based photopolymerization initiator, or Ton ketone-based photopolymerization initiator. 583506 9927 pif 1 acetophenone-based photopolymerization initiators are, for example, diethoxyacetophenone, 2-meryl-2-methyl_1-phenylpropanone, benzyldimethylketal, 2_hydroxy_2_methyl-W4- (2-hydroxyethoxy) phenyl] propane ketone, hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino 4- (4-methyl Thiophenyl) propane_; μ 嗣, hydroxy_2_methylmethylvinyl) phenyl] propanone oligomers and the like. The benzophenone-based photopolymerization initiator is exemplified by benzophenone, benzophenone methyl ether, benzophenone ethyl ether, benzophenone isopropyl ether, and benzophenone isobutyl Ether. Examples of the triazine-based photopolymerization initiator are 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -13,5_triazabenzene, 2,4 · Bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5 · Triazabenzene, 2,4-bis (trichloromethyl) -6-piperyl-1 , 3,5-triazabenzene, 2,4 · bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5_triazabenzene, 2,4- Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazabenzene, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-triazabenzene, 2,4-bis (trichloromethyl) -6- [2- (4-ethyl Amino-2_methylphenyl) ethenyl] -1,3,5-triazabenzene, 2,4-bis (trichloromethyl) -6- [2_ (3,4-dimethoxybenzene Group) vinyl] -1,3,5-triazabenzene and the like. Examples of the benzophenone-based photopolymerization initiator are benzophenone, 0-benzophenone benzoate, 4-phenylbenzophenone, and 4-phenylfluorenyl-4'-methyl. Diphenyl sulfide, 3,3 ', 4,4, -tetra (t · butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like. The thioxanthone-based photopolymerization initiator is, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, or 2,4-dichlorothioxanthone. Ketones, 1-chloro-4-propoxythioxanthone and the like. Examples of the active radical generator are 2,4,6-trimethylphenyldiphenylphosphine oxide, 2,2, -bis (0-chlorophenyl) -4,4,5,5, -tetramethane Phenyldiimidazole, 10 · 15 9927 pifl Butyl-2-chlorodiabenidone, 2-ethylallioquinone, fluorenyl, 9,10-phenanthrenequinone, awakening, phenylglyoxylate Esters, titanocene compounds, etc. As the acid generator, for example, 4-hydroxyphenyldimethylfluorene p-toluenesulfonyl ester, 4-hydroxyphenyldimethylfluorene hexafluoroantimonate, 4-acetoxyphenyldimethylfluorene P- Tosylsulfonium I purpose, 4 · Acetyl hetero · methyl · | Hexafluoroalkanoate, Triphenylsulfonium P-toluenesulfonyl ester, Triphenylsulfonium hexafluoroantimonate, Diphenyliodohydrogen p-methylbenzyl, iron salts such as monoiodohydrohexafluoroantimonate, or nitrobenzyl p-toluenesulfonate's diphenylethanolone p-toluenesulfonate. / Among the above-mentioned compounds that are active radical generators, there are also compounds that generate both active radicals and acids. For example, active radical generators such as triazine photopolymerization initiators, can also be used as acid generators. use. These photopolymerization initiators can be used individually or in combination of two or more. Among the photopolymerization initiators, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propanone and triazabenzene-based photopolymerization are preferably used as the acetophenone-based photopolymerization initiator. As the polymerization initiator, it is preferred to use 2,4 · bis (dichloromethyl) piperidyl- ,,% triazabenzene. The content of the photopolymerization initiator of the colored photosensitive resin composition is usually 1% or more and 25% or less, and preferably 3% or more and 20% or less of the mass fraction of the colored photosensitive resin composition. The colored photosensitive resin composition of the present invention may contain a photopolymerization initiator. A photopolymerization initiator is used in combination with a photopolymerization initiator to promote polymerization of a photopolymerizable compound. Examples of the photopolymerization initiation aid include amine-based photopolymerization initiation aids, alkoxy onion-based photopolymerization initiation aids, and the like. Examples of the amine-based photopolymerization initiation aid are triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethanolamine benzoate, ethyl 4-dimethanolamine benzoate, and 4-dimethanol. Ethyl amine benzoate isoamyl, 2-dimethyl 583506 9927 pif 1 alcohol amine ethyl ester, 4-dimethanolamine benzoic acid 2-ethylhexyl ester. N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamine) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamine) benzophenone, 4,4'-bis (ethylmethylamine) benzophenone and the like. Examples of the alkoxy onion-based photopolymerization initiation aid are, for example, 9,10-dimethoxy onion, 2-ethyl-9,10-dimethoxy onion, and 9,10-diethoxymethyl. Scallions, 2-ethyl-9, 10-diethoxymethoxy scallions, etc. In the case of using a photopolymerization initiation aid, the amount of the photopolymerization initiator used is 1 mol or less, preferably 0. 〇1 mol or more and 5 mol or less. When a photopolymerization initiator and a photopolymerization initiation aid are used, the molar fraction of the total amount of the polymer binder and the photopolymerizable compound is usually 3% to 48%, preferably 5 Above 36%. (E) The solvents are the same as those used for the conventional colored photosensitive resin composition, and examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols, esters, and amidines. The ethers are exemplified by tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutylene. Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethyl ether Glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl ethylene glycol ether acetate, ethyl ethylene glycol ether acetate, ethyl acetate Ethoxyethoxyethanol acetate, butylethoxyethoxyethanol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, benzyl Ether, phenyl ether, methyl anisole, etc. Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and xylene. Ketones are exemplified by methyl ethyl ketone, acetone, methyl pentanone, methyl isobutyl 17 9927 pif 1 ketone, 2-butanone, 2-heptanone, 4-methyl-2-pentanone, cyclic Hexanone, etc. Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and propylene glycol. The esters are, for example, ethyl acetate, acetic acid: n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid Ethyl ester, butyl butyrate, alkyl esters, methyl propionate, ethyl propionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl oxymethyl acetate, oxymethyl acetate Ethyl acetate, butyl oxymethyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxypropionate Propyl ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate Ethyl acetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2-methylpropionate, methylpyruvate, ethylpyruvate, propylpyruvate, ethylacetate, ethylacetate Ethyl, 2-carboxy methyl butyrate, ethyl 3-methoxybutyl group, 3-methyl-3-methoxybutyl acrylate, butyrolactone Amides like. The amidines are, for example, N, N'-2-dimethylformamide, N, N'-dimethylacetamide, and the like. Other solvents are, for example, N-methylpyrrolidone, dimethylsulfoxide, and the like. Among the above solvents, methyl 3-methylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl glycol ethyl ether acetate, and propionic acid are preferably used. Ethyl ester, diethylene glycol dimethyl ether, butyl acetate, ethyl ethoxyethoxyethanol acetate, butyl ethoxyethoxy ethanol acetate, propylene glycol monomethyl ether acetate, 2-heptane Ketones, etc. These solvents can be used individually or in combination of two or more. The amount used is based on the mass of the colored photosensitive resin composition in a solvent-diluted state. The 9927 pif 1 fraction is usually 50% to 90%, preferably 60% to 85%. When the colored photosensitive resin composition contains a raw material as a colorant, a pigment dispersant may be contained. By containing a pigment dispersant, the contained pigment can have a uniform dispersion state, and a uniformly colored coloring pattern can be obtained. Pigment dispersants are, for example, dispersants such as polyester-based polymer dispersants, acrylic polymer-based polymer dispersants, polyurethane-based polymer dispersants, cationic surfactants, and anionic surfactants. , Non-ionic surfactants and other surfactants. When a pigment dispersant is contained, its content is usually 0 to 1 part by mass of the colorant. 01 parts by mass or more, preferably 0.05 parts by mass or more, usually 1 part by mass or less, preferably 0. 5 parts by mass or less. The coloring photosensitive resin material may contain additives other than the filler, the polymer binder (B), adhesion promoter, antioxidant, ultraviolet absorber, anti-agglomerating agent, organic acid, organic ammonia compound, and hardener. . The filler is, for example, fine particles such as glass and aluminum. The high molecular compound is, for example, polyvinyl alcohol, polyacrylic acid ', ethylene glycol monoalkyl ether, polychloroalkylpropylene glycol, and the like. Adhesion promoters are, for example, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri (2-methoxyethoxy) silane, and N- (2-aminoethyl) -3-amino group. Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4_ Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylmethylpropyltrimethoxysilane, 3-hydrothio Propyltrimethoxysilane, etc. Antioxidants are for example 2. 2-thiobis (4-methylbutylphosphonium), 2,6-di-t-butylphenol and the like. The ultraviolet absorber is, for example, a benzotriazole system such as 2- (2-hydroxy-3-t-butylmethylbenzene 583506 9927 pif 1 group) -5-benzotriazole, 2-hydroxy-4-octyl Benzophenones such as hydroxybenzophenone, benzoates such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate class. Examples of the anti-agglomerating agent include sodium polyacrylate and salts. The organic acids are, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, hexanoic acid, diethylacetic acid, heptanoic acid, and octanoic acid; Diacid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, melamine Methylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanecarboxylic acid, mesuccinic acid, cis methylbutenedioic acid, maleic acid, transbutenedioic acid Aliphatic dicarboxylic acids such as acids, methyl transbutenedioic acid, etc., aliphatic tricarboxylic acids such as trimellitic acid, propylene-1, 2,3-carboxylic acid, camphor tricarboxylic acid, benzoic acid, toluic acid , Aromatic monocarboxylic acids such as p-isopropylbenzoic acid, trimellitic acid, mesitylene, etc., aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as pyromellitic acid, trimellitic acid and pyromellitic acid. The organic amine compound is, for example, η-propylamine, i-propylamine, η-butylamine, i-butylamine, sec-butylamine, t-butylamine, η-pentylamine, η-hexylamine, η-heptylamine , Η-octylamine, η-nonylamine, η-decylamine, η_ ~ [-amine, η-dodecylamine, and other single-amine amines, cyclohexylamine, 2-methylcyclohexylamine, 3-methylamine Monocycloalkylamines such as methylcyclohexylamine, 4-methylcyclohexylamine, methylethylamine, dimethylamine, methylη-propylamine, ethylη-propylamine, diη-propylamine, and di-propylamine , Di-n-butylamine, di-i-butylamine, disec-butylamine, di-t-butylamine, 20 583506 9927 pif 1 dialkylamines such as di-n-pentylamine, di-n-hexylamine, methyl Monoalkyl monocycloalkylamines such as cyclohexylamine, ethylcyclohexylamine, bicycloalkylamines such as dicyclohexylamine, dimethylethylamine, methyldiethylamine, triethylamine, dimethyl Η-propylamine, diethylη-propylamine, methyldiη-propylamine, ethyldiη-propylamine, tri-η-propylamine, tri-i-propylamine, tri-n-butylamine, tri-i-butylamine, trisec -Trialkylamines such as butylamine, tri-t-butylamine, tri-n-pentylamine, and tri-n-hexylamine; dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine Class, Monocyclobicycloalkylamines such as dicyclohexylamine, ethyldicycloethylamine, tricycloalkamines such as tricyclohexylamine, 2-aminoethanol, 3-amino-1-propanol Monoalkanolamines such as 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1 -Monocycloalkanolamines such as cyclohexanol, diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine Dialkanolamines such as di-n-hexanolamine, dicycloalkanols such as di (4-cyclohexanol) amine, triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri Trialkanolamines such as η-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, and tri-n-hexanolamine; tricycloalkanols such as tris (4-cyclohexanol) amine Class, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethyl Amino-alkanediols such as amine-1,2-propanediol, 2-dimethylamine-1,3-propanediol, 3-diethylamine-1,2-propanediol, 2-diethylamine-1,3-propanediol , 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, etc. Aminocycloalkanediols, 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol and the like containing aminocycloalkanone 21 583506 9927 pif 1 methanol, 1-aminocyclohexanone methanol, 4-aminocyclohexanone Amino-containing cycloalkanones such as ketomethanol, 4-dimethylcyclopentanemethanol, 4-diethylcyclopentanemethanol, 4-dimethylcyclohexanemethanol, 4-diethylcyclohexanemethanol, etc. Methanol, β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminopentanoic acid, 5-aminopentanoate Amino acids such as acids, 6-aminoheptanoic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, aniline, 0-methylaniline, m-formyl Aniline, p-methylaniline, p-ethylaniline, pn-propylaniline, pi-propylaniline, p-η-butylaniline, pt-butylaniline, 1-naphthylamine, 2- Aromatic amines such as naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-dimethylaniline, o-aminobenzylethanol, m-aminobenzylethanol , P-aminobenzylethanol, p-dimethylaminobenzylethanol, P-diethyl Aminobenzylethanols such as aminobenzylethanol, o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol, etc., m- Aminobenzoic acids such as aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and P-diethylaminobenzoic acid. The curing agent is, for example, a compound capable of reacting with a carboxyl group in the polymer binder (B) by heating to bridge the polymer binder. Also mentioned are compounds which are individually polymerized to harden a colored pattern. These compounds are exemplified by epoxy compounds and oxetane compounds. The epoxy compound is exemplified by a bisphenol A-based epoxy resin, a hydrogenated bisphenol A-based epoxy resin, a bisphenol F-based epoxy resin, a hydrogenated bisphenol F-based epoxy resin, a phenolic epoxy resin, and others Aromatic epoxy resins, cycloaliphatic epoxy resins 22 583506 9927 pif 1 epoxy resins, such as epoxy resins, complex cyclic epoxy resins, glycidate resins, glycidylamine resins, epoxy resins, etc. Or the brominated derivatives of these epoxy resins, aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, and (co) polymers of butadiene Epoxides, epoxides of (co) polymers of isoprene, (co) polymers of glycidyl (meth) acrylates, triglycidyl isoamidine esters, and the like. The oxetane compound is exemplified by carbonate dioxetane, xylene dioxetane, adipate dioxetane, terephthalate dioxetane Alkane, cyclohexanedicarboxylic acid dioxetane, and the like. When the colored photosensitive composition of the present invention uses an epoxy compound or an oxetane compound as a hardener, it may also include a compound obtained by ring-opening polymerization of an epoxy group of an epoxy compound or an oxetane compound. These compounds are, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like. The polyvalent carboxylic acids are, for example, phthalic acid, 3,4-dicarboxylic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, naphthalenetetracarboxylic acid, 3 Aromatic polyvalent carboxylic acids such as, 3 ', 4,4'-benzophenonetetracarboxylic acid, succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid Aliphatic polyvalent carboxylic acids such as maleic acid, trans-butenedioic acid, mesuccinic acid, hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroiso Phthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, 1,2,4, Cycloaliphatic polyvalent carboxylic acids such as 5-cyclohexanetetracarboxylic acid. The polyvalent anhydride is, for example, aromatic polyvalent anhydrides such as phthalic anhydride, pyromellitic anhydride, partial dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, and the like. Carboxylic anhydrides, methylsuccinic anhydride, succinic anhydride, cis methylbutanedioic anhydride, dodecene succinic anhydride, glyceric anhydride, maleic anhydride, butanetetracarboxylic acid 23 583506 9927 pifl Aliphatic polyvalent carboxylic anhydrides such as dianhydride, hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2, Cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, alicyclic polyvalent carboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid, dianhydride, dicycloheptene dicarboxylic anhydride Anhydrous alicyclic polyvalent carboxylic acids, such as chlorazine anhydride, carboxylic acid anhydrides containing ester groups, such as ethylene glycol bistrimellitic acid and glycerol bistrimellitic anhydride. As the carboxylic acid anhydride, for example, a commercially available epoxy resin hardener can be used. The epoxy resin hardener is, for example, the trade name "ADEKA HARDENER-EH-700" ^ (Asahi Denka Kogyo Co., Ltd.), and the trade name "Rikasid (!; Rishy H ') HH" (new Japan Physico Chemical Co., Ltd.), trade name "MH-700" (New Japan Physico Chemical Co., Ltd.), etc. The hardener can be used alone or in combination of two or more. In the colored photosensitive resin composition, (A) the colorant is a pigment that is used, and the pigment is usually dispersed in the composition. When a dye is used as the colorant (A), the dye may be dispersed in the composition or dissolved in a solvent. (B) The polymer binder, (C) the photopolymerizable compound, and (D) the photopolymerization initiator are dissolved in the (E) solvent. The storage method of the first embodiment of the present invention is to maintain the colored photosensitive resin composition _ at a temperature of -6 ° C or more and 15 ° C or less. When the colored photosensitive resin composition is stored without shaking, if it exceeds 15 ° C, the viscosity during long-term storage will easily change, and if it is below 8 ° C, and if it is less than -6 ° C, gelation will easily occur. The storage method of the first embodiment of the present invention is to store a colored photosensitive resin composition in a container, and store the colored photosensitive resin composition in a void portion obtained by subtracting the volume occupied by the colored photosensitive resin composition from the content of the container. The product of the ratio of the internal volume (void ratio,%) and the oxygen partial pressure (hPa) of the ambient gas in the void portion is 24 583506 9927 pif 1 2000 (% · hPa) or more, preferably 4000 (% · hPa) or more. Ambient gas. If the product of the partial pressure of oxygen with the ambient gas in the space is less than 2000 (% · hPa), gelation is liable to occur. The storage method according to the second embodiment of the present invention is a storage method in which the colored photosensitive resin composition is shaken. The method of shaking the colored photosensitive resin composition is, for example, filling the colored photosensitive resin composition into a container and shaking the container. In the second embodiment of the present invention, the colored photosensitive resin composition can fill a container with a filling rate of 50% to 100%. It can also be less than 50 #%, but it is not good due to the low efficiency of charging. If the filling rate is less than 100%, a void will be generated in the container. This void can also be filled with inert gas such as nitrogen, argon, or air. For container vibration, for example, a shaker can be used to shake the container horizontally or vertically. Furthermore, the container filled with the colored photosensitive resin composition may be closed and repetitively turned upside down. The container can be continuously vibrated, and the vibration and standing can be repeated at intervals of 30 minutes. In the second embodiment of the present invention, the storage temperature is above -10 ° C, preferably above -7 ° C, below 30 ° C, and more preferably below -10 ° C. In the first and second embodiments of the present invention, the container is a colorless and transparent visible light transmissive material, such as a container made of inorganic glass. Specifically, a colorless and transparent glass container can be used. However, it is preferably Containers stored in the transmittance range of 250 nm to 440 nm with a wavelength range of 0% to 8%, and preferably 5% or less, can be suppressed by storing in a colored glass bottle or the like, for example. Generation of gels. It can also be used in a container with a light transmittance in the wavelength range of 250 nm to 440 nm exceeding 8%, such as a colorless and transparent glass bottle containing 25 583506 9927 pifl into the colored photosensitive resin composition, and then placing this container into light A container with a transmittance in the wavelength range of 250 nm to 440 nm is 8% or less, preferably 5% or less. For example, it is a cardboard box, black plastic bag, colored plastic storage container, metal storage container, etc. To save. The light transmittance exceeding the wavelength range of 440 nm may exceed 8% ′, however, it is preferably 8% or less, and more preferably 5% or less. It is also possible to use a container that completely blocks light in the wavelength range of 250 nm to 440 nm (transmittance is 0%) ° A colored pattern is formed from the colored photosensitive resin composition after storage. For example, it can be patterned as usual The colored photosensitive resin composition after storage. Specifically, the colored photosensitive resin composition after being stored is coated on the substrate 3 to remove the (E) solvent to form a colored photosensitive layer 4 (Figure 2A), and then the colored photosensitive layer is exposed by exposure (Figure 2B) ) And developing methods to form. The substrate 3 is, for example, a flat glass substrate, a silicon substrate, a polycarbonate substrate, a polyethylene substrate, an aromatic polyimide resin substrate, a polyimide substrate, or a polyimide resin substrate. Substrate. These substrates can also be subjected to pretreatments such as pharmaceutical treatments such as silane coupling agents, plasma treatments, ion plating, sputtering, chemical vapor deposition, and vacuum evaporation. When a silicon substrate is used as the substrate, a surface such as a charge-coupled device (CCD), a thin film transistor (TFT), or the like can also be formed on the surface of the silicon substrate. The method of coating the photosensitive resin composition with a uniform thickness on a substrate is, for example, a spin coating method, a cast coating method, a roll coating method, and a slit and spin coating method. And other ordinary coating methods. After the application (E), the solvent can be removed, for example, by heating. The coloring photosensitive layer 4 to be formed thereafter is a layer formed by removing solid components of the coloring photosensitive resin composition from volatile components such as (E) solvents. Next, the colored photosensitive layer 4 is exposed (FIG. 2B). The exposure may be, for example, 26 583506 9927 pifl and irradiate the light 6 with the mask 5. The light 6 usually uses ultraviolet rays called g-line (wavelength 436 nm) and i-line (wavelength 365 nm). The light is irradiated by a spaced photomask. Here, the photomask 5 is, for example, a light shielding layer 52 formed on the surface of the glass substrate 51 to block light. The portion of the glass substrate Η where the light-shielding portion 52 is not provided is a light-transmitting portion 53 ′ through which the pattern is exposed to the colored photosensitive layer 4 according to the pattern of the light-transmitting portion to form an unirradiated area 41 that is not irradiated with light and irradiation with light. Area 42. The amount of light irradiated from the irradiated area 42 can be determined according to (A) the type or content of the colorant, (B) the weight average molecular weight of the polymer binder, the content, the monomer unit composition, and (C) the photopolymerizable compound. The kind, content, (D) kind and content of the photopolymerization initiator are appropriately selected. After exposure, it is developed (Figure 2C). The development is performed by, for example, bringing the colored photosensitive layer 4 after exposure into contact with a developing solution, and specifically immersing the substrate 3 having the colored photosensitive layer 4 formed on the surface into the developing solution. The developer is usually an alkaline aqueous solution. The alkaline aqueous solution is, for example, an aqueous solution of basic compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide. The unirradiated area 41 which is not irradiated with light is removed by development. On the other hand, the remaining light irradiated area 42 constitutes the colored pattern 2. After development, the desired coloring pattern 2 is usually obtained by washing and drying. It can also be heated after drying. Increasing the hardness by heating the colored pattern can increase its mechanical strength. When the colored photosensitive resin composition contains a hardener, the mechanical strength can be further improved. The heating temperature is usually 180 ° C or higher, and preferably 200 ° C or higher. Usually below 250 degrees Celsius. On the substrate 3 on which the colored pattern 2 is formed, a colored photosensitive resin composition containing colorants of different colors is coated, and the colored photosensitive layer 4 'is formed by removing the solvent, and exposed (Figure 3B) and developed (Figure 3C). The photosensitive layer 4 'is colored, and a colored pattern 2' can be formed again. Furthermore, by using colored photoresist group 27 583506 9927 pifl containing coloring agents of different colors and repeating the above-mentioned operations, the colored pattern 2 ”can be sequentially formed (FIGS. 4A to 4C), and it can be manufactured with coloring. Color filters 1 in patterns 2, 2 ', 2 "(Figs. 1A to 1B). The coloring photosensitive resin composition for producing the above-mentioned color filter 1 can be used directly by the user's manufacture, a short-term saver, or a saver by the method of the present invention. According to the storage method of the first embodiment of the present invention, even if the storage period is 12 months, the quality of the colored photosensitive resin composition does not change. Also, '' does not produce glue. Therefore, a colored pattern can be formed with the use of the colored photosensitive resin composition after manufacture, and the colored pattern can be formed under the same conditions. In addition, since the colored photosensitive resin composition can be stored for a long period of time without major changes in quality ', it can be manufactured in large quantities at one time, and the productivity of the colored photosensitive resin composition can be improved. The effect of improving the productivity of the colored photosensitive resin composition is increased as the storage period increases in March, June, and December. The preservation method according to the first embodiment of the present invention 'Since the colored photosensitive resin composition during storage hardly generates gels, the same conditions as those for forming a colored pattern using the colored photosensitive resin composition after manufacture' can be used to form the same colored pattern. Hereinafter, the present invention will be described in more detail through experimental examples. However, the present invention is not limited to the following experimental examples. In addition, in the following experimental examples and comparative examples, the quality of the colored photosensitive resin composition, the rate of change in viscosity, and the presence or absence of a gel were evaluated. The viscosity change rate is calculated from the formula (1) obtained by measuring the viscosity U Q) before the start of storage and measuring the viscosity U) after the storage. Viscosity change rate = ¥ (!) The presence or absence of gelatinization of the colored photosensitive resin composition was evaluated by visual observation. 28 583506 9927 pif 1 The first experimental example [green colored photosensitive resin composition] will contain: (A) pigment [c 丄 Pigment Green 36, particle size of about 30 to 80 nanometers], 0704 parts by mass, ( A) Pigment [C. I · Pigment Yellow 150, particle size is about 30 ~ 80 nm] 0. 340 parts by mass, (B) a copolymer of methacrylic acid and benzyl methacrylate [composition ratio of methacrylic acid unit to benzyl methacrylate unit is mass ratio (molar ratio) 0 and is 35: 65, weight average molecular weight (Mw) is 35,000, acid value is 135] 0. 787 parts by mass, (C) dipentaerythritol hexaacrylate 0.1 472 parts by mass, (D) a photopolymerization initiator [2-methyl-2-morpholino-small (4-methylthiophenyl) propane-1-one] 0. 189 parts by mass, photopolymerization initiation aid [4,4’_bis (diethylamine) benzophenone] 0. 063 parts by mass, (E) about 11.8 parts by mass of propylene glycol monomethyl ether acetate, an epoxy compound [n-cresol awakening epoxy resin, "Sumiepoxy ESCN_195_XL-80" (manufactured by Sumitomo Chemical Industries, Ltd.) ] 0. 315 parts by mass and non-ionic surfactant 0. 318 · Mass parts of the colored photosensitive resin composition (green) are placed in a storage container [light-shielding with a light transmittance of 25 nm to 440 nm of 5% or less], and the container is sealed and stored individually at -0 ° C 5 degrees and 10 degrees Celsius. Table 6 shows the viscosity change rate of the colored photosensitive resin composition after 6 months and 12 months. Also, ‘colored photosensitive resin composition after storage for 6 months or 12 months’, no gelatinous substance was formed at any temperature. The above-mentioned colored photosensitive resin composition 'stored after 12 months' was coated with 29 9927 pif 1 on the substrate 3, and the solvent was volatilized to form a colored photosensitive layer 4 (FIG. 2A), and the photosensitive layer 4 was colored by this By exposing (Figure 2B) and then developing (Figure 2C), the same green transparent colored pattern as the colored pattern formed using the colored photosensitive resin composition before the start of storage can be obtained. The first comparative example [green colored photosensitive resin composition] The same colored photosensitive resin composition as in the first experimental example was placed in the same storage container as the first experimental example, and it was individually stored and stored at minus 8 degrees Celsius and 20 degrees Celsius. With 30 degrees Celsius. Preservation at minus 8 degrees Celsius produced gelatin after 1 week. The viscosity changes after 3 months, 6 months and 12 months are shown in Table 1.尙 Furthermore, gelatine will not be produced after 6 months of storage at 20 ° C, and gelatine will not be generated at 1 ° C and 3 months after storage at 30 ° C. The second experimental example [long-term storage of red colored photosensitive resin composition] will contain: (A) pigment [C. I · Pigment Red 254, particle size is about 30 ~ 40 nm] 0. 794 parts by mass, (A) pigment [C. I_Pigment Yellow 139, particle size is about 30 ~ 80 nm] 0. 211 parts by mass, (B) a copolymer of methacrylic acid and benzyl methacrylate [composition ratio of methacrylic acid unit to benzyl methacrylate unit is mass ratio (molar ratio) and is 27 : 73, weight average molecular weight (Mw) is 30,000, acid value is 102] 0.860 parts by mass' (C) dipentaerythritol hexaacrylate 0. 546 parts by mass, (D) photopolymerization initiator [2-methyl-2-morpholino-1- (4-methylthiophenyl) propane 583506 9927 pif 1 -1-_] 〇82 (D) Photopolymerization initiator [2,4_bis (trichloromethyl) -6-piperyl-1,3,5-triazabenzene] 0. 082 parts by mass, photopolymerization initiation aid [2,4-diethylthioxanthone,] 0.082 parts by mass, (E) propylene glycol monomethyl ether acetate 12. About 0 parts by mass and non-ionic surfactants 352 parts by mass of the colored photosensitive resin composition (red) were placed in the same storage container as in the first experimental example, and the container was sealed, and individually stored at -5 ° C, 5 ° C, and 10 ° C. The viscosity change rate of the colored photosensitive resin composition after 6 months and 12 months are shown in Table 1. In addition, the coloring photosensitive resin composition after 6 months or 12 months of storage did not form a gel-like substance at any temperature. The colored photosensitive resin composition, which has been stored for 12 months, is coated on the substrate 3, and the solvent is volatilized to form the colored photosensitive layer 4 (Figure 2A), and the colored photosensitive layer 4 is exposed (No. 2B image), and then developed (FIG. 2C), and the same red transparent coloring pattern as the coloring pattern formed using the coloring photosensitive resin composition before the start of storage can be obtained. Second Comparative Example [Red-colored photosensitive resin composition] The same colored photosensitive resin composition as in the second experimental example was placed in the same storage container as the first experimental example, and was individually stored at 20 ° C and 30 ° C. The viscosity changes after 3 months, 6 months and 12 months are shown in Table 1.尙 Furthermore, gelatine will not be produced after 6 months of storage at 20 ° C, and gelatine will not be generated at 1 ° C and 3 months after storage at 30 ° C. 31 583506 9927 pif 1 = [blue colored photosensitive resin composition] will contain: (A) Pigment ⑴ 丄 Pigment Blue 15: 6, particle size is about 30 ~ 90 nm] 1. 303 parts by mass, (A) pigment [C. I. Pigment Violet 23 with a particle size of about 20-60 nm] 0.016 parts by mass, (B) a copolymer of methacrylic acid and benzyl methacrylate [methacrylic acid unit and benzyl The composition ratio of the methacrylic acid ester units is a mass ratio (molar ratio) and is 30:70, a weight average molecular weight (dish ... 25000, acid value 113) 0. 756 parts by mass, 1 (C) dipentaerythritol hexaacrylate 0.1 887 parts by mass, (D) a photopolymerization initiator [2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one] 0. 197 parts by mass, photopolymerization initiation aid [2,4-diethylthioxanthone] 0. 099 parts by mass, (E) about 11-7 parts by mass of propylene glycol monomethyl ether acetate and non-ionic surfactant 0. 314 parts by mass of the coloring photosensitive resin composition was placed in the same storage container as the first experimental example, and the container was sealed, and each was left standing and stored at minus 5 ° C, 5 ° C, and 毎 10 ° C. The viscosity change rate of the colored photosensitive resin composition is shown in Table 1 after 6 months and after 12 months. In addition, "colored photosensitive resin composition after 6 months or I2 months of storage" did not form a gel-like substance at any temperature. The colored photosensitive resin composition, which has been stored for 12 months, is coated on the substrate 3, and the solvent is volatilized to form the colored photosensitive layer 4 (Figure 2A), and the colored photosensitive layer 4 is exposed (No. (Figure 2B), and then developed (Figure 2C), to obtain the same blue transparent coloring pattern as that of the "32 " 27pifl " 27pifl" color scheme formed using the colored photosensitive resin composition before the start of storage. The fourth experimental example [green will contain:

[綠色著色感光樹脂組成物] •顏料綠36,粒徑爲30〜80奈米左右]0.540質 (A)顏料[C.I·顏料黃138，粒徑爲3〇〜6〇奈米左右]〇·54〇 質量份， (Β)甲基丙烯酸與苄基甲基丙烯酸酯的共聚合物[甲基丙 嫌酸單位與苄基甲基丙烯酸酯單位的組成比爲質量比(莫耳比) 並爲35 : 65，重量平均分子量(Mw)爲35000，酸價爲135]0.787 質量份， (C) 二季戊四醇六丙烯酸酯0.472質量份， (D) 光聚合引發劑[2,4-雙（三氯甲基)-6-胡椒基-1，3,5-三氮 雜苯]0.189質量份， (Ε)丙二醇單甲醚乙酸酯11.8質量份左右、環氧化合物[正 甲酚酚醛型環氧樹脂、「Sumiepoxy ESCN_l95_XL-8〇」（住友 化學工業(株)製)]〇_315質量份以及非離子系界面活性劑0.318 質量份 的著色感光樹脂組成物置入與第一實驗例相同的保存容器並 將容器密封，個別靜置保存在攝氏零下5度與攝氏10度。經 過6個月後以及經過丨2個月後，著色感光樹脂組成物的黏度 變化率如表1所示。尙且，經過6個月或是經過12個月保存 後的著色感光樹脂組成物，無論是在何溫度保存者皆未生成膠 狀物。 上述經12個月保存後的著色感光樹脂組成物，將之塗佈 33 583506 9927 pifl 於基板3上，將溶劑揮發以形成著色感光層4(第2A圖），藉由 對此著色感光層4進行曝光(第2B圖），再進行顯影(第2C圖）， 而能夠得到與使用保存開始前之著色感光樹脂組成物所形成 之著色圖案相同的綠色透明著色圖案。， 第三比較例[綠色著色感光樹脂組成物] 將與第四實驗例相同之著色感光樹脂組成物置入與第一 實驗例相同之保存容器’個別靜置保存在攝氏零下8度 '攝氏 20度與攝氏30度。於攝氏零下8度保存者在1週後產生膠化 物。經過3個月、經過6個月與經過12個月的黏度變化如表1 所示。尙且，於攝氏20度保存者在經6個月保存後亦不會產 生膠狀物，於攝氏30度保存者’經過1個月保存以及經3個 月保存亦不會產生膠狀物。 第五實驗例 將與第四實驗例相同之著色感光樹脂組成物置入與第一 實驗例相同之保存容器’在氧分壓爲2〇4hPa的空氣環境氣體 下，使空隙率爲10%的封入後保存於攝氏5度，於3個月後取鲁 出容器並確認容器內的溶液，溶液的黏度未增加並且未產生凝 集物的保持在初期狀態。 第六實驗例 將與第四實驗例相同之著色感光樹脂組成物置入與第一 實驗例相同之保存容器，在氧分壓爲2〇4hPa的空氣環境氣體 下，使空隙率爲20%的封入後保存於攝氏5度，於3個月後取 出容器並確認容器內的溶液，溶液的黏度未增加並且未產生凝 34 583506 9927 pif 1 集物的保持在初期狀態。 第四比較例 將第五實驗例的空隙率變更爲5%以外，其他與第五實驗 例相同的進行保存。於30日後確認容器內的溶液，而確認溶 液的黏度增加並產生凝集物。 第五比較例 將第五實驗例的空氣環境氣體以氮氣環境氣體取代以 φ 外，其他與第五實驗例相同的進行保存。於30日後確認容器 內的溶液，而確認溶液的黏度增加並產生凝集物。 第一參考例 將第一實驗例的（A)顏料[C.I.顏料綠36]、[C.I.顏料黃150] 與非離子系界面活性劑除外，使用與第一實驗例相同的物質組 成感光樹脂組成物(無色），將之置入與第一實驗例相同的保存 容器中並將容器密封，靜置保存於攝氏零下10度，經過12個 月後的感光樹脂組成物未產生膠狀物。 鲁 35 583506 9927 pif 1 表1 保存溫度 黏度變化率(％) 3個月後 6個月後 12個月後 (綠色） 第一實驗例 -5°C 一 、 1 2 5°C — 1 2 10°C 一 3 5 第一比較例 20°C — 10 14 30°C 5 9 — (紅色） 第二實驗例 -5°C 一 2 2 5°C 一 2 3 10°C 一 2 4 第二比較例 20°C 一 9 12 30°C 4 11 — (藍色） 第三實驗例 -5°C 一 1 1 5°C 一 1 1 10°C _ 1 3 (綠色） 第四實驗例 -5°C 一 1 3 5°C 一 2 3 10°C 一 4 5 第三比較例 20°C 9 16 24 30°C 18 42 —[Green coloring photosensitive resin composition] • Pigment green 36, particle size of about 30 to 80 nm] 0.540 quality (A) pigment [CI · Pigment Yellow 138, particle size of about 30 to 60 nm] 〇 · 54 mass parts, (B) a copolymer of methacrylic acid and benzyl methacrylate [composition ratio of methacrylic acid unit to benzyl methacrylate unit is mass ratio (molar ratio) and is 35: 65, weight average molecular weight (Mw) is 35,000, acid value is 135] 0.787 parts by mass, (C) dipentaerythritol hexaacrylate 0.472 parts by mass, (D) photopolymerization initiator [2,4-bis (trichloro) (Methyl) -6-piperyl-1,3,5-triazabenzene] 0.189 parts by mass, (E) about 11.8 parts by mass of propylene glycol monomethyl ether acetate, epoxy compound [n-cresol novolac epoxy Resin, "Sumiepoxy ESCN_l95_XL-8〇" (manufactured by Sumitomo Chemical Industries, Ltd.) 〇_315 parts by mass and 0.318 parts by mass of a non-ionic surfactant, and a colored photosensitive resin composition was placed in the same storage container as the first experimental example And the container was sealed, and each was kept at -5 ° C and 10 ° C. The viscosity change rate of the colored photosensitive resin composition is shown in Table 1 after 6 months and after 2 months. In addition, the colored photosensitive resin composition after 6 months or 12 months of storage did not form a gel at any temperature. The above-mentioned colored photosensitive resin composition after 12 months of storage is coated with 33 583506 9927 pifl on the substrate 3, and the solvent is volatilized to form the colored photosensitive layer 4 (FIG. 2A), and the photosensitive layer 4 is colored by this By exposing (Figure 2B) and then developing (Figure 2C), the same green transparent colored pattern as the colored pattern formed using the colored photosensitive resin composition before the start of storage can be obtained. The third comparative example [green colored photosensitive resin composition] The same colored photosensitive resin composition as in the fourth experimental example was placed in the same storage container as the first experimental example 'individually stored at minus 8 degrees Celsius' and 20 degrees Celsius With 30 degrees Celsius. Preservation at minus 8 degrees Celsius produced gelatin after 1 week. The viscosity changes after 3 months, 6 months and 12 months are shown in Table 1. Also, those who were kept at 20 ° C did not produce gelatin after 6 months of storage, and those who were kept at 30 ° C ’did not produce gelatin after 1 month of storage and 3 months of storage. In the fifth experimental example, the same colored photosensitive resin composition as that in the fourth experimental example was placed in the same storage container as in the first experimental example, and it was sealed under an air ambient gas with an oxygen partial pressure of 204 hPa and a void ratio of 10% It was then stored at 5 degrees Celsius. After 3 months, the container was taken out and the solution in the container was confirmed. The viscosity of the solution did not increase and no agglomerates were generated. The initial state was maintained. In the sixth experimental example, the same colored photosensitive resin composition as in the fourth experimental example was placed in the same storage container as in the first experimental example, and the porosity was sealed at 20% in an air atmosphere with an oxygen partial pressure of 204 hPa. It was stored at 5 degrees Celsius. After 3 months, the container was taken out and the solution in the container was confirmed. The viscosity of the solution did not increase and no coagulation occurred. 34 583506 9927 pif 1 The aggregate was kept in the initial state. Fourth Comparative Example The porosity of the fifth experimental example was changed to other than 5%, and the rest was stored in the same manner as the fifth experimental example. After 30 days, the solution in the container was confirmed, and it was confirmed that the viscosity of the solution increased and agglomerates were generated. Fifth Comparative Example The air in the fifth experimental example was replaced with a nitrogen ambient gas by φ, and the rest were stored in the same manner as in the fifth experimental example. After 30 days, the solution in the container was confirmed, and it was confirmed that the viscosity of the solution increased and agglomerates were generated. First Reference Example Excluding the (A) pigments [CI Pigment Green 36], [CI Pigment Yellow 150] and non-ionic surfactants of the first experimental example, and using the same material as the first experimental example to form a photosensitive resin composition (Colorless), put it in the same storage container as in the first experimental example, sealed the container, and stored it at -10 ° C. After 12 months, the photosensitive resin composition did not produce a gel. Lu 35 583506 9927 pif 1 Table 1 Change rate of viscosity at storage temperature (%) After 6 months and after 12 months (green) First experimental example -5 ° C I, 1 2 5 ° C — 1 2 10 ° C-3 5 First comparative example 20 ° C — 10 14 30 ° C 5 9 — (red) Second experimental example-5 ° C-2 2 5 ° C-2 3 10 ° C-2 4 Second comparison Example 20 ° C-9 12 30 ° C 4 11 — (blue) Third experimental example -5 ° C-1 1 5 ° C-1 1 10 ° C _ 1 3 (green) Fourth experimental example -5 ° C-1 3 5 ° C-2 3 10 ° C-4 5 Third Comparative Example 20 ° C 9 16 24 30 ° C 18 42 —

36 583506 9927 pif 1 第七實驗例[紅色著色感光樹脂組成物] 將含有： (A)顔料[C.I·顏料紅254，粒徑爲30〜40奈米左右]0.794 質量份， ， (A) 顏料[C.I·顏料黃139，粒徑爲30〜80奈米左右]0.211 質量份， (B) 甲基丙烯酸與苄基甲基丙烯酸酯的共聚合物[甲基丙 烯酸單位與苄基甲基丙烯酸酯單位的組成比爲質量比（莫耳比) 並爲27 : 73，重量平均分子量(Mw)爲300〇〇，酸價爲i〇2]〇.86〇 質量份， (C) 二季戊四醇六丙烯酸酯0.546質量份， (D) 光聚合引發劑[2-甲基-2-嗎啉代-1-(4-甲硫基苯基)丙烷 -1-酮]0.082質量份， (D) 光聚合引發劑[2,4-雙（三氯甲基）-6-胡椒基-1，3,5-三氮 雜苯]0.082質量份， 光聚合引發助劑[2,4-二乙基噻噸酮]0.082質量份 (E) 丙二醇單甲醚乙酸酯12.0質量份左右以及非離子系界 面活性劑0.352質量份 的著色感光樹脂組成物於大氣中，以75%的塡充率塡充入250 奈米〜440奈米之光透過率在5%以下的容器，並將容器拴緊、 密封，個別在在攝氏零下25度、攝氏零下5度、攝氏5度與 攝氏23度以10分鐘的速率上下反轉容器’並保存1曰。 保存於攝氏零下25度的著色感光樹脂組成物’於1日後 產生膠化物。 保存於攝氏零下5度的著色感光樹脂組成物’於1日後觀 察未產生膠化物，黏度變化率爲4% ° 37 583506 9927 pif 1 保存於攝氏5度的著色感光樹脂組成物’於1日後觀察未 產生膠化物，黏度變化率爲3% ° 保存於攝氏23度的著色感光樹脂組成物’於1日後觀察 未產生膠化物，黏度變化率爲5%以下。 第六比較例[紅色著色感光樹脂組成物] 除了不對容器進行上下反轉而在靜置狀態保存之外，係進 行與第七實驗例相同的操作以保存著色感光樹脂組成物。 保存於攝氏零下25度的著色感光樹脂組成物，於1日後 產生膠化物。 保存於攝氏零下5度的著色感光樹脂組成物，於1日後觀 察未產生膠化物，黏度變化率爲50%。 保存於攝氏5度的著色感光樹脂組成物，於1日後觀察未 產生膠化物，黏度變化率爲80%。 第八實驗例[綠色著色感光樹脂組成物] 將第t實驗例所使用的著色感光樹脂組成物以下述組成 取代： (1顏料[C.I·顏料綠36,粒徑爲30〜80奈米左右]0.740質 量份， / 38 1 顏料[C.I·顏料黃150，粒徑爲30〜80奈米左右]〇 340 質量份， 甲基芮烯酸與苄基甲基丙烯酸酯的共聚合物[甲基丙 嫌酸單位與节基甲基丙烯酸酯單位的組成比爲質量比（莫耳比) 並爲35 : 65，蔞量平均分子量(Mw)爲35000，酸價爲135]0.787 質量份， 583506 9927 pif 1 (C) 二季戊四醇六丙烯酸酯0.472質量份， (D) 光聚合引發劑[2_甲基_2_嗎啉代甲硫基苯基)丙烷 -1-酮]0.189質量份， 光聚合引發助劑[4,4’_雙（二乙胺)二苯甲酮]0·063質量份， (Ε)丙二醇單甲醚乙酸酯11.8質量份左右、環氧化合物[正 甲酚酚醛型環氧樹脂、「Sumiepoxy ESCN-l95_XL_8〇」（住友 化學工業(株)製)]〇·315質量份以及非離子系界面活性劑〇.318 質量份， 除外以與第七實驗例相同的方法保存。 保存於攝氏零下25度的著色感光樹脂組成物，於1曰後 產生膠化物。 保存於攝氏零下5度的著色感光樹脂組成物，於1日後觀 察未產生膠化物，黏度變化率爲5%。 保存於攝氏5度的著色感光樹脂組成物，於1日後觀察未 產生膠化物，黏度變化率爲3%。 保存於攝氏23度的著色感光樹脂組成物，於1日後觀察 未產生膠化物，黏度變化率爲5%以下。 第七比較例[綠色著色感光樹脂組成物] 除了不對容器進行上下反轉而在靜置狀態保存之外’係進 行與第八實驗例相同的操作以保存著色感光樹脂組成物。 保存於攝氏零下25度的著色感光樹脂組成物’於1曰後 產生膠化物。 保存於攝氏零下5度的著色感光樹脂組成物，於1日後觀 察未產生膠化物，黏度變化率爲80%。 保存於攝氏5度的著色感光樹脂組成物，於1日後觀察未 39 9927 pifl 產生膠化物，黏度變化率爲50%。 第九實驗例[藍色著色感光樹脂組成物] 將第七實驗例所使用的著色感光樹脂組成物以下述組成 取代： (A)顏料[C.I·顔料藍15: 6,粒徑爲30〜90奈米左右]1.303 質量份， (A) 顏料[C.I·顏料紫23,粒徑爲20〜60奈米左右]0.016質 量份， (B) 甲基丙烯酸與苄基甲基丙烯酸酯的共聚合物[甲基丙 立與苄基甲基丙烯酸酯單位的組成比爲質量比(莫耳比) 並爲30 : 70，重量平均分子量(Mw)爲25000，酸價爲113]0.756 質量份， (C) 二季戊四醇六丙烯酸酯0.887質量份， (D) 光聚合引發劑[2_甲基_2_嗎啉代甲硫基苯基)丙烷 -1_酮]0.197質量份， 光聚合引發助劑[2,4-二乙基噻噸酮]0.099質量份 (Ε)丙二醇單甲醚乙酸酯η·7質量份左右以及非離子系界 面活性劑0.314質量份， 除外以與第七實驗例相同的方法保存。 保存於攝氏零下25度的著色感光樹脂組成物，於丨日後 觀察未產生膠化物，黏度變化率爲20%。 保存於攝氏零下5度的著色感光樹脂組成物，於丨日後觀 察未產生膠化物，黏度變化率爲4%。 保存於攝氏5度的著色感光樹脂組成物，於1日後觀察未 產生膠化物，黏度變化率爲1%。 9927 pifl 保存於攝氏23度的著色感光樹脂組成物’於1日後觀察 未產生膠化物，黏度變化率爲5 %以下。 第八比較例[藍色著色感光樹脂組成物]， 除了不對容器進行上下反轉而在靜置狀態保存之外’係進 行與第九實驗例相同的操作以保存著色感光樹脂組成物。 保存於攝氏零下25度的著色感光樹脂組成物’於1曰後 產生膠化物。 保存於攝氏零下5度的著色感光樹脂組成物’於1日後觀 察未產生膠化物，黏度變化率爲30% ° 保存於攝氏5度的著色感光樹脂組成物，於1日後觀察未 產生膠化物，黏度變化率爲15%。36 583506 9927 pif 1 The seventh experimental example [red colored photosensitive resin composition] will contain: (A) pigment [CI · Pigment Red 254, particle size of about 30 to 40 nm] 0.794 parts by mass, (A) pigment [CI · Pigment Yellow 139, particle size of about 30 to 80 nm] 0.211 parts by mass, (B) Copolymer of methacrylic acid and benzyl methacrylate [methacrylic unit and benzyl methacrylate The composition ratio of the unit is a mass ratio (molar ratio) of 27:73, a weight average molecular weight (Mw) of 300,000, an acid value of 102, 0.886 parts by mass, and (C) dipentaerythritol hexaacrylic acid. 0.546 parts by mass of ester, (D) photopolymerization initiator [2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one] 0.082 parts by mass, (D) photopolymerization 0.082 parts by mass of an initiator [2,4-bis (trichloromethyl) -6-piperyl-1,3,5-triazabenzene], a photopolymerization initiation aid [2,4-diethylthioxanthine] Ketone] 0.082 parts by mass (E) of about 12.0 parts by mass of propylene glycol monomethyl ether acetate and 0.352 parts by mass of a non-ionic surfactant in the atmosphere, and charged at a charge rate of 250% to 250 Nanometer ~ 440 Nanometer Containers with a light transmittance of less than 5%, and the containers are fastened and sealed. Individually, the containers are inverted at a rate of 10 minutes at minus 25 degrees Celsius, minus 5 degrees Celsius, 5 degrees Celsius, and 23 degrees Celsius. 1 said. The colored photosensitive resin composition 'stored at minus 25 ° C produced a gel after one day. Coloured photosensitive resin composition stored at minus 5 degrees Celsius 'No gelation was observed after 1 day, and the viscosity change rate was 4% ° 37 583506 9927 pif 1 Coloured photosensitive resin composition stored at 5 degrees Celsius' observed after 1 day No gelation occurred, and the viscosity change rate was 3%. The coloring photosensitive resin composition 'stored at 23 ° C was observed to have no gelation after one day, and the viscosity change rate was less than 5%. Sixth Comparative Example [Red colored photosensitive resin composition] A colored photosensitive resin composition was stored in the same manner as in the seventh experimental example except that the container was stored in a standing state without inverting the container. The colored photosensitive resin composition stored at minus 25 degrees Celsius produced gelatin after one day. The colored photosensitive resin composition stored at minus 5 degrees Celsius did not produce gelatin after one day, and the viscosity change rate was 50%. The coloring photosensitive resin composition stored at 5 ° C was observed after one day without gelation, and the viscosity change rate was 80%. Eighth experimental example [Green colored photosensitive resin composition] The colored photosensitive resin composition used in the t-th experimental example was replaced with the following composition: (1 pigment [CI · Pigment Green 36, particle size of about 30 to 80 nm] 0.740 parts by mass, / 38 1 pigment [CI · Pigment Yellow 150, particle size of about 30 to 80 nm] 0340 parts by mass, a copolymer of methyl renenoic acid and benzyl methacrylate [methacryl The composition ratio of the acidic unit and the benzyl methacrylate unit is a mass ratio (molar ratio) of 35:65, the weight average molecular weight (Mw) is 35000, and the acid value is 135] 0.787 parts by mass, 583506 9927 pif 1 (C) 0.472 parts by mass of dipentaerythritol hexaacrylate, (D) 0.189 parts by mass of photoinitiator [2_methyl_2_morpholinomethylthiophenyl) propane-1-one, initiation of photopolymerization Auxiliary [4,4'_bis (diethylamine) benzophenone] 0.063 parts by mass, (E) about 11.8 parts by mass of propylene glycol monomethyl ether acetate, epoxy compound [n-cresol novolac ring Oxyresin, "Sumiepoxy ESCN-l95_XL_8〇" (manufactured by Sumitomo Chemical Industries, Ltd.) 0.35 parts by mass and 0.318 parts by mass of a nonionic surfactant, Except for saving in the same manner as in the seventh experimental example. The colored photosensitive resin composition stored at minus 25 degrees Celsius generates gelatin after one day. The colored photosensitive resin composition stored at minus 5 degrees Celsius did not produce gelatin after one day, and the viscosity change rate was 5%. The coloring photosensitive resin composition stored at 5 degrees Celsius was observed after one day without gelation, and the viscosity change rate was 3%. The coloring photosensitive resin composition stored at 23 ° C was observed after one day, and no gelation was observed, and the viscosity change rate was 5% or less. The seventh comparative example [green colored photosensitive resin composition] The same operation as in the eighth experimental example was performed to save the colored photosensitive resin composition except that the container was stored in a standing state without inverting the container upside down. The colored photosensitive resin composition 'stored at minus 25 degrees Celsius produced a gel after 1 day. The colored photosensitive resin composition stored at minus 5 degrees Celsius did not produce gelatin after one day, and the viscosity change rate was 80%. The coloring photosensitive resin composition stored at 5 degrees Celsius was observed after one day. 39 9927 pifl did not produce gel, and the viscosity change rate was 50%. Ninth Experimental Example [Blue Colored Photosensitive Resin Composition] The colored photosensitive resin composition used in the seventh experimental example was replaced with the following composition: (A) Pigment [CI · Pigment Blue 15: 6, particle size 30 to 90 About nanometers] 1.303 parts by mass, (A) pigment [CI · Pigment Violet 23, particle size of about 20 to 60 nanometers] 0.016 parts by mass, (B) copolymer of methacrylic acid and benzyl methacrylate [The composition ratio of methacrylic and benzyl methacrylate units is 30:70 by mass ratio (molar ratio), weight average molecular weight (Mw) is 25000, and acid value is 113] 0.756 parts by mass, (C ) 0.887 parts by mass of dipentaerythritol hexaacrylate, (D) Photopolymerization initiator [2_methyl_2_morpholinomethylthiophenyl) propane-1_one], 0.197 parts by mass, photopolymerization initiation aid [ 2,4-Diethylthioxanthone] 0.099 parts by mass of (E) propylene glycol monomethyl ether acetate η · 7 parts by mass and 0.314 parts by mass of nonionic surfactant, except that the same as the seventh experimental example Method saved. The coloring photosensitive resin composition stored at minus 25 degrees Celsius was observed to have no gelation in the future, and the viscosity change rate was 20%. The colored photosensitive resin composition stored at minus 5 degrees Celsius did not produce gelatin in the future, and the viscosity change rate was 4%. The coloring photosensitive resin composition stored at 5 ° C was observed after one day without gelation, and the viscosity change rate was 1%. 9927 pifl The colored photosensitive resin composition 'stored at 23 ° C was observed after one day. No gelation occurred, and the viscosity change rate was less than 5%. In the eighth comparative example [blue colored photosensitive resin composition], the same operation as in the ninth experimental example was performed to save the colored photosensitive resin composition, except that the container was stored in a standing state without inverting the container. The colored photosensitive resin composition 'stored at minus 25 degrees Celsius produced a gel after 1 day. The colored photosensitive resin composition stored at minus 5 degrees Celsius has no gelation observed after 1 day, and the viscosity change rate is 30%. The colored photosensitive resin composition stored at 5 degrees Celsius has no gelation observed after 1 day. The viscosity change rate is 15%.

Claims (1)

583506 9927 pif 1 第1項至第4項之其中之一項所述之著色感光樹脂組成物之保 存方法所保存的著色感光樹脂組成物塗佈至一基板上，除去該 溶劑以形成一著色感光層，接著曝光並顯影該著色感光層。 6. —種具有著色圖案之彩色濾光片之形成方法，其特徵爲 使用申請專利範圍第5項所述方法形成著色圖案。583506 9927 pif 1 The colored photosensitive resin composition stored in the preservation method of the colored photosensitive resin composition described in one of items 1 to 4 is coated on a substrate, and the solvent is removed to form a colored photosensitive Layer, followed by exposure and development of the colored photosensitive layer. 6. A method for forming a color filter with a colored pattern, characterized in that the colored pattern is formed using the method described in item 5 of the scope of patent application. 4343
TW091119214A 2001-09-03 2002-08-26 Preserving method for color resist TW583506B (en)

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US8263675B2 (en) 2007-09-04 2012-09-11 Cheil Industries Inc. Photosensitive resin composition for color filter and color filter made using the same

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KR920020277A (en) * 1991-04-03 1992-11-20 김광호 How to prevent dark reaction when storing photoresist
JPH09204052A (en) * 1996-01-26 1997-08-05 Sumitomo Chem Co Ltd Method for preserving positive type photoresist over long period of time
JP3766165B2 (en) * 1997-03-07 2006-04-12 株式会社ニコン Image forming method and photosensitive material
JP3965738B2 (en) * 1997-10-13 2007-08-29 住友化学株式会社 Stable preservation method of positive photoresist
JP2000010308A (en) * 1998-06-23 2000-01-14 Canon Inc Preserving method of paint for electrophotographic photoreceptor and electrophotographic photoreceptor
JP2000098606A (en) * 1998-09-22 2000-04-07 Sumitomo Chem Co Ltd Colored photosensitive resin composition
JP4075243B2 (en) * 1999-09-03 2008-04-16 Ｊｓｒ株式会社 Radiation sensitive composition for color filter and color filter
JP2001305733A (en) * 2000-04-18 2001-11-02 Sumitomo Chem Co Ltd Method for preserving photosensitive composition

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Publication number Priority date Publication date Assignee Title
US8263675B2 (en) 2007-09-04 2012-09-11 Cheil Industries Inc. Photosensitive resin composition for color filter and color filter made using the same

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