TW473647B - Photosensitive resin composition - Google Patents
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47364 A7 B7 五、 發明說明( 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 本發 進行顯影 優異顯影 強度佳的 _ __ A/t» nsL 濾、光片之 料分散法 、藍、綠 於顏料分 之耐光性 主流。 本發 1 〇〜60%之 等效應, 較半導體 型光阻劑 光反應系 物;上述 型光阻劑 低成本等 括:多官 、溶劑及 昔往 性不足, 當之光起 明係有 之感光 性及密 感光性 而言, 方法, 四種, 三·原色 散法所 與耐熱 關一種可以藉光照射聚合,再以鹼 性樹脂組成物。詳言之,即有關一 著性,透光性佳且顯影色差甚小、 樹脂組成物。 基於製作成本及品質考量,時下製 較常用的有染色法、印刷法、電著 彩色濾光片之製作是在玻璃基板上 之有機顏料,製作在每一個畫素之 製作之彩色濾光片,具有高精密度 性,因此’目前己成為彩色濾光片 性溶液 種具有 硬化膜 作彩色 法及顏 ,將紅 内。由 及較佳 之製造 明所述之感光性樹脂組成物的固體含量中,佔 顏料會對曝光時所使用之UV光源產生吸收、散射 故本發明之感光性樹脂組成物對UV光之透過率遠 用之正型光阻劑為低,基於上述原因,顏料分散 必須採用高感度之光反應系統;而最具代表性之 統則為丙烯酸系自由基聚合型之感光性樹脂組成 丙烯酸系自由基聚合型之感光性樹脂組成物為負 ’其具有高感度、材料安定性佳、設計多樣性、 優點’為目前最被廣泛使用之材料。.其成分則包 能基單體、顏料、感光性起始劑、有機性黏結劑 添加劑等。 所使用之顏料分散型光阻劑,由於紅色顏料透光 組成成份間的比例未做良好控制,且沒有選擇適 始劑’故無法兼顧顯影性、密著性及顯影色差, 第 頁 本纸張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 47364747364 A7 B7 V. Description of the invention (Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, developed and developed with excellent development strength. _ __ A / t »nsL Filter, light sheet dispersion method, blue and green are divided into pigments The light resistance is mainstream. The effect of 10 ~ 60% of this hair is lower than the photoresist of semiconductor photoresist. The low cost of the above photoresist includes: multiple organs, solvents and past properties are insufficient. In terms of the sensitivity and dense sensitivity of the Ming system, there are four methods, three, and three. The primary dispersion method and the heat resistance method can be polymerized by light irradiation, and then the basic resin composition. Specifically, it is related to a Based on production cost and quality considerations, dyeing, printing, and electronic color filters are commonly used in the production of color filters on glass substrates. Organic pigments, color filters made at each pixel, have high precision, so 'currently, it has become a color filter solution with a hardened film for color and color The inside of the red. The solid content of the photosensitive resin composition described in the preferred and preferred manufacturing method accounts for the pigment that absorbs and scatters the UV light source used during exposure. Therefore, the photosensitive resin composition of the present invention is sensitive to UV light. The positive photoresist used in the transmission is far lower. For the above reasons, pigment dispersion must use a high-sensitivity photoreaction system; the most representative system is acrylic radical polymerization type photosensitive resin composed of acrylic acid. The radical polymerizable photosensitive resin composition is negative. It has high sensitivity, good material stability, design diversity, and advantages. It is the most widely used material at present. Its ingredients include energy-based monomers and pigments. , Photosensitive initiators, organic binder additives, etc. The pigment-dispersed photoresist used, because the ratio between the light-transmitting components of the red pigment is not well controlled, and the proper initiator is not selected, so it cannot take into account the development Properties, adhesion, and development chromatic aberration. Page size of this paper applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back first Then fill out this page) 473 647
其透光性亦不佳。 本案發明人為了改善上述H經銳意Μ Μ Ρ月之感光性樹脂組成物經由選用特定之 叫 ,iket。啊。lGPyrrGle)系之紅色顏料,並 之有機性黏結性樹脂與含乙烯性不飽和基化合物之使用: 量比調控’將可達成本發明…。更進一步來說,本: 明之感光性樹脂組成物若配合特定的光起始劑, 二 璃基板之密著性'顯影性、顯影色差及透光 更 顯著的效果。 寺”有更為 故本發明為一種感光性樹脂組成物,其組成包括.人 (B)、二二二 婦性不飽和基之化合物 (B)先起始劑(C)、有機溶劑(D)、顏料(盆 含:基之有機性黏結劑⑴係由含一個或一個…之 乙烯性不飽和單體5〜5〇重量%,以 羧基之 飽和單體95,重量%所組成,而二):;之乙稀性不 并吡略糸夕,1, 顋枓(Μ係為二羰代吡咯 系之、..工色顏料;而且含乙烯性不飽 (B)與含…有機性黏結劑⑴…之化二 1〇〇/1〇(Μ6〇/1〇{)。 史用比例為 以下對於本發明之各組成做一詳細的說明: (A)含羧基之有機性黏結劑: 。盆;光性樹脂組成物均會加入有機性黏結劑 塗佈性、顯ir成物長期貯存安定性、密著性、 ^r顯影性、耐熱性及耐溶劑性 感光性樹脂組成物能溶解於驗性顯影液,'常使::::: 第 4 頁 本紙張尺度顧巾® (CNS)A4規格(210 X 297公爱) (請先閱讀背面之注意事項再填寫本頁) Φ 計 i l· 線--. 473647 Α7 Β7 經濟部智慧財產局員工消費合作社印製Its light transmission is also poor. In order to improve the above-mentioned photosensitive resin composition, the inventors of this case determined to use a specific name, iket. what. lGPyrrGle) series of red pigments, and the use of organic adhesive resins and ethylenically unsaturated compounds: the amount ratio control will reach the cost of invention ... Furthermore, if the photosensitive resin composition of the present invention is compounded with a specific photoinitiator, the adhesiveness of the glass substrate, the developability, the chromatic aberration of the development, and the light transmittance are more significant. "Si" has the reason that the present invention is a photosensitive resin composition, the composition of which includes: human (B), two-two two-female unsaturated compounds (B) first initiator (C), organic solvent (D ), Pigments (basin-based organic binders) are composed of 5 to 50% by weight of ethylenically unsaturated monomers containing one or one, and 95% by weight of carboxyl saturated monomers, and two ) :; of ethylenic pyridoxine, 1, 顋 枓 (M series is dicarbonylpyrrole series, .. color pigments; and containing ethylenic unsaturated (B) and organic bonding Agent ⑴ ... of the two 100/1 0 (M60 / 10/1). The historical ratio is as follows to make a detailed description of the components of the present invention: (A) carboxyl-containing organic binder:. Pot; the light resin composition will be added with organic binder coating properties, long-term storage stability of the product, adhesion, ^ r development, heat resistance and solvent-resistant sexy light resin composition can be dissolved in Diagnostic developer, 'Often use :::::' Page 4 This paper size Gu towel ® (CNS) A4 specification (210 X 297 public love) (Please read the note on the back first Items and then Complete this page) Φ i l · meter line -. 473647 Α7 Β7 Ministry of Economic Affairs Intellectual Property Office employees consumer cooperatives printed
五、發明說明(3 ) 含緩基之丙稀酸系或甲基丙稀酸系樹脂。 本發明所使用含羧基之有機性黏結劑(A)係—種含幾 基之共聚物’尤指包括含一個或一個以上羧基之乙稀性不 飽和單體5〜50重量% ’以及可共聚合之乙烯性不飽和單體 95~50重量%之共聚物。 上述含羧基之乙烯性不飽和單體可舉例如下:丙烯酸 、甲基丙烯酸、丁烯酸、α -氯丙烯酸、乙基丙烯酸及肉 桂酸等之不飽和·一元緩酸類;馬來酸、馬來酸酐、富馬酸 、衣康酸、衣康酸酐、檸康酸、檸康酸酐及中康酸等之不 飽和二元羧酸(酐)類;3價以上之不飽和多價羧酸(酐)類 等等。該等含羧基之乙烯性不飽和單體可單獨或混合兩種 以上使用;而前述其他可共聚合之乙烯性不飽和單體乃例 如:苯乙烯、α -曱基苯乙烯、乙烯基甲苯、氯乙烯、甲 氧基苯乙烯等之芳香族乙烯基化合物;丙烯酸甲酯、曱基 丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯 、曱基丙烯酸丙酯、丙烯酸丁酯、曱基丙烯酸丁酯、丙烯 酸2 -羥乙基酯、甲基丙烯酸2 -羥乙基酯、丙烯酸苯甲酯及 甲基丙烯酸苯甲酯、曱基丙烯酸十二烷基酯、曱基丙烯酸 十四烷基酯、甲基丙烯酸十六烷基酯、甲基丙烯酸十八烷 基酯、曱基丙烯酸二十二烷基酯、甲基丙烯酸二十烷基醋 等之不.飽和羧酸酯類;丙烯酸氨乙酯、曱基丙烯酸氨乙醋 、丙烯酸氨丙酯、甲基丙烯酸氨丙酯等之不飽和羧酸氣烧 酯類;丙烯酸環氧丙基酯、曱基丙烯酸環氧丙基酯等之不 飽和羧酸環氧丙基酯類;乙酸乙烯酯、丙酸乙烯酯、丁酸 乙烯酯、安息香酸乙烯酯等之羧酸乙烯酯類;乙烯基甲醚 第5頁 _ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 473647 A7 五、發明說明(4 、乙烯基乙喊、烯丙基環氧丙基醚、甲代婦丙基環氧丙基 醚類;丙烯腈、甲基丙稀胯、"丙稀腈 、氰化亞乙烯專之氰化乙烯基化合物;丙烯酸胺、甲基丙 稀醯胺、《-氯丙烯醯胺、N_羥乙基丙烯醯胺、N_羥乙基 曱基丙烯醯胺、馬來酿胺等之不飽和酿胺或不飽㈣亞胺 類,1」3-丁二歸、異丙稀、氯丙婦等之脂肪族共輕二稀類 ;聚苯乙烯、聚丙烯酸曱酯、聚曱基丙烯酸甲酯、聚丙烯 酸丁醋、聚曱基丙烤酸丁醋、聚石夕氧烧等在聚合物分子键 末端具有單丙烯醯基或單曱基丙烯醯基之巨大單體類等。 此等其他不飽和單體可單獨或混合兩種或兩種以上使 用;而本發明之較佳含羧基的共聚物係為①5〜5〇重量%之 丙烯酸及/或曱基丙烯酸,以及095〜5〇重量%之選自由甲 基丙烯酸甲酯、丙烯酸2 —羥乙基酯、甲基丙烯酸2_羥乙基 酯、丙烯酸苯曱酯、甲基丙烯酸苯甲酯、苯乙烯、聚苯乙 烯巨大單體及聚甲基丙烯酸甲酯巨大單體所構成之組群中 之至少一種其他不飽和單體的共聚物。 經濟部智慧財產局員工消費合作社印製 較佳含羧基之共聚物的具體例可舉有:丙烯酸/丙烯 酸苯甲醋共聚物、丙烯酸/丙烯酸笨曱酯/苯乙烯共聚物、 丙烯酸/丙烯酸甲酯/苯乙烯共聚物、丙烯酸/丙烯酸笨甲 醋/聚乙烯巨大單體共聚物、丙烯酸/丙烯酸苯甲酯/聚甲 基丙烯酸甲酯巨大單體共聚物、丙烯酸/丙烯酸甲酯/聚乙 烯巨大單體共聚物、丙烯酸/丙烯酸曱酯/聚曱基丙烯酸曱 醋巨大單體共聚物' 丙烯酸/甲基丙烯酸苯甲酯共聚物、 丙烯酸/曱基丙烯酸笨曱酯/苯乙烯共聚物、丙烯酸/甲基 丙烯酸甲酯/苯乙烯共聚物、丙烯酸/曱基丙烯酸苯甲酯/ 頁 (請先Μ讀背面之注意事項再填寫本頁) 第 Μ氏張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 473647 A7 ' '_B7_/五、發明說明(5 ) 聚乙烯巨大單體共聚物、丙烯酸/曱基丙烯酸苯甲酯/聚甲 基丙烯酸曱酯巨大單體共聚物、丙烯酸/甲基丙烯酸甲酯/ 聚乙烯巨大單體共聚物、丙烯酸/曱基丙烯酸曱酯/聚曱基 ; 丙烯酸曱酯巨大單體共聚物、丙烯酸/甲基丙烯酸2 -羥乙 基酯/甲基丙烯酸苯甲酯/聚乙烯巨大單體共聚物、丙烯酸 /曱基丙烯酸2 -羥乙基酯/曱基丙烯酸苯曱酯/聚曱基丙烯 酸曱酯巨大單體共聚物、甲基丙烯酸/丙烯酸苯甲酯/苯乙 烯共聚物、曱基丙烯酸/丙烯酸曱酯/苯乙烯共聚物、甲基 烯 丙酸 酸 丙 曱 . 苯酯 酸曱 烯苯 丙酸 ,稀 酯 聚 烯曱 丙、 基物 甲聚 、共 物體 聚單 共大 體巨 單酯 大甲 巨酸 烯烯 乙丙 聚基 /甲 (請先閱讀背面之注意事項再填寫本頁) 丙 基酸 酸 烯 烯 丙 烯基 丙甲 基、 曱物 、 聚 物共 聚體 共單 體大 單巨 大酯 巨甲 烯酸 乙烯 聚丙 /基0 Μ 曱 曱」 -聚 酸/; 烯酯 丙曱 酸 烯 酸丙 烯基 丙曱 基/ 酸 烯 物丙 聚基 共曱 匕日 、 酉 曱物 苯聚 酸共 烯烯 丙乙 基苯 甲旨 // 酸曱 烯苯 丙酸 甲 烯 丙 基 甲5. Description of the invention (3) Acrylic acid or methyl acrylic resin containing a retarding group. The carboxyl group-containing organic binder (A) used in the present invention is a copolymer containing several groups, especially 5 to 50% by weight of an ethylenically unsaturated monomer containing one or more carboxyl groups, and a copolymerizable copolymer. A copolymer of 95-50% by weight of a polymerized ethylenically unsaturated monomer. Examples of the carboxyl group-containing ethylenically unsaturated monomers are as follows: unsaturated, monobasic, slow-acids such as acrylic acid, methacrylic acid, butenoic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; maleic acid, and maleic acid Unsaturated dicarboxylic acids (anhydrides) such as anhydrides, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; unsaturated polyvalent carboxylic acids (anhydrides of 3 or more valences) ) Class and so on. These ethylenically unsaturated monomers containing carboxyl groups can be used alone or as a mixture of two or more of them; the aforementioned other copolymerizable ethylenically unsaturated monomers are, for example, styrene, α-fluorenylstyrene, vinyltoluene, Aromatic vinyl compounds such as vinyl chloride and methoxystyrene; methyl acrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl acrylate, butyl acrylate, Fluorenyl butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate and benzyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate Alkyl esters, cetyl methacrylate, octadecyl methacrylate, behenyl methacrylate, eicosyl methacrylate, and the like. Saturated carboxylic acid esters; Unsaturated carboxylic acid gas-fired esters such as aminoethyl acrylate, ethyl methacrylate, aminopropyl acrylate, aminopropyl methacrylate, etc .; epoxy propyl acrylate, epoxy propyl acrylate, etc. Unsaturated carboxylic acid propylene oxide Esters; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc .; vinyl methyl ether page 5 _ This paper size applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm) --------- install -------- order --------- line (please read the precautions on the back before filling this page) 473647 A7 V. Description of the invention (4, vinyl ethene, allyl epoxy propyl ether, methylidene glycidyl ether; acrylonitrile, methacrylic acid, " acrylonitrile, cyanation Vinylidene vinyl cyanide compound; amine acrylate, methacrylamide, "-chloroacrylamide, N_hydroxyethylacrylamide, N_hydroxyethylamylamine, malays Unsaturated fermented amines or unsaturated amines such as amines, 1 "3-butane diisocyanate, isopropyl chloride, chloropropane, etc., aliphatic co-dilutes; polystyrene, polyacrylate, polyacrylate Large monomers such as methyl acrylate, polybutyl acrylate, polybutyl propylene butyl vinegar, polylithium oxalate, etc. which have a monopropenyl group or a monopropenyl propionate group at the end of the molecular bond of the polymer, etc. ... such Other unsaturated monomers can be used alone or as a mixture of two or more; and the preferred carboxyl-containing copolymer of the present invention is ① 5 to 50% by weight of acrylic acid and / or fluorenyl acrylic acid, and 095 to 50%. % By weight selected from the group consisting of methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, phenethyl acrylate, benzyl methacrylate, styrene, and polystyrene macromonomers And at least one other unsaturated monomer in the group consisting of polymethyl methacrylate macromonomer. Specific examples of carboxyl-containing copolymers printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be cited. Available: acrylic acid / acrylic acid acrylate copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl acrylate / styrene copolymer, acrylic acid / acrylic acid styrene / polyethylene macromonomer copolymer, acrylic acid / Benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl acrylate / polyethylene macromonomer copolymer, acrylic acid / methyl acrylate / polymethyl acrylic acid vinegar huge monomer Bulk copolymers' acrylic acid / benzyl methacrylate copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl methacrylate / styrene copolymer, acrylic acid / benzyl acrylate / Page (Please read the notes on the back before filling in this page) The M-sheet scale is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 473647 A7 '' _B7_ / V. Description of the Invention (5) Polyethylene macromonomer copolymer, acrylic acid / benzyl acrylate / polymethylmethacrylate macromonomer copolymer, acrylic acid / methyl methacrylate / polyethylene macromonomer copolymer, acrylic acid / methyl acrylic acid Acrylate / Polymeryl; Acrylic acid acrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polyethylene macromonomer copolymer, acrylic acid / fluorenyl acrylic acid 2- Hydroxyethyl ester / Phenyl methacrylate / Polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl acrylate / styrene copolymer, methacrylic acid / methyl acrylate / styrene copolymer Methallylic acid曱. Phenyl Acrylic Acid, Allyl Phenyl Acrylic Acid, Dilute Polyalkenyl Acrylic Acid, Polymethyl Acrylate, Copolymer Monomer, Macromonomer Macromonomer, Macromethylene Alkenyl Ethylene Polypropylene / A (Please read the back Note: Please fill in this page again.) Propionic acid alkenyl propenyl propyl methyl, methacrylate, polymer copolymer comonomer large monomer huge ester macromethacrylate ethylene polypropylene / group 0 Μ 曱 曱 "-polyacid / ; Allyl Acrylic Acid Acrylic Acrylic Acrylic Acrylic Acid / Acrylic Acrylic Acrylic Acid Polymer Acrylic Polymer Propyl A
匕曰 酉 曱 S 巨丙 烯基 乙甲 聚聚 / / 匕曰 匕曰 s S 甲甲 苯苯 酸酸 烯烯 丙丙 基基 甲曱 / / 酸酸 烯烯 丙丙 基基 曱曱 、 、 物物 聚聚 共共 烯體 乙單 苯大 ? 匕曰 9— 酉 酸曱 烯酸 丙烯 基丙 甲基if 酉 / 烯酸 丙烯 基丙 甲基 、 甲 物、 聚物 共聚 體共 單體 大單 巨大 酯巨 曱烯 酸乙 烯聚 匕曰 酉 聚 經濟部智慧財產局員工消費合作社印製 曱酯 酸基 烯乙 丙羥 基2-曱酸 酸 烯 丙 基 曱 烯 丙 基 曱 聚 匕曰 巨 基 曱 物酯 聚甲 共苯 體酸 單烯 大 丙 烯物 丙聚 基共 曱體 單 大 巨 烯 乙 聚 酸 烯 丙 基 甲 酯 曱 苯 酸 烯 丙 基 〇 甲 - / 等 酯等 基物 乙聚 羥共 2-體 酸單 烯大 丙巨 基酯 曱曱 I酸 丙 中丙基 物基/ 聚曱酸 共、烯 之物丙 基聚基 羧共甲 含酯、 述甲物 上苯聚 酸共 烯烯 烯 丙乙、 基苯物 甲I/聚 / 酉 - 稀苯 ' Θ酸U 基稀A 曱丙酯 為基曱 佳曱酸 特 ii# 第 頁 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 47364! A7 B7 五、發明說明(6 ) 曱基丙烯酸/曱基丙烯酸笨曱酯/聚乙烯巨大單體共聚物、 曱基丙烯酸/曱基丙烯酸笨曱酯/聚甲基丙烯酸曱_巨大單 體共聚物、曱基丙烯酸/甲基丙烯酸甲酯/聚乙稀巨大單體 共聚物、曱基丙烯酸/曱基丙烯酸曱酯/聚甲基丙烯酸甲酯 巨大單體共聚物、曱基丙烯酸/甲基丙烯酸2_羥乙基醋/甲 基丙稀酸笨曱醋/聚乙烯巨大單體共聚物、甲基丙曱 基丙烯酸2-羥乙基酯/曱基丙烯酸苯甲酯/聚曱基丙烯酸曱 酯巨大單體共聚物。 再者,本發明所使用含羧基之有機性黏結劑(A)若含 有Clfl〜CM烷基之羧酸酯單元,可使其塗膜之密著性更佳 ’顯影性良好。 (請先閱讀背面之注意事項再填寫本頁)Glycol S Polyacryl Ethylene Polymer / // Glycol S Allyl Toluene Benzoate Acrylic Acid Allyl Acrylic Acid // Allyl Acrylic Acid Polycomonomer ethylene monobenzene? 9-9—Acrylic acid acrylic acid propyl propyl methyl if fluorene / acrylic acid propylene propyl methyl, formate, polymer comonomer comonomer large monomer huge ester giant Polyethylenic acid polymer printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives, Printed Polyethylenic Acid Allyl Alkyl Hydroxyl 2-Allanoic Acid Allyl Alkyl Allyl Polyalcohol Polyester Co-benzoic acid, mono-ene, macro-propylene, propylene-co-polymer, mono-macroene, ethylene-acrylic acid, allyl methyl ester, benzoic acid, allyl-, etc. Monoene macropropyl giant ester 曱 曱 I acid propyl propyl group / polyacrylic acid copolyene, olefinic material propyl polycarboxy co-methyl ester, benzene polyacrylic acid propylene allyl allyl ethylene, Benzylmethyl I / Polyene / Phenyl- Dilute Benzene 'Θ Acid U Dilute A Dipropyl Acetyl Acetate II # The paper size of this page applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 47364! A7 B7 V. Description of the invention (6) Acrylic acid / Arythyl acrylate / polyethylene macromonomer copolymer, Fluorenyl acrylic acid / fluorenyl acrylic acid methacrylate / polymethacrylic acid 曱Ester / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methacrylic acid 2-hydroxyethyl vinegar / methacrylic acid stupid vinegar / polyethylene megamonomer copolymer, methacryl 2-hydroxyethyl acrylate / benzyl methacrylate / poly fluorenyl acrylate macromonomer copolymer. Furthermore, if the carboxyl group-containing organic binder (A) used in the present invention contains a carboxylic acid ester unit of Clfl to CM alkyl group, the adhesion of the coating film can be made better. (Please read the notes on the back before filling this page)
經濟部智慧財產局員工消費合作社印制衣 (B、C)含乙烯性不飽和基之化合物、光起始劑 、感光性樹脂組成物係利用自由基連鎖反應,以得到高 感度之特性;㈣由基聚合型光阻劑之主要缺點為容易= 到乳氣終止聚合反應之影響’造成感度下降,$了改益此 =象,以往係在光阻膜上再塗佈_層氧氣遮斷膜,目前 則疋經由選擇適當之多官能基單體、光起始劑,並找出其 與有機性黏結劑、多官能基單體、 、 到具有良罐,殘膜率高且顯影==例:“ 成物。 4子之感光性树脂組 本發明所使用的含乙烯性不飴 具有丨個或2個或2個以上之乙 二之:合*⑻可為 和化合物,其中,具有丨個乙稀性==之乙稀性不飽 和化合物之例子有:丙稀酿胺、(;=:乙稀性不飽 、T暴)丙烯醯嗎啉、7_氨 第 8 頁 本纸張尺度適用中國國家標準(CNS)A4規1^.297公楚.---- 計 I I 4 1 經濟部智慧財產局員工消費合作社印製 頁 473647 A7 ------ B7 五、發明說明( 基-3’7 —二曱基辛基(甲基)丙烯酸酯、異丁氧基甲基(甲基 )丙烯醯胺、異冰片基羥乙基(甲基)丙烯酸酯、異冰片基( 甲基)丙烯酸醋、2-乙基己基(甲基)丙烯酸酯、乙基二乙 二醇(甲基)丙烯酸酯、第三辛基(甲基)丙烯醯胺、二丙_ (曱基)丙烯醯胺、二甲基氨基乙基(曱基)丙烯酸酯、十二 烧基(曱基)丙烯酸酯、二環戊烯羥乙基(曱基)丙烯酸酯、 二環戊烯(曱基)丙烯酸酯、N,N -二曱基(甲基)丙烯醯胺、 四氯苯基(曱基)丙烯酸酯、2 -四氯苯氧基乙基(甲基)丙埽 酸醋、四氫糠基(甲基)丙烯酸酯 '四溴笨基(甲基)丙烯酸 醋、2-四溴笨氧基乙基(甲基)丙烯酸酯、2_三氯苯氧基乙 基(甲基)丙烯酸酯、三溴苯基(曱基)丙烯酸酯、2 —三溴笨 氧基乙基(曱基)丙烯酸酯、2-羥乙基(甲基)丙烯酸酯、2_ 羥丙基(曱基)丙烯酸酯、乙烯基己内醯胺、N_乙烯基b比洛 烧_、苯氧基乙基(甲基)丙烯酸酯、五氯苯基(甲基)丙稀 酸酯、五溴苯基(曱基)丙烯酸酯、聚乙二醇單(曱基)丙稀 酸醋、聚丙二醇單(甲基)丙烯酸酯、冰片基(曱基)丙稀酸 酯、甲基三乙二醇(曱基)丙烯酸酯。 具有2個或2個以上乙烯性不飽和基之乙烯性不飽和化 合物,可舉例如下:乙二醇二(甲基)丙烯酸酯、二環戍稀 二(曱基)丙稀酸酯、三乙二醇二丙稀酸酯、四乙二醇二( 曱基)丙烯酸酯、三環癸烷二醇二甲撐基二(曱基)丙稀酸 6旨、三(2 -羥乙基)異氰酸酯二(曱基)丙烯酸酯、三(2 _經 乙基)異氰酸酯三(曱基)丙烯酸酯、己内酯改質之三(2_經 乙基)異氰酸酯三(曱基)丙烯酸酯、三羥曱基丙炫三(甲基 )丙烯酸酯、環氧乙烷(以下簡稱為「E0」)改質之三經甲 第 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) I----^--------訂---------線 f請先閱讀背面之>1意事項再填寫本頁,> 473647 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(8 ) 基丙烷三(曱基)丙烯酸酯、環氧丙烷(以下簡稱為「P0」) 改質之三羥甲基丙烷三(曱基)丙烯酸酯、三丙二醇二(甲 基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、雙酚A二縮水 甘油喊之兩末端(曱基)丙稀酸附加物、1,4 -丁二醇一(甲 基)丙烯酸酯、Ί,6-己二醇二(甲基)丙烯酸酯、季戊四脖 三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、聚_二 (曱基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二季戊四 醇六(曱基)丙烯酸酯、二季戊四醇五(曱基)丙烯酸酯、二 季戊四醇四(曱基)丙稀酸酯、己内酯改質之二季戊四醇六 (.曱基)丙浠酸醋、己内酯改質之二季戍四醇五(曱基)丙稀 酸酯、雙三羥甲基丙烷四(甲基)丙烯酸酯、Ε0改質之雙酚 Α二(曱基)丙烯酸酯、Ρ0改質之雙酚Α二(曱基)丙烯酸酯、 E0改質加氫之雙酚A二(曱基)丙烯酸酯、p〇改質加氫之雙 酚A二(曱基)丙烯酸酯、E0改質之雙酚F二(曱基)丙稀酸酯 、苯盼聚縮水甘油鍵之(甲基)丙烯酸酯等等。 前述乙烯性不飽和化合物中,特佳者為三經甲基丙烷 三(甲基)丙烯酸酯、E0改質之三羥甲基丙烧三(甲基)丙烯 酸醋' P0改質之三羥曱基丙烷三(甲基)丙烯酸酯、季戊四 醇三(曱基)丙烯酸酯、季戊四醇四(曱基)丙烯酸酯、二季 戊四醇六(曱基)丙烯酸醋、二季戊四醇五(甲基)丙烯酸醋 、二季戊四醇四(甲基)丙烯酸酯、己内酯改質之二季戍四 醇六(曱基)丙烯酸酯、己内酯改質之二牽 ^ , ^ A ^ 字戊四醇五(曱基) 丙烯酸酯、雙三羥曱基丙烷四(曱基)丙埽酸酿。 以100重量份的含羧基之有機性黏結劑為基準, 本發明所使用含乙稀性不飽和基之化合物./I y* a 切(B)的使用量 第10頁 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) —ΓΙ;----------------.訂—l·------線—.^vi (請先閱讀背面之注意事項再填寫本頁) 47364 A7 B7 經濟部智慧財產局員工消費合作社印製Ministry of Economic Affairs, Intellectual Property Bureau, Employees' Cooperative Printed Clothing (B, C) Compounds containing ethylenically unsaturated groups, photoinitiators, and photosensitive resin compositions use free-radical chain reactions to obtain high-sensitivity characteristics; ㈣ The main disadvantage of the photopolymerization based photoresist is that it is easy = the influence of the polymerization reaction to the termination of the emulsion gas causes the sensitivity to decrease, and the benefit is changed. This is the phenomenon in the past, which was coated on the photoresist film with a layer of oxygen blocking film. At present, through the selection of appropriate polyfunctional monomers and photoinitiators, and the identification of organic binders, polyfunctional monomers, and high-quality cans, high residual film rate and development == example : "Material. Photosensitive resin group of 4 sons. The ethylenic resin used in the present invention has one or two or two or more of them. The compound * can be a compound, of which, one has Examples of ethylenically unsaturated compounds with ethylenicity == are: acrylic amines, (; =: ethylenic unsaturated, T violent) acrylic morpholine, 7_ ammonia page 8 This paper is applicable to paper China National Standard (CNS) A4 Regulation 1 ^ .297 Gongchu. ---- Design II 4 1 Member of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Industrial and Consumer Cooperatives Page 473647 A7 ------ B7 V. Description of the Invention (Methyl-3'7-Dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylic acid) Amine, isobornyl hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, Third octyl (meth) acrylamide, dipropyl- (fluorenyl) acrylamide, dimethylaminoethyl (fluorenyl) acrylate, dodecyl (fluorenyl) acrylate, dicyclopentyl Enol ethyl (fluorenyl) acrylate, dicyclopentene (fluorenyl) acrylate, N, N -difluorenyl (meth) acrylamide, tetrachlorophenyl (fluorenyl) acrylate, 2- Tetrachlorophenoxyethyl (meth) propionate, tetrahydrofurfuryl (meth) acrylate 'tetrabromobenzyl (meth) acrylate, 2-tetrabromobenzyloxyethyl (methyl ) Acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (fluorenyl) acrylate, 2-tribromobenzyloxyethyl (fluorenyl) acrylate, 2-hydroxyethyl (meth) acrylate, 2_ hydroxypropyl (fluorenyl) acrylate, vinyl caprolactam, N_vinyl b-pylon, phenoxyethyl (meth) acrylic acid Ester, pentachlorophenyl (meth) acrylate, pentabromophenyl (fluorenyl) acrylate, polyethylene glycol mono (fluorenyl) acrylic acid ester, polypropylene glycol mono (meth) acrylate, Bornyl (fluorenyl) acrylic ester, methyl triethylene glycol (fluorenyl) acrylate. Ethylene unsaturated compounds with two or more ethylenically unsaturated groups, for example: ethylene glycol Di (meth) acrylate, dicyclofluorene di (fluorenyl) acrylate, triethylene glycol dipropionate, tetraethylene glycol di (fluorenyl) acrylate, tricyclodecanediol Dimethylene di (fluorenyl) acrylic acid 6 purpose, tris (2-hydroxyethyl) isocyanate di (fluorenyl) acrylate, tris (2-ethyl) isocyanate tri (fluorenyl) acrylate, hexamethylene Lactone modification three (2-ethyl) isocyanate tri (fluorenyl) acrylate, trihydroxyfluorenyl propyl tris (meth) acrylate, ethylene oxide ( (Hereinafter referred to as "E0") The modified paper size of the third paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) I ---- ^ -------- Order-- ------- Line f, please read the > 1 notice on the back before filling out this page, > 473647 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (8) Fluorenyl) acrylate, propylene oxide (hereinafter referred to as "P0") modified trimethylolpropane tri (fluorenyl) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (methyl Base) acrylate, bisphenol A diglycidyl, both terminal (fluorenyl) acrylic acid additions, 1,4-butanediol mono (meth) acrylate, fluorene, 6-hexanediol di (formaldehyde) Base) acrylate, pentaerythritol tris (meth) acrylate, pentaerythritol tetra (meth) acrylate, poly-di (fluorenyl) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol Modification of hexa (fluorenyl) acrylate, dipentaerythritol penta (fluorenyl) acrylate, dipentaerythritol tetra (fluorenyl) acrylic acid ester, caprolactone modification Modification of pentaerythritol hexa (.fluorenyl) propionate, caprolactone Modification of pentaerythritol tetrakis (pentyl) propionate, ditrimethylolpropane tetra (meth) acrylate, E0 modified Modified bisphenol A di (fluorenyl) acrylate, PO modified bisphenol A di (fluorenyl) acrylate, E0 modified hydrogenated bisphenol A di (fluorenyl) acrylate, p0 modified Hydrogen bisphenol A di (fluorenyl) acrylate, E0 modified bisphenol F di (fluorenyl) acrylic acid ester, phenoxy polyglycidyl bond (meth) acrylate, etc. Among the aforementioned ethylenically unsaturated compounds, particularly preferred are trimethylolpropane tri (meth) acrylate, E0 modified trimethylolpropane tris (meth) acrylate vinegar 'P0 modified trihydroxyamidine Propane tri (meth) acrylate, pentaerythritol tri (fluorenyl) acrylate, pentaerythritol tetra (fluorenyl) acrylate, dipentaerythritol hexa (fluorenyl) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Tetrakis (meth) acrylate, caprolactone modified second quaternary fluorene tetraol hexa (fluorenyl) acrylate, caprolactone modified quaternary ^, ^ A ^ word pentaerythritol penta (pentyl) acrylate 2, Bis (trimethylol) propane tetra (fluorenyl) propanoic acid. Based on 100 parts by weight of a carboxyl-containing organic binder, the ethylenically unsaturated group-containing compound used in the present invention. / I y * a Cut (B) usage page page 10 This paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) —ΓΙ; ----------------. Order—l · ------ line —. ^ Vi (Please (Read the notes on the back before filling out this page) 47364 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
五、發明說明( 為100~ 160重量份,尤以110〜150重量份為較佳;當含乙烯 性不飽和基之化合物(B)的使用量小於1 0 0重量份時,樹脂 組成物的塗膜密著性會變差,前述化合物之使用量若大於 1 6 0重量份,則樹脂組成物之顯影性不佳。 本發明所使用之光起始劑(C)係選自至少一種選自 笨乙酮系化合物 (acetophenone)及至少一種選自二σ米嗤 系化合物 (bi imidazole),其中,苯乙_系化合物 (Acetophenone)如對-二甲 胺笨乙 asj (p-dimethylaminoacetophenone) , α,α’一二甲氧基氧<匕偶氮 苯乙 _ ( α , α dimethoxyazoxyacetophenone) , 2,2’-二 曱 基 -2- 苯基 苯乙酮 (2, 2 ’-d i me thy 1-2-phenylacetophenone),對-甲氧基苯乙洞{(卩-11161;11〇又7-acetophenone),2 -甲基-[4-(曱硫基)苯 ^]{2-methyl-[4-(methylthio)phenol]} , 2-嗎 °林代-1-丙酮(2- morpholino-1-propanone),2-辛基- 2-N,N-二曱胺-1-(4-嗎0林代苯基)-1-丁嗣[2-l;enzyl-2-N,N-dimethylamino-1-(4-raorpholinophenyl)-l-butanone] ° 而二 π米0坐系化合物 (Bi imidazole),如 2,2’-雙(鄰-氯笨基)-4,4’,5,5’-四苯 基 °米 °坐[2,2’-bis(o-chlorophenyl)-4,4’,5,5’-tertphenyl-imidazole],2,2’-雙(鄰-氟苯基)-4,4’,5,5’-四苯基咪唑 [2, 2’-bis(〇-f luorophenyl)-4, 4’,5, 5’-tertphenylimidazole], 2, 2’-雙(鄰-曱氧基苯基)-4, 4’5, 5’ -四苯基咪唑(2,2’-bis(o-methoxyphenyl)-4,4,5, 5’-tertphenylimidazole) ,2,2’-雙(對-甲氧基笨基)-4,4’5,5’-四笨基咪唑[2,2’-bis(p-methoxyphenyl)-4,4’5,5’-tertphenylimidazole] 第11頁 . 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -------------装--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 473647 經濟部智慧財產局員工消費合作社印製 A7 ------Β7__ 五、發明說明(10 ) ’ 2, 2’-雙(2, 2’,4, 4’-四甲氧基苯基)-4,4,5, 5’-四苯基咪唑 [2,2’-bis(2,2’,4,4’-tertmethoxyphenyl)-4,4’5,5’-tertphenyl-111^(132〇16],2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基-1,2’-二 〇米。坐[2, 2’-bis(2-chlorophenyl)-4, 4’,5, 5’-tetraphenyl-l, 2’-biimidazole]等。其中,以2 -苯基- 2- N,N-二曱胺-1-(4-嗎0林代苯基)-1-丁酮[2-benzyl-2-N, N-dimethylamin〇-l-(4-morpholinophenyl)-l-butanone]與 2, 2’ -雙(2-氯苯基 )-4,4’,5,5’_ 四苯基-1,2,-二咪唑[2,2’-1^3(2-chlorophenyl)-4, 4’,5, 5’-tetraphenyl-l, 2’-biimidazole] ο 本發明之感光性樹脂組成物可進一步添加二苯曱酮 (benzophenone)系化合物為光起始劑,上述二苯曱酮系化 合物乃例如·· 17塞嘲酮(Thioxanthone),2, 4-二乙基0塞嘲酮 (2, 4-diethyl thioxanthanone) , 口塞0頓酮-4-楓 (thioxanthone-4-sulfone),二苯曱酮(benzophenone), 4,4’-雙(二曱胺)二苯曱酮[4,4’-1313((1111161:1171&111111〇 )benzophone] ,4,4’-雙(二乙胺)二苯甲 _ [4,4’-bis(diethylamino) benzophenone]等;其他尚可進一步 添加之光起始劑乃例如:笨偶感(b e n z i 1),乙酿基(a c e t y 1) 等之a -二酮(α-diketone)類,二苯乙醇_(匕61^〇111)等 之酮醇(acyloin)類,二苯乙醇酮曱醚(benzoin methylether),二苯乙醇酮乙醚(benzoinethylether),二 苯乙醇酮異丙醚(benzoin isopropyl ether)等之酮醇鱗 (acyloin ether)類,2, 4,6-三甲基苯醯二苯基膦氧化物 (2,4,6-trimethyl-benzoyl diphenylphosphineoxide), 第12頁 ^纸張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ~ --------------------、訂 ii;-------線 (請先閱讀背面之注意事項再填寫本頁) 0. 經濟部智慧財產局員工湞費合作社印制π 473647 A7 ' 丨 _B7__ -五、發明說明(11 ) 雙- (2, 6-二曱氧基笨醯)-2,4, 4-三曱基苯基膦氧化物 [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylbenzyl phosphineoxide]等之醯膦氧化物(acylphosphineoxide) 類,蒽醌(anthraquinone), 1,4-萘醌(1,4-naphthoquinone )等之酿i(quinone)類,苯醯甲基氯(phenacyl chloride), 三溴甲基苯楓(tribromomethyl phenylsulfone),三(三 氣曱基)-s-三口秦[tris (trichloromethyl)-s-triazine] 專之鹵化合物,二-第三丁基過氧化物(di-tert-I butylperoxide)等之過氧化物。其中,以二苯曱酮 (benzophenone)系化合物為佳,尤以4, 4,-雙(二乙胺)二 本曱酮[4, 4 -bis(diethylamino) benzophenone]效果最 佳。使用本發明所選用之光起始劑(C ),可得到顯影色差 小之感光性樹脂組成物’前述光起始劑的使用量以含 乙烯性不飽和基之化合物(B)為基準之卜5〇重量%。 CD)有機溶劑 感光性樹脂組成物通常均含有機溶劑,其主要目的為 調整其流動性及黏度,當有機溶劑選擇不恰當,會造成感 光性樹脂組成物之貯存安定性不佳及塗佈性變差。 本發明所使用之溶劑為可和其它有機成分完全溶解, 而且其揮發性必須高到在常壓下,只須少許熱量便可使其 從分散液中蒸發。因此,常壓下沸點低於18〇t之溶劑最 常使用,這些溶劑包括芳香族(Aromatic)系,如苯、曱苯 及二曱苯;醇(Alcohol)系,如曱醇及乙醇;醚類,二烷 基醚如乙二醇單正丙醚;醋類,如二乙二醇二甲 第 13 頁 -------------裝--------訂- (請先閱讀背面之注音?事項再填寫本頁) 線 473647 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(l2 ) (diethyleneglycol dimethyl ether)、四氫11夫0南、乙二醇 一曱 ϋ (ethy1eneg1yco1 monomethyl ether)、乙二醇一 乙 ϋ (ethyleneglycol monoethyl ether)、乙二醇一甲喊 乙酸酯(methyl cellosolve acetate)、乙二醇一乙謎乙 酸酯(ethyl cellosolve acetate)、二乙二醇一甲醚 (diethyleneglycol monomethyl ether)、二乙二醇一乙 SI (diethyleneglycol monoethyl ether)、二乙二醇一丁 ϋϋ (diethyleneglycol monobutyl ether)、丙二醇一曱醚 乙酸醋(propyleneglycol monomethyl ether acetate)、 丙二醇一乙醚乙酸醋(propyleneglycol monoethyl ether acetate)、丙二醇一丙鰱乙酸醋(propyleneglycol monopropyl ether acetate);酮(Ketone)系,如曱乙酮 、丙酮,其中以酯類為較佳;又以丙二醇曱韃乙酸酯 (propyleneglycol methyl ether acetate)、丙二醇乙醚 乙酸酯(propyleneglycol ethyl ether acetate),或兩 者併用’對於感光性樹脂組成物之貯存安定性及塗佈性最 佳,本發明之有機溶劑(D)的使用量乃佔全部感光性樹 脂組成物之6 0〜9 0重量%。 (E)顏料: 本發明所使用之顏料(E)為二羰代D比咯并吨哈 (diketopyrrolopyrrole)系之紅色顏料,其具體例有:c. j 顏料紅2 5 4以及C · I.顏料紅2 5 5等。 前述顏料可單獨或混合2種以上使用,以1 〇〇重量份含 羧基之有機性黏結劑(A)為基準’顏料(E)的使用量為 __第14頁 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公楚) —*1—.1 ^--------------訂—U-------線! (請先閱讀背面之注意事項再填寫本頁) ------ 473647 A75. Description of the invention (100 to 160 parts by weight, especially 110 to 150 parts by weight is preferred; when the amount of the ethylenically unsaturated group-containing compound (B) is less than 100 parts by weight, The adhesiveness of the coating film will be deteriorated, and if the amount of the aforementioned compound is more than 160 parts by weight, the developability of the resin composition is not good. The photoinitiator (C) used in the present invention is selected from at least one selected Acetophenone and at least one compound selected from bi imidazole, wherein Acetophenone such as p-dimethylaminoacetophenone, α, α'-dimethoxyoxy < Azo acetophenone (α, α dimethoxyazoxyacetophenone), 2,2'-difluorenyl-2-phenylacetophenone (2, 2'-di me thy 1-2-phenylacetophenone), p-methoxyphenethyl hole {(卩 -11161; 11〇 and 7-acetophenone), 2-methyl- [4- (fluorenylthio) benzene ^] {2-methyl- [4- (methylthio) phenol]}, 2-morpholino-1-propanone, 2-octyl-2-N, N-difluorenamine-1- (4- 0 linyl phenyl)- 1- 丁 嗣 [2-l; enzyl-2-N, N-dimethylamino-1- (4-raorpholinophenyl) -l-butanone] ° and two π 米 0 sitting compounds (Bi imidazole), such as 2,2 ' -Bis (o-chlorobenzyl) -4,4 ', 5,5'-tetraphenyl °°°° [2,2'-bis (o-chlorophenyl) -4,4', 5,5'- tertphenyl-imidazole], 2,2'-bis (o-fluorophenyl) -4,4 ', 5,5'-tetraphenylimidazole [2, 2'-bis (〇-f luorophenyl) -4, 4 ', 5, 5'-tertphenylimidazole], 2, 2'-bis (o-methoxyphenyl) -4, 4'5, 5'-tetraphenylimidazole (2,2'-bis (o-methoxyphenyl ) -4,4,5,5'-tertphenylimidazole), 2,2'-bis (p-methoxybenzyl) -4,4'5,5'-tetraphenylimidazole [2,2'-bis (p-methoxyphenyl) -4,4'5,5'-tertphenylimidazole] Page 11. The paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ---------- --- install -------- order --------- line (please read the precautions on the back before filling out this page) 473647 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7- ---- Β7__ V. Description of the invention (10) '2, 2'-bis (2, 2', 4, 4'-tetramethoxyphenyl -4,4,5,5'-tetraphenylimidazole [2,2'-bis (2,2 ', 4,4'-tertmethoxyphenyl) -4,4'5,5'-tertphenyl-111 ^ (132 〇16], 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-20 meters. [2, 2'-bis (2-chlorophenyl) -4, 4 ', 5, 5'-tetraphenyl-l, 2'-biimidazole] and the like. Among them, 2-phenyl-2- 2-N, N-diamidoamine-1- (4-morpholinophenyl) -1-butanone [2-benzyl-2-N, N-dimethylamin〇-1 -(4-morpholinophenyl) -l-butanone] and 2, 2'-bis (2-chlorophenyl) -4,4 ', 5,5'_ tetraphenyl-1,2, -diimidazole [2, 2'-1 ^ 3 (2-chlorophenyl) -4, 4 ', 5, 5'-tetraphenyl-l, 2'-biimidazole] ο The photosensitive resin composition of the present invention may be further added with benzophenone The compound is a photoinitiator, and the aforementioned benzophenone compound is, for example, 17 thioxanthone, 2, 4-diethyl thioxanthanone, and mouth stopper 0 Thioxanthone-4-sulfone, benzophenone, 4,4'-bis (diamine) benzophenone [4,4'-1313 ((1111161: 1171 & 111111〇) benzophone], 4,4'-bis (diethylamine) dibenzoyl _ [4,4'-bis (diethylamino) benzophenone], etc .; other light initiators that can be further added are, for example, stupidity (Benzi 1), a-diketones such as acety 1 and acyloins such as diphenylethanol- (d 61 ~ 〇111), Acyloin ethers such as benzoin methylether, benzoinethylether, benzoin isopropyl ether, 2, 4, 6-three 2,4,6-trimethyl-benzoyl diphenylphosphineoxide, page 12 ^ Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ~ --- ----------------- 、 Order ii; ------- line (please read the notes on the back before filling this page) 0. Staff of Intellectual Property Bureau of the Ministry of Economic Affairs Π 473647 A7 '丨 _B7__ printed by the co-operative cooperative-V. Description of the invention (11) Bis- (2, 6-dioxobenzyl) -2,4,4-tris-phenylphenylphosphine oxide [ bis- (2,6-dimethoxy-benzoyl) -2,4,4-trimethylbenzyl phosphineoxide] and other acylphosphineoxides, anthraquinone, 1,4-naphthoquinone ), Etc. (quinone), phenacyl chloride, tribromomethyl phenylsulfone, tris (trifluoromethyl) -s- 三口 秦 [tris (trichloromethyl) -s -triazine] Specialized halogenated , Di - tert-butyl peroxide (di-tert-I butylperoxide) etc. peroxide. Among them, a benzophenone-based compound is preferred, and 4,4, -bis (diethylamino) dibenzophenone [4, 4-bis (diethylamino) benzophenone] is most effective. By using the photoinitiator (C) selected in the present invention, a photosensitive resin composition having a small developmental color difference can be obtained. The amount of the aforementioned photoinitiator is based on the ethylenically unsaturated group-containing compound (B). 50% by weight. CD) Organic solvents. The photosensitive resin composition usually contains organic solvents. Its main purpose is to adjust its fluidity and viscosity. When the organic solvent is not selected properly, it will cause poor storage stability and coating properties of the photosensitive resin composition. Worse. The solvent used in the present invention can be completely dissolved with other organic ingredients, and its volatility must be so high that it can be evaporated from the dispersion with only a small amount of heat. Therefore, solvents with a boiling point of less than 180 ° t under normal pressure are most commonly used. These solvents include aromatic (Aromatic) systems such as benzene, toluene, and dioxane; Alcohol systems, such as methanol and ethanol; ether Dialkyl ethers such as ethylene glycol mono-n-propyl ether; vinegars such as diethylene glycol dimethyl Order-(Please read the phonetic on the back? Matters before filling out this page) Line 473647 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (l2) (diethyleneglycol dimethyl ether), Tetrahydro 11 husband 0 South, Ethylene glycol monoethyl ether (ethy1eneg1yco1 monomethyl ether), ethylene glycol monoethyl ether (ethyleneglycol monoethyl ether), ethylene glycol monomethyl acetate (methyl cellosolve acetate), ethylene glycol monoethyl ether acetate (ethyl cellosolve acetate), diethyleneglycol monomethyl ether, diethyleneglycol monoethyl ether, diethyleneglycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether acetate ( propyleneglycol monomethyl ether acetate), Propyleneglycol monoethyl ether acetate, propyleneglycol monopropyl ether acetate; ketone (Ketone), such as ethyl ethyl ketone, acetone, of which esters are preferred; and propylene glycol ethyl acetate Propyleneglycol methyl ether acetate, propyleneglycol ethyl ether acetate, or a combination of the two, is used for the best storage stability and coating properties of the photosensitive resin composition. The organic solvent (D ) Is used in an amount of 60 to 90% by weight of the entire photosensitive resin composition. (E) Pigment: The pigment (E) used in the present invention is a dicarbonyl Diketopyrrolopyrrole red pigment, and specific examples thereof are: c. J Pigment Red 2 5 4 and C · I. Pigment Red 2 5 5 and so on. The aforementioned pigments can be used alone or as a mixture of two or more. Based on 100 parts by weight of a carboxyl-containing organic binder (A), the amount of pigment (E) used is __ page 14 This paper applies Chinese national standards (CNS) A4 Specifications (210 X 297 Gongchu) — * 1—.1 ^ -------------- Order—U ------- line! (Please read the notes on the back before filling this page) ------ 473647 A7
經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
20~5⑽重讀’ g卩可製得透純良好之感光性樹脂组成秒 ,於本發明中,顏料依據所期望 八劑 上述分散劑可舉:陽離子系、陰離子系、非離Si政: I·生聚石夕乳院系、氟系等之界面活性劑為例;其中’,、界面 活性劑舉例而言有:綮瑷氫 ' 水衣孔乙烷十二烷基醚、聚環氧乙烧 硬脂驢醚、聚環氧乙烷油等 ^ AWW叫寸 < 钬锿氧乙烧炫基醚類;聚 ί哀乳乙烧辛基苯喊、來摄备7 t ^ 乳乙烷壬基苯醚等之聚環氧乙烷 烷基苯醚類;聚乙二醢-H^ 尺 K G —私一月桂酸酯、聚乙二醇二硬脂酸酯 4聚 醇—Sa類,山梨糖醇酐脂肪酸酯類;脂肪酸改 質之聚酯類;3級胺改質之聚胺基甲酸酯类員;以下為市面 販賣之商品名:KP341(信越化學工業製)、普利弗隆 No. 75’ No. 90, No. 95(共榮社油脂化學工業製)、s〇lsperse 3000,5000,9000,12000,13240,13940,17000,20000,24000 ’ 2 6 0 0 0 ’ 2 8 0 0 〇 (捷利康精細化學品公司)、美卡夫克 F171’F172’ F173(大日本印墨化學工業製)、弗洛多 FC430,FC431(住友3M製)、阿魏卡多AG71〇、薩弗隆 S382,SC-101, SC-102, SC-103, SC-104, SC-105, SC-1068C 旭硝子製)等等;此等界面活性劑可單獨或混合2種以上使 用’相對於1 00重量份之顏料(E),前述界面活性劑一般 係使用低於1 0 0重量份,而以使用5〜5 0重量份為佳。 本發明之組成物中,必要時可進一步添加各種添加物 ’例如:填充劑、本發明含羧基之有機性黏結劑(A)以外 的高分子聚合物、密著促進劑、抗氧化劑、紫外線吸收劑 、防凝集劑等。 此等添加物之具體例可舉有:玻璃、铭等之填充劑; 第15頁 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明說明(l4 ) (請先閱讀背面之注意事項再填寫本頁) 也乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、聚氟丙烯酸烷 酯等之有機性黏結劑(A)以外的高分子化合物;乙烯基三 甲氧基石夕烧、乙烯基三乙氧基矽烷、乙烯基三(2_甲氧乙 氣基)矽烷、N-(2-氨基乙基)-3-氨基丙基甲基二曱氧基矽 烷、N-(2-氨基乙基)-3-氨基丙基三曱氧基矽烷、3_氨基 丙基二乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3_ 袞氧丙氧基丙基甲基二曱氧基石夕貌、2_(3,4-環氧環己基) 乙基二甲氧基矽烷、3-氯丙基曱基二曱氧基矽烷、3_氯丙 基三曱氧基矽烷、3-甲基丙烯氧基丙基三曱氧基矽烷、 氫硫基丙基三曱氧基矽烷等之密著促進劑;2,2_硫代雙(4〜 甲基-6-第三丁基苯酚)、2,6-二-第三丁基苯酚等之抗氧 化劑;2-(3-第三丁基-5-曱基-2-羥基苯基)_5_氯苯并三 坐、烷氧基苯并苯酮等之紫外線吸收劑;及聚丙烯酸鈉等 之防凝集劑。 本發明之組成物係上述成分(A)〜(£ ),必要時可使用 各種混合機、分散機進行混合分散,而調製其他添加劑與 溶劑混合。混合機、分散機可使用迄今所公知者。舉例而 言有:均化器、捏和機、球磨機、2或3軸式研磨機、塗 經濟部智慧財產局員工消費合作社印制农 料振動器、砂石研磨機'達依隆研磨機(夕"4夕$小)等之 砂石研磨機。 較佳的調製法係將顏料(E)與有機性黏結劑(A)加入溶 劑均勻混合,必要時使用丨或2攪拌器一邊加熱一邊混練, 使顏料(E)與有機性黏結劑(A)完全溶合,即可獲得均—之 著色體。其次’於所得之著色體中加入溶劑,必要時可加 入分散劑或各種添加劑,再使用以球磨機或玻璃珠作為分 ________第 16 頁 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 473647 五、發明說明(15 ) 散媒之各種混砂機(如達依隆研磨機)進行分散。此時 玻璃珠的粒徑愈小,即可獲得愈小的分散體。同時使 液控制在-定的溫度,亦可獲得再現性良好的分散結果月。 於此所得之分散體,必要時可藉由離心分離或傾析而 將粗大的粒子摘除。以此所得之分散液的顏料粒子捏 以1μ以下為佳’上述粒徑又以〇 〇2μ〜。·知為較佳。將以 此所得之著色分散體與含乙烯性不飽和基化合物以及光起 始劑混合,即可得本發明之感光性樹脂組成物。 本發明之組成物係於基板上藉由旋轉塗布、流延 、:式塗布等之塗布方法塗布而形成感放射線性組成:声 ”1於所指定之掩膜圖案間曝光,並浸潰於23±2。心 分鐘進行顯像,再經著色而形成圖案。此時 使用之放射線,以使心線、h線、i線等之紫外線為佳。 基板’舉例而言有用於液晶顯示裝置等之低納玻璃、 透(派勒斯玻璃)、石英玻璃及於此等玻 換裝置基板(”::)等ί用==影裝置等之光電變 畫素之黑色矩陣 等此4基板-般係形成隔離各 顯影液係使用如:氫氧化納、氫氧化鉀、碳酿 氨碳酸!、碳酸氯卸,納、曱基卿 物、四乙Α鍵厂乙胺、二甲基乙醇胺、四曱基銨羥化洽 "5Γ〇' 用量一 。且使用& # &卜 之經/合解的鹼性水溶液 使用此專驗性水溶液所構成之顯影液時,一般係於顯 經濟部智慧財產局員工消費合作社印制衣 473647 A7 ----- ------------Β7 _______ 五、發明說明(π ) 影後再以水洗淨。 本發明進一步藉下列實施例說明之。 〔實施例1〕 將設置一氮氣入口、攪拌器、加熱器、冷凝管及一溫 度計之1000ml四頸圓底燒瓶在氮氣氣氛下導入丙二醇一甲 醚乙酸醋25.7重量份、甲基丙烯酸苯甲酯24.2重量份、丙 稀酸5 · 2重量份之可聚合單體混合物。當四頸圓底燒瓶之 内容物被攪拌時,油浴之溫度被提升至1 〇 〇 °c,然後將2,2,-偶氮曱基雙丁腈0.6重量份溶於3〇g丙二醇一曱醚乙酸酯之 溶液’以五等分之量在一小時間隔下添加在四頸圓底燒瓶 中。完成聚合後’將聚合產物自四頸圓底燒瓶中取出,轉 化程度為99. 5%以上,以上樹脂溶液之固體含量為35%。 將以上製備的含羧基之有機性黏結劑(A)13. 29重量 份與含乙烯性不飽和基之化合物(B)5. 58重量份、2—苄基 -2-N,N-二曱胺-1-(4-嗎啉代苯基)-卜丁酮[00重量份、 4, 4’-雙(二乙胺)二苯曱酮i_q〇重量份、乙基(三—乙氧基) 丙烯酸酯43.13重量份,以及6.〇〇重量份之CI254,並以搜 拌器混合製成感光性樹脂組成物。然後,在玻璃基板上以 旋轉塗佈方式得到約2 # m之塗膜,並在85t下預烤5分鐘 後再以紫外光(曝光機Canon PLA-501F) 200mJ/cni2照射, 之後浸潰於2 3 °C之顯影液2分鐘,再以純水洗淨,並在2 〇 〇 °C下烘烤60分鐘’即可得到玻璃基板上之鍍膜,所製得之 鍍膜依以下之方式評價其顯影性、密著性、顯影色差(△ Eab*)以及透光性,評價結果如表一所示。 〔實施例2〜5及比較例卜7〕 第18頁 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐巧 ---- --------------------•訂—和------ (請先間讀背面之注意事項再填寫本頁) Α720 ~ 5⑽Reread 'g 卩 can make a transparent resin composition with good transparency. In the present invention, the pigment can be based on the desired eight dispersants: cationic, anionic, non-ionizing Si: I · Examples of surfactants in raw polysilicone milk faculty, fluorine series, etc .; among them, the surfactants include, for example, tritium hydrogen, water-coating hole ethane dodecyl ether, and polyethylene oxide. Stearyl donkey ether, polyethylene oxide oil, etc. ^ AWW is called < ethoxylated ethyl ethers; polyethoxylated octylbenzene, 7 t ^ lactyl nonyl Poly (ethylene oxide) alkyl phenyl ethers such as phenyl ether; polyethylene glycol-H ^ k KG—private monolaurate, polyethylene glycol distearate 4-polyol—Sa, sorbitol Anhydride fatty acid esters; fatty acid modified polyesters; grade 3 amine modified polyurethanes; the following are commercially available trade names: KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Priveron No. 75 'No. 90, No. 95 (manufactured by Kyoeisha Oil Chemical Industry), solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 20000, 24000' 2 6 0 0 '2 8 0 0 〇 (Jie Kang Fine Chemicals Co., Ltd.), Mekafke F171'F172 'F173 (made by Dainippon Ink Chemical Industry), Frodo FC430, FC431 (made by Sumitomo 3M), Ferocardo AG71〇, Saffron S382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-1068C (made by Asahi Glass), etc .; these surfactants can be used alone or as a mixture of two or more kinds, relative to 100 parts by weight For the pigment (E), the aforementioned surfactant is generally used in an amount of less than 100 parts by weight, but preferably in an amount of 5 to 50 parts by weight. Various additives may be further added to the composition of the present invention, for example, a filler, a high-molecular polymer other than the carboxyl-containing organic binder (A) of the present invention, an adhesion promoter, an antioxidant, and ultraviolet absorption Agent, anti-aggregation agent, etc. Specific examples of these additives can include: fillers such as glass, Ming, etc. Page 15 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Packing -------- Order --------- line (please read the notes on the back before filling this page) A7 B7 V. Description of the invention (l4) (please read the notes on the back before filling this page) Also vinyl alcohol, Polymer compounds other than organic binders (A), such as polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; vinyltrimethoxylithium, vinyltriethoxysilane, vinyl Tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Trimethoxysilane, 3-aminopropyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3_oxopropyloxypropylmethyldioxolith, 2_ ( 3,4-epoxycyclohexyl) ethyldimethoxysilane, 3-chloropropylfluorenyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, hydrothiopropyl Adhesion promoters such as trimethoxysilane; 2,2_thiobis (4 ~ methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and other antioxidants ; 2- (3-Third-butyl-5-fluorenyl-2-hydroxyphenyl) _5-chlorobenzobenzotris, alkoxybenzophenone and other ultraviolet absorbers; and the prevention of sodium polyacrylate Coagulant. The composition of the present invention is the above-mentioned components (A) to (£), and if necessary, various mixers and dispersers can be used for mixing and dispersing, and other additives are mixed with the solvent. As the mixer and the disperser, conventionally known ones can be used. Examples include: homogenizers, kneaders, ball mills, 2 or 3-axis grinders, printed agricultural material vibrators printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and gravel grinders. Xi " 4 Xi $ small) and other sand and stone grinders. A better preparation method is to add the pigment (E) and the organic binder (A) to the solvent and mix uniformly. If necessary, use a 丨 or 2 mixer to knead while heating to make the pigment (E) and the organic binder (A). Completely dissolved, you can get a homogeneous-colored body. Secondly, add a solvent to the obtained colored body, and if necessary, add a dispersant or various additives, and then use a ball mill or glass beads as the branch. ________ page 16 This paper is applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 473647 V. Description of the invention (15) Various sand mixers (such as Da Yilong mill) for dispersing the media for dispersion. The smaller the particle size of the glass beads at this time, the smaller the dispersion can be obtained. At the same time, the liquid is controlled to a fixed temperature, and the dispersion results with good reproducibility can be obtained. The dispersion obtained here can be used to remove coarse particles by centrifugation or decantation if necessary. The pigment particles of the dispersion liquid thus obtained are preferably kneaded at 1 µm or less', and the above-mentioned particle size is 0.02 µ ~. · Know better. The coloring dispersion thus obtained is mixed with an ethylenically unsaturated group-containing compound and a photoinitiator to obtain the photosensitive resin composition of the present invention. The composition of the present invention is coated on a substrate by a coating method such as spin coating, casting, and coating to form a radiation-sensitive composition: "Sound" 1 is exposed between the specified mask patterns and immersed in 23 ± 2. The image is developed in a minute, and then patterned by coloring. The radiation used at this time is preferably ultraviolet rays of the heart line, h line, i line, etc. The substrate is used for example in liquid crystal display devices. Low-Sodium Glass, Transparent (Palex Glass), Quartz Glass, and the substrates of these glass-changing devices (": :), etc. = black matrices of optoelectronic variable pixels such as shadow devices, etc. Form the isolation of each developing solution system such as: sodium hydroxide, potassium hydroxide, carbon and ammonia carbonic acid! , Chlorine carbonate, sodium, ammonium base, tetraethyl A bond plant ethylamine, dimethylethanolamine, tetramethylammonium hydroxylation " 5Γ〇 'Amount of one. And the use of &# & Buzhijing / combined alkaline aqueous solution using the developer solution composed of this specialized aqueous solution is generally printed on clothing 473647 A7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs --- ------------- Β7 _______ 5. Description of the invention (π) After washing, wash with water. The invention is further illustrated by the following examples. [Example 1] A 1000 ml four-necked round-bottomed flask equipped with a nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer was introduced under a nitrogen atmosphere into 25.7 parts by weight of propylene glycol monomethyl ether acetate and benzyl methacrylate. A polymerizable monomer mixture of 24.2 parts by weight and 5.2 parts by weight of acrylic acid. When the contents of the four-necked round-bottomed flask were stirred, the temperature of the oil bath was raised to 100 ° C, and then 0.6 parts by weight of 2,2, -azobisbisbutyronitrile was dissolved in 30 g of propylene glycol. Diethyl ether acetate solution 'was added to the four-necked round bottom flask in five equal portions at one hour intervals. After the completion of the polymerization, the polymerization product was taken out of the four-necked round-bottomed flask, and the degree of conversion was more than 99.5%, and the solid content of the above resin solution was 35%. 13.29 parts by weight of the carboxyl group-containing organic binder (A) prepared above and 5.58 parts by weight of the ethylenically unsaturated group-containing compound (B), 2-benzyl-2-N, N-difluorene Amine-1- (4-morpholinophenyl) -bubutanone [00 parts by weight, 4, 4'-bis (diethylamine) benzophenone i_q〇 parts by weight, ethyl (tri-ethoxy ) 43.13 parts by weight of acrylate and CI254 by 6.0 parts by weight, and mixed with a blender to prepare a photosensitive resin composition. Then, a coating film of about 2 # m was obtained by spin coating on a glass substrate, and pre-baked at 85t for 5 minutes, and then irradiated with 200 mJ / cni2 of ultraviolet light (Canon PLA-501F exposure machine), and then immersed in The developing solution at 2 ° C for 2 minutes, then washed with pure water and baked at 2000 ° C for 60 minutes to obtain a coating film on a glass substrate. The obtained coating film was evaluated in the following manner The developability, adhesion, developmental color difference (Δ Eab *), and light transmittance are shown in Table 1. [Examples 2 to 5 and Comparative Example 7] Page 18 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- ------------ -------- • Order—and ------ (Please read the precautions on the back before filling this page) Α7
Α7 I 經濟部智慧財產局員工消費合作社印製 五、發明說明(17 ) 依照實施例1之製法,成份物按表一所示之各該重量 :製得實施例2〜5及比較例卜7之感光性樹腊組成物:玻璃 基板上之鑛帛製備及評價Μ皆如f施例卜以賈结果如 表一所示。 、 〔實施例6〕 依照實施例1之製法,成份物除將2_苄基_2_N N_二甲 胺(4-嗎琳代苯基)_卜丁酮丨.⑽重量份改為二笨銅丨⑽ 重量份外’其它成份及重量份同實施例丨;而玻璃基板上 之鍍膜亦按照實施例i製備之,所製得之錢膜的顯影性、 役著性及透光性佳,顯影色差(△仏1/)為2.Α7 I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (17) According to the method of Example 1, the ingredients are shown in Table 1 according to the weight: Examples 2 to 5 and Comparative Example 7 The photosensitive tree wax composition: the preparation and evaluation of the ore on the glass substrate are as in Example f. The results are shown in Table 1. [Example 6] According to the production method of Example 1, except for the component, 2_benzyl_2_N N_dimethylamine (4-morpholinophenyl) _bubutanone 丨. ⑽ parts by weight was changed to dibenzyl The other components and parts by weight of copper are the same as those in the embodiment; and the coating film on the glass substrate is also prepared according to the embodiment i. The developed film has good developability, durability, and light transmission. The developing color difference (△ 仏 1 /) is 2.
[評價方式] (1)顯影性:觀察於玻璃基板上圖像形成之完整性。 〇:圖像線條平整 X:圖像線條不平整,有毛邊 (2)密著性:根據於JIS. 54〇〇(19〇〇)8.5密著性試驗中之 8. 5. 2測足方法,以小刀割成j 〇 〇個基盤目,再以膠帶 沾黏後撕下,計算被撕下基盤目之數目,根據下列之 基準評價: 〇:5個以下 △ : 6~49個 X: 50個以上 ---------裳--------訂---------線 (請先閱讀背面之注意事項再填寫本頁)[Evaluation method] (1) Development property: Observe the completeness of image formation on a glass substrate. 〇: The image lines are flat X: The image lines are uneven and have burrs (2) Adhesiveness: According to JIS. 54〇〇 (19〇) 8.5 Adhesion Test 8.5 Foot measurement method , Cut into j 00 basic disks with a small knife, and then remove them with adhesive tape. Calculate the number of removed basic disks, and evaluate according to the following criteria: 0: 5 or less △: 6 ~ 49 X: 50 More than --------- Shang -------- Order --------- line (Please read the precautions on the back before filling this page)
^7364 經濟部智慧財產局員工消費合作社印製 A7 B7 五 ' 發明說明(18 ) (3) 顯影色差(AEab*):在玻璃基板上將感光性樹脂組成 物以旋轉塗佈方式得到2μπι之塗膜,在85。(:下預烤5分 鐘,再以紫外光(曝光機Canon PLA-501F) 200MJ/cm2照 射後以色度計測量色度後,將塗膜浸潰於2 3 r顯影液2 分鐘,再以純水洗淨,乾燥後再測量色度。前後色度 值之差異即可求得顯影色差(AEab*)。 (4) 透光性:在玻璃基板上將感光性樹脂組成物以旋轉塗 佈方式得到約2μπι之塗膜,在85 °C下預烤5分鐘,以色 度計測量色度’色度值固定X值約〇. 5 7 4 ± 0. 0 2時,所 得Y值: 〇:Y值大於25. 0,透光性佳 △ :Υ值介於23.5與25.0間,透光性尚可 Χ:Υ值小於23. 5,透光性差 依照本發明所述之感光性樹脂組成物於含乙烯性不飽 和基之化合物(Β)與含羧基之有機性黏結劑(Α)比例為 1 〇 0 / 1 0 0〜1 6 0 Π 0 0之範圍,並選用二羰代吡咯并吡咯系之 紅色顏料,可進一步搭配特定之光起始劑組合,即可得到 顯影性、密著性、it光性佳且顯影色差甚小之感光性樹脂 組成物。 惟以上所述僅為本發明數較佳可行實施例,舉凡熟習 此項技藝人仕,其依本發明精神範疇所作之修飾或變更, 均理應包含在本案申請專利範圍内。 第20頁 (請先閱讀背面之注意事項再填寫本頁) ’--— 11--'訂--fc------線 — ^^ 7364 A7 B7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (5) Invention description (18) (3) Development color difference (AEab *): The photosensitive resin composition is spin-coated on a glass substrate to obtain a 2 μm coating. Film, at 85. (: Pre-bake for 5 minutes, and then irradiate with UV light (Canon PLA-501F) 200MJ / cm2 and measure the color with a colorimeter, then immerse the coating film in 2 3 r developer for 2 minutes, and then Wash with pure water and measure the chromaticity after drying. The difference between the chromaticity values before and after can be used to determine the development color difference (AEab *). (4) Light transmission: The photosensitive resin composition is spin-coated on a glass substrate A coating film of about 2 μm was obtained, and pre-baking was performed at 85 ° C for 5 minutes, and the chromaticity was measured by a chromaticity meter. The chromaticity value was fixed at an X value of about 0.5 7 4 ± 0.02, and the obtained Y value was: 〇 : Y value is greater than 25.0, good light transmittance △: Υ value is between 23.5 and 25.0, light transmittance is acceptable X: Υ value is less than 23.5, poor light transmittance according to the photosensitive resin composition of the present invention The ratio between the ethylenically unsaturated compound (B) and the carboxyl group-containing organic binder (A) is in the range of 100/1 0 0 ~ 1 6 0 Π 0 0, and dicarbonylpyrrolo is selected. The pyrrole-based red pigment can be further combined with a specific photoinitiator combination to obtain a photosensitive resin group having good developability, adhesion, it light properties, and small development color difference. However, the above are just a few of the preferred and feasible embodiments of the present invention. For those skilled in the art, any modifications or changes made in accordance with the spirit of the present invention should be included in the scope of patent application in this case. Page 20 (Please read the notes on the back before filling this page) '--- 11-' Order --fc ------ line-- ^
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TWI406062B (en) * | 2005-07-29 | 2013-08-21 | Sumitomo Chemical Co | A photosensitive resin composition for optical spacers, an optical spacers, and a liquid crystal display device |
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TWI406062B (en) * | 2005-07-29 | 2013-08-21 | Sumitomo Chemical Co | A photosensitive resin composition for optical spacers, an optical spacers, and a liquid crystal display device |
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