1283791 玖、發明說明： 【發明所屬之技術領域】 本發明為關於-種電泳顯示裝置用顯示液。本發明亦 為關於一種電泳顯示裝置用顯示液之製造方法。 【先前技術】 利用電場作用使視認狀態可逆變化之顯示方法，有如 =面谷信監修之「數位文獻之最新技術」初版，cmc出版 中坪細記載之液晶、電致變色、電泳、磁泳等，進年來已 研究開發。利用其之顯示界面為一對電極基板及 =其中：顯示元件所構成，該顯示界面上再連接於各 極顯不影像用之外加信號之驅動電路。 本發明為關於其中利用雷、、炎土 干w盆制、…電泳顯示裝置用顯 不液及其製造方法，以下所示即為其技術動向。 ”電冰顯不裳置用顯示液之作用原理大致可分 第1類為將染料溶於電絕緣性溶劑中著色，、，“ 、° 或顏料-樹脂複合體粒子分 ，亚將顏料粒子 置用顯示液，第2類為將二=者色液中之電泳顯示裝 樹脂複合體粒子分散於I 5色調之顏料粒子或顏料_ 置用顯示液。 、無色之電絕緣性溶劑之電泳顯示裝 使用第1類電泳顯示裝置用 泳顯示裝置用顯示液封裝 :不液之發明，例如將電 元件裝置於電極間構成 垓微膠囊為顯示 人电冰顯示裝 號公報）者，該電泳顯示穿 罝（曰本專利第2551783 射率無機顏料分散於溶有/二吹疋將二氧化鈦等高折 ，、千之著色分散液中。 315086 5 ⑽3791 著色粒子：二!例如將由帶不同極性之2種不同色調之 -方為透明顯示：置用顯示液，裝入於至少 構成之電泳顯示裝Wi包極間介由間隔片所形成之槽中而 M (日本特開昭第62-269124號公報、國 丨不么開第98/038%號公韶、女、人 示裝置用顯示液之例)亦包含微膠囊中内包電泳顯 相n L p員提案之其他方法例如將至少分散有2種電極性 二：及電泳速度互異之電泳性粒子之電泳顯示裝置 用顯不液，裝入至少一 衣置 隔片所形成之槽中而構成^ 片對向電極間介由間 50886號公報）。 成之電冰顯示裝置（特開昭第63- 凝聚:方在===帶不:電荷之電泳性粒子 t ^ ^ 且^或電何調節劑達成立體或 電的相斥效果之提案（特表平第8_51〇79〇號公報）。1283791 发明Invention Description: [Technical Field] The present invention relates to a display liquid for an electrophoretic display device. The present invention also relates to a method of producing a display liquid for an electrophoretic display device. [Prior Art] The display method of reversible change of the visual state by the action of the electric field is as follows: the first edition of the "Newest Technology of Digital Documents" by Megumi Shinji, and the liquid crystal, electrochromic, electrophoresis, magnetic swimming, etc. In the past years, research and development has been carried out. The display interface is composed of a pair of electrode substrates and = display elements, and the display interface is connected to a driving circuit for adding signals to the respective pixels. The present invention relates to a display liquid for use in a thunder, an analytic soil, a liquid crystal display device, and a method for producing the same, and the following is a technical trend thereof. "Electric ice is not used in the display liquid. The principle of action can be roughly divided into the first class for coloring the dye in an electrically insulating solvent, ", ° or pigment-resin composite particles, and the pigment particles are placed. In the case of the display liquid, the second type is a pigment particle or a pigment-distributing display liquid in which the electrophoretic display-packed resin composite particles in the two color liquids are dispersed in an I 5 color. The electrophoretic display device of the colorless electrically insulating solvent is packaged with the display liquid for the swimming display device of the first type electrophoretic display device: the invention is not liquid, for example, the electric component device is formed between the electrodes to form the microcapsule for displaying the electric ice display. In the installation bulletin, the electrophoresis shows that the electrophoresis shows 罝 (罝 专利 Patent No. 2551783, the inorganic pigment is dispersed in the soluble/two-blow 疋, and the titanium dioxide is high-fold, and in the colored dispersion. 315086 5 (10) 3791 Colored particles: two For example, it will be transparently displayed by two different hues with different polarities: the display liquid is applied to at least the electrophoretic display pack Wi-pack formed in the slot formed by the spacers and M (Japanese special Kaizhao No. 62-269124, the example of the 98/038% public display, female, and human display device for the display of the device, also includes other proposals for the inclusion of electrophoretic phase in the microcapsules. For example, an electrophoretic display device in which at least two kinds of electrophoretic particles having different electrophoretic velocities are dispersed is filled with at least one groove formed by a spacer to form a counter electrode. Inter-media 508 Bulletin No. 86). The electric ice display device (Special opening: 63-aggregation: square === with no charge: electrophoretic particles t ^ ^ and ^ or electric regulator to achieve stereo or electrical repellent effect of the proposal (special Table 8:51〇79〇).
大障蔽用白1 :另，法，亦有由樹脂及白色顏料製成之較 大用白色粒子gg ~ m L 泳顯示裝置用顯示^提宰(=者色粒子及溶劑構成之電 報）。 夜之W(特開平第叫_號公 ，此外•亦有同時分別包含第卜第2類之例，即由八 至少…電粒子與界面活性劑之分散介質構成，其前： 電冰性粒子t至少1種中含有4級銨化合物（ ^ 1 19704號公報）。 丁弟11· 然：、:上述方法有電泳顯示裝置用顯示液之電安定性 不足、電泳速度太低等問題。 315086 6 1283791 本發明之目& + & 係利用不易凝取 種電泳顯示裝置用顯示液，其 的亦在提電泳速度快之帶電微粒者。本發明之目 【發明内容】‘顯不裝置用顯示液之製造方法。 示裝3::為關於一種電泳顯示裝置用顯示液，該電泳顯 特汽矣义，、,、不液至少含1種帶電微粒及電絕緣性溶劑，其 * ’、、、刖述帶電微粒係含二 環稀金屬催化劑合成之樹脂者。 她日為以方 以芳ΐ::亦為關於上述電泳顯示裝置用顯示液，其中， 以…金屬催化劑合成之樹脂為聚乙埽者。-中 電、發Γ又為關於上述電泳顯示裝置用顯示液，其中， 劑合成之=1:另含其中不含以芳環稀金屬催化 风 < 树月日的帶電微粒者。 本發明X為關於上述電泳顯示裝置 對1重量份經處理之帶電微粒另含（ΜΠ至、1G、重旦;:中： 基琥珀酸酐、酯或亞胺者。 里”之烯 本發明又為關於一種微膠囊， 置用顯示液者。 震”係合上边電泳顯示裝 本發明又為關於一種電泳顯示裝置 顯示裝置用顯示液者。 八，、3上迷電沬 本為關於一種電泳顯示裝置用顯示 方法，係含至少1種帶電微粒鱼 裝置用顯示液之製造方法，其中將入以;劑之電泳_示 合成之樹脂及著色劑之混合物粉碎之步：：烯金屬催化劑 3ΐ5〇8β 7 1283791 【貫施方式】 本發明為關於一種電泳顯示裝置用顯示液，係至少] 種帶電微粒及電絕緣性溶劑。電泳顯示裝置用顯示液之作 用原理大致可分為2類’第！類為將染料溶於電絕緣性溶 劑中著色，並將帶電微粒分散於著色之電絕緣性溶劑之電 泳顯示裝置用顯示液’帛2類為將2種不同色調之帶電微 粒分散於電絕緣性溶劑中而製成之電泳顯示裝置用顯示 液。本發明之電泳顯示裝置用顯示液在上述第i類、第2 類之任一種中均可使用。 +本發明中所使用之帶電微粒其特徵為至少含樹脂及 著色劑’且該樹脂為含以芳環烯金屬催化劑合成之樹脂 者。 芳環烯金屬催化劑為例如二氯二茂錯（士晴㈣㈣與 甲基鋁氧烷（methylaluminoxane)組合之物，為聚合活性 高、活性點均-之物。本發明人等發現含該以㈣稀金屬 催化劑合成之樹脂之粒子不會與相反極性之粒子凝聚，而 完成本發明。其例如使用芳環烯金屬催化劑聚合之聚乙烯 稱為芳環稀金屬PE(Polyethylene)，其特徵為側鏈分枝少、 分子量分布集中、低分子量成份少等。 作為芳環烯金屬催化劑用之芳環烯金屬化合物為例 如鈦、锆、鎳、鈀、銓、鈮、鉑等四價過渡金屬上至少與 1们以上含環戊一浠基骨架之配位基配位之化合物之總 稱。含環戊二稀基骨架之配位基可例舉如環戊二烯基、甲 基％戊二烯基、乙基環戊二烯基、正或異丙基環戊二烯基、 315086 8 1283791 正、異、第二、第三丁基環戊二烯基、己基環戍二烯基、 辛基環戊一烯基等燒基取代環戊二烯基，二甲基環戊二浠 基、甲基乙基環戊二烯基、曱基丙基環戊二烯基、甲基丁 基環戊二烯基、甲基己基環戊二烯基、乙基丁基環戊二稀 基、乙基己基環戊二烯基等烷基二取代環戊二烯基，三甲 基環戊二烯基、四甲基環戊二烯基、五甲基環戊二烯基等 烧基多取代環戊二烯基，甲基環己基環戊二烯基等環烷基 取代環戊二烯基，茚基、4,5，6,7-四氫茚基、芴基等。 含環戊二烯基骨架之配位基以外之配位基可例舉如 氯、>臭等一價陰離子配位基，二價陰離子螯合配位基、烴 基、醇鹽基、醯胺基、芳醯胺基、芳氧化基、磷基、芳磷 基、甲矽烧基、取代甲矽烷基等。上述之烴基為例如碳原 子數約1至12者，可例舉如甲基、乙基、丙基、丁基、異 丁基、戊基、異戊基、己基、庚基、辛基、壬基、癸基、 十一烧基、2-乙基己基等烧基，環己基、環戊基等環烧基， 苯基、甲苯基等芳基，苯甲基、新苯基等芳烷基，壬基苯 基等。 以含環戊二烯基骨架配位基配位之芳環烯金屬化合 物之具體例可舉如環戊二烯化鈦參（二甲醯胺）、甲基環戍 二烯化鈦參（二甲醯胺）、二氯化雙（環戊二烯基）化鈦、二氯 化二甲基甲矽烷基四甲基環戊二烯基-第三丁基醯胺化 錯、一氣化二甲基甲石夕烧基四甲基環戊二稀基正丁基苯 基醯胺化鍅、二氯化甲基苯基甲矽烷基四甲基環戊二烯基_ 第三丁基醯胺化給、二氯化二甲基甲石夕烧基四甲基環戊二 315086 9 1283791 烯二酸共聚物等乙烯系、尼龍系、矽膠系、脲烷系、三聚 氰胺系、苯并鳥糞胺系、酚系、氟化（四氟乙烯）系、二氣 乙烯系、4級吡啶鍚鹽系、合成橡膠、纖維素、乙酸纖維 素、幾丁聚醣、褐藻酸鈣、聚二氯乙烯樹脂、硝基纖維素、 醇酸樹脂、酚樹脂、聚酯樹脂、聚乙烯丁縮醛樹脂、聚異 氰酸酯樹脂、聚醯胺樹脂、環氧樹脂等，但並不限於此等 聚合物材料。 本發明中之著色劑可使用任意之著色劑，第2類電泳 顯示裝置用顯示液以使用白色著色劑及白色以外之著色劑 為佳。 本發明中所使用之白色著色劑，可使用如氧化鈦、氧 化鋅、氧化锆、矽、矽酸鈣、氧化鋁、硫化辞、鉛白、辞 白、辞鋇白、二氧化録、高嶺土、雲母、硫酸鎖、克羅斯 白、滑石等。此等著色劑在帶電微粒中之含量比例以印 至90重量％範圍為佳。 不贫明中所使 廿 ，、π 〇 '用7 1例举如鎘 貫、编鋇黃、氧化鐵黃、鈦黃、鈦鋇黃、純、鎮鎖撥 銦橙、氧化鐵紅、紅丹、銀朱n、制紅、昂 氧化鐵棕、鋅鐵鉻棕、鉻綠、氧化鉻、維利迪安綠 録鉻綠、鈦㈣、紺青、姑藍、群f、赛❹μ、: 鉻藍、姑紫、猛紫'碳黑、鐵黑、鍾鐵酸黑、钻鐵酸里 銅鉻黑、銅隸黑、鈦黑、㈣、銅粉、㈣… 胺黑、酸性黃、雙偶氮黃、縮合偶氮黃、蒽㈣ 噪滿黃、甲块亞胺銅黃、_黃、苯并咪錢黃了二膀 315086 11 1283791 黃、單偶氮黃色澱、二硝基苯胺橙、吡唑啉酮橙、赫里奥 橙、納夫妥紅、甲苯胺紅、二硝基苯胺胭脂紅、酸性豔猩 紅、吡唑啉酮紅、鹼性蕊香紅6G色澱、二硝基苯胺紅、 入漆硃、邦紅色澱、色澱紅、豔胭脂紅、棗紅丨〇B、納夫 妥紅、唾D丫酮洋紅 '縮合偶氮紅、納夫妥胭脂紅、苑猩紅、 縮合偶氮猩紅、苯并咪唑酮胭脂紅、蒽醌紅、花紅、花紫 蘇紅、喹吖酮紫蘇紅、喹吖酮猩紅、喹吖酮紅、二酮吼略 並吡咯、苯并咪唑酮棕、酞菁綠、維多利亞藍色澱、酞菁 藍、酸性天藍、驗性藍調色劑、標準還原藍、驗性蕊香紅 B色殿、甲基紫色殿、L紫、納夫妥紫等。此等著色 J可以單獨或混合使用。此等著色劑在帶電微粒中之含量 以0 · 1至6 0重量％為佳。 两便者已劑分散在樹脂中，亦可再添加一般已知之彥 料衍生物、離子鍵聚合物、低分子量離子鍵聚合物、各希 ==良好分散效果之添加劑。特別是低分子量離子鍵秀 、有良好之顏料分散效果。離子鍵聚合物可例舉如乙烯 丙烯酸共聚物以金屬中和之物，Large barriers use white 1 : In addition, the method also has a large white particle gg ~ m L made of resin and white pigment. The display device uses a display to show the weight of the particles (the color particles and the solvent). The night of W (Special Kaiping is called _ _ public, in addition • also contains the second class of the two, which is composed of eight at least ... the dispersion of dielectric particles and surfactants, before: Electro-ice particles At least one of the above-mentioned compounds contains a quaternary ammonium compound (J1919704). Dingdi 11·:: The above method has problems such as insufficient electrical stability of the display liquid for the electrophoretic display device and too low electrophoresis speed. 315086 6 1283791 The object of the present invention is a display liquid for electrophoretic display devices which is not easily condensed, and which is also capable of extracting charged particles having a fast electrophoresis speed. The object of the present invention is "display of display device" Method for producing a liquid. Display 3:: For a display liquid for an electrophoretic display device, the electrophoretic display has at least one type of charged particles and an electrically insulating solvent, and *', A description of the charged particles of a resin containing a bicyclic dilute metal catalyst. Her day is Fang Yifang:: It is also a display liquid for the above electrophoretic display device, wherein the resin synthesized by the metal catalyst is a polyethylene - Zhongdian, hairpin Further, the display liquid for an electrophoretic display device according to the above, wherein the composition of the agent is =1: further comprising a charged particle which is catalyzed by an aromatic ring-dense metal < And 1 part by weight of the treated charged particles further containing (ΜΠ, 1G, heavy denier;: medium: succinic anhydride, ester or imine.) The invention is further related to a microcapsule, using a display liquid The present invention relates to a display liquid for an electrophoretic display device display device. The display device for an electrophoretic display device is a display method for at least one type of electrophoretic display device. The method for producing a display liquid for a charged particle fish device, wherein the electrophoresis of the agent is shown as a step of pulverizing a mixture of a synthetic resin and a coloring agent: an olefin metal catalyst 3ΐ5〇8β 7 1283791 [The present invention] The display liquid for an electrophoretic display device is at least a kind of charged particles and an electrically insulating solvent. The principle of action of the display liquid for an electrophoretic display device can be roughly classified into two types: the first class is to dissolve the dye. Electrophoresis in an insulating solvent, in which the charged particles are dispersed in a colored electrically insulating solvent, and the display liquid ''2' is used for electrophoresis in which two kinds of charged particles of different colors are dispersed in an electrically insulating solvent. A display liquid for a display device. The display liquid for an electrophoretic display device of the present invention can be used in any of the above-mentioned i-class and second-class. The charged fine particles used in the present invention are characterized by containing at least a resin and a coloring agent. 'And the resin is a resin containing an aromatic cycloolefin metal catalyst. The aromatic cycloolefin metal catalyst is, for example, a combination of dichlorodi Mao (Shi (4)) and methylaluminoxane, which has high polymerization activity. The present inventors have found that the particles containing the resin synthesized by the (four) dilute metal catalyst do not aggregate with particles of opposite polarities, and have completed the present invention. The polyethylene which is polymerized, for example, using an aromatic cycloolefin metal catalyst is referred to as an aromatic ring metal PE (Polyethylene), which is characterized by less side chain branching, concentrated molecular weight distribution, and low molecular weight component. The aromatic cycloolefin metal compound used as the aromatic cycloolefin metal catalyst is a ligand having at least one or more cyclopentanyl skeletons on a tetravalent transition metal such as titanium, zirconium, nickel, palladium, rhodium, iridium or platinum. The general term for the compound of the coordination. The ligand having a cyclopentadienyl skeleton may, for example, be a cyclopentadienyl group, a methyl pentadienyl group, an ethylcyclopentadienyl group, a n- or isopropylcyclopentadienyl group, and 315086 8 1283791 Anthracene, iso, second, tert-butylcyclopentadienyl, hexylcyclodecadienyl, octylcyclopentenyl, etc., alkyl substituted cyclopentadienyl, dimethylcyclopentadienyl , methylethylcyclopentadienyl, decylpropylcyclopentadienyl, methylbutylcyclopentadienyl, methylhexylcyclopentadienyl, ethylbutylcyclopentadienyl, An alkyldisubstituted cyclopentadienyl group such as an ethylhexylcyclopentadienyl group, a polysubstituted group such as a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group or a pentamethylcyclopentadienyl group A cyclopentadienyl group such as a cyclopentadienyl group, a methylcyclohexylcyclopentadienyl group, a cyclopentadienyl group, a fluorenyl group, a 4,5,6,7-tetrahydroindenyl group, a fluorenyl group or the like. The ligand other than the ligand having a cyclopentadienyl skeleton may, for example, be a monovalent anionic ligand such as chlorine or odor, a dianion chelating ligand, a hydrocarbon group, an alkoxide group or a decylamine. A group, an arylamine group, an aryloxy group, a phosphorus group, an arylphosphino group, a formazan group, a substituted formyl group, and the like. The above hydrocarbon group is, for example, a carbon number of about 1 to 12, and may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group or a fluorene group. a group such as a thiol group, a fluorenyl group, an eleven alkyl group, a 2-ethylhexyl group, a cycloalkyl group such as a cyclohexyl group or a cyclopentyl group, an aryl group such as a phenyl group or a tolyl group, or an aralkyl group such as a benzyl group or a neophenyl group. , mercaptophenyl and the like. Specific examples of the aromatic cycloolefin metal compound coordinated to the cyclopentadienyl skeleton-containing ligand include cyclopentadienide (dimethylamine) and methylcyclodecadiene oxide (second). Methionine), bis(cyclopentadienyl)titanium dichloride, dimethylformamidinyltetramethylcyclopentadienyl-t-butylammonium amide, monomethylated dimethyl Tetramethyl sulphate tetramethylcyclopentadienyl n-butylphenyl hydrazide hydrazine, methyl phenyl decyl alkyl tetramethyl cyclopentadienyl _ tert-butyl amide Ethylene, nylon, tannin, urethane, melamine, benzoguanamine, etc., such as dimethyl methacrylate, tetramethylcyclopentane 315086 9 1283791 enedionic acid copolymer , phenolic, fluorinated (tetrafluoroethylene), diethylene, 4, pyridinium, synthetic rubber, cellulose, cellulose acetate, chitosan, calcium alginate, polyvinyl dichloride resin, Nitrocellulose, alkyd resin, phenol resin, polyester resin, polyvinyl butyral resin, polyisocyanate resin, polyamide resin, epoxy resin, etc., but not Within such a polymer material. In the coloring agent of the present invention, any coloring agent can be used, and the display liquid for the second type of electrophoretic display device is preferably a white coloring agent or a coloring agent other than white. The white coloring agent used in the present invention may be, for example, titanium oxide, zinc oxide, zirconium oxide, cerium, calcium citrate, aluminum oxide, sulfuric acid, lead white, white, rhyme, dioxin, kaolin, Mica, sulphuric acid lock, Kroos white, talc, etc. The proportion of such colorants in the charged fine particles is preferably in the range of 90% by weight. Not in the poor, the π 、, π 〇 ' use 7 1 examples such as cadmium, braided yellow, iron oxide yellow, titanium yellow, titanium yttrium, pure, Zhendeng dial indium orange, iron oxide red, red , Silver Zhu n, made red, ang iron oxide brown, zinc iron chrome brown, chrome green, chrome oxide, Villidian green chrome green, titanium (four), indigo, green, group f, celluloid μ,: chrome blue, Gu Zi, Meng Zi 'carbon black, iron black, ferro-tin black, ferritic acid copper chrome black, copper black, titanium black, (four), copper powder, (four)... amine black, acid yellow, bisazo yellow, Condensed azo yellow, bismuth (four) noise full yellow, a block of imine copper yellow, _ yellow, benzopyrene yellow two bladders 315086 11 1283791 yellow, monoazo yellow lake, dinitroaniline orange, pyrazolone Orange, Herriot Orange, Nafto Red, Toluidine Red, Dinitroaniline Carmine, Acid Scarlet Red, Pyrazolone Red, Basic Rutin Red 6G Lake, Dinitroaniline Red, Painted Zhu, Banghongdian, Sediment Red, Yanzhizhihong, Jujube B, Nafto Red, Salivation D-ketone, Red, Condensed Azo Red, Nafto Carmine, Court Scarlet, Condensed Azo Scarlet, Benzene Imidazoxanone rouge Red, blush, safflower, flower perilla red, quinacridone perilla red, quinacridone scarlet, quinophthalone red, diketone oxime pyrrole, benzimidazolone brown, phthalocyanine green, Victoria blue lake, Phthalocyanine blue, acid blue, blue blue toner, standard reduction blue, temperament red B color hall, methyl purple temple, L purple, nalfitux purple. These colorings J can be used singly or in combination. The content of such colorants in the charged fine particles is preferably from 0.1 to 60% by weight. The two agents are dispersed in the resin, and may be further added with generally known derivatives, ionomers, low molecular weight ionomers, and additives having a good dispersion effect. In particular, it has a low molecular weight ion bond and a good pigment dispersion effect. The ionomer polymer may, for example, be an ethylene-acrylic copolymer which is neutralized with a metal.
龠口々^ ^ ’由阿來德公司以ACLYI 販售者。^有Ca鹽、Man 1 具有顏料分散絲。其酸價考慮其與樹脂之親和二 I妒以下耗圍為佳’或60 mgK〇H/g以下更佳， 無酉夂價者亦可。其重量平均分子量 下更佳 低分子量離子鍵聚合物為佳。 _G範圍之 帶電微粒中使用帶電劑之 化合物、杯芳烴(Caiixarene)化合物“列可例舉如鐵 金屬皂類，再與樹脂、 315086 12 1283791 著色劑、電絕緣性溶劑、添加劑組合使其帶正或負電。p 化合物可自由選擇1級至4級者，可自銨化合物、銃化: 物、鎮化合物中選擇。與氮、硫或磷原子鍵結之取代基為 例如烷基、芳基。一般以鹽存在而可成對者有以氯為代表 之鹵系元素或羥基、叛酸基等，但並不限定於此等。其中 特別以1至3級之胺鹽或4級之銨鹽為佳。此外，亦可使 用嗪系之笨胺黑衍生物帶電荷性染料、胺系樹脂。 本發明之帶電微粒最短徑及最長徑之比以1:〗至ι ·· 5〇之比例為佳。因係非球形，其優點為能表現立體位阻、 且其表面積大，因此可發揮存在於表面之帶電劑之最大效 果。其比例在1 ·· 1.5至1 : 20範圍時更佳。 帶電微粒之平均粒徑以20 # m下為佳，要獲得更好之 電泳性及分散安定性時，其比例以丨至1〇//m範圍較佳。 其分散安定性不足時，亦可再添加一般所知之界面活 性劑等分散劑，在不致阻礙其電絕緣性之情況，可添加烯 基琥珀酸酐、酯或亞胺、矽烷化合物等。烯基琥珀酸酐、 酯或亞胺可例舉如聚異丁烯琥珀酸酐、聚異丁烯琥珀酸 酯、聚異丁烯琥珀酸亞胺等。此等分散安定劑之添加量， 以其所處理之帶電微粒重量為i時以〇〇1至1〇之範圍為 佳。 本發明中所使用之電絕緣性溶劑，可使用介電常數3 ·〇 以下且其谷積電阻係數在1 00Ω·cm以上者。可例舉如 EXON化學（股）製造之艾索貝-GHLm·、艾索爾〇3〇、 D40、D80、D 11〇、D 13〇，sheU公司製造之西爾索 13 315086 1283791 (Shellsol)A、AB ’曰本石油（股）製造之奈福德膠l、μ、pj 及甲苯、二甲苯。 二甲苯之取代基為鄰位、間位、對位之任意者均可， 亦可為任意組合之混合物。對電絕緣性溶劑而言總帶電微 粒之重量比例以1至50重量％之範圍為佳。 弟1類電永顯示裝置用顯示液中，可使用將染料溶於 電絕緣性溶劑中所製成之著色電絕緣性溶劑。 其&料可使用油溶性染料’例如醇溶黑（$ B、s s B B、 AB)、苯胺黑底色（sa、SAP、SAPL、EE、EEL、EX、EXBP、 EB)、油溶黃（105、107、129、3G、ggs)、油溶橙（2〇1、 PS、PR)、酸性橙、油溶紅（5B、rr、〇G)、油溶猩紅、油 粉紅312、油溶紫#730、馬克隆勒克斯藍RR、斯米普拉斯 特綠G、油溶棕（GR、416)、蘇丹黑X60、油溶綠（5〇2、BG)、 油溶藍（613、2N，BOS)、油溶黑（HBB、860、BS)、巴黎 酸性黃（1101、11〇5、31〇8、412〇)、巴黎酸性橙（32〇9 321〇)、 巴黎酸性紅（1306、1355、2303、3304、3306、3320)、巴 秦酸性粉紅23 10N、巴黎酸性棕（24〇2、34〇5)、巴黎酸性 監（3405、1501、1603、1605、1607、2606、2610)、巴黎 酉夂性备、（1701、1702)、巴黎酸性黑（18〇2、18〇7、38〇4、381〇、 3820、3830)等。 本發明電泳顯示裝置用顯示液之製造方法中，包含將 3以芳％稀金屬催化劑合成之樹脂與著色劑之混合物加以 粉碎的步驟。 以下對本發明電泳顯示裝置用顯示液製造方法流程 14 315086 1283791 之—例加以說明。首券 θ 散於樹腊中。必要時拌步驟將顏料(著色劑)完全分 再將所得之混摔LI;:加:料分散劑加以混拌。繼之 上亦可。亦#田 π碎。粉碎步驟1次亦可，2次以 亦可採用數種粉碎太4 預粉碎，再進扞m 例如先以乾式粉碎進行 驟中可、仃濕“碎。該情況下在最後之濕式粉碎步 r化二广電絶緣性溶劑及帶電齊卜使微粒機能化。機 別是濕式粉碎二二二並表現非球狀之意。其中特 什心万式對其形成非球狀尤適合。 力…、此拌步驟中’樹脂與著色劑可適當地配合分散 t ’再以韓蘇式混合機、冷卻式混合機、諾塔混合機、鼓 ::合器、磨砂機等混合後’再以班伯里混拌機、扎淫和 μ機、雙軸磨碎機、三軸磨碎機、單軸擠壓機、二轴掩 機等將著色劑與樹脂加熱混拌。加熱混拌步驟後含著色 劑與樹脂之混拌混合物亦可加以粗粉碎。 乾式粉碎步驟以低溫冷來粉碎操作為佳。以下再說明 本發明中所使用之低溫冷;東粉碎。—般粒狀熱可塑性樹脂 不易在常溫下進行粉碎。但將含樹脂及著色劑之混掉混合 物與渦輪粉碎機等粉碎機以液態氮冷卻至_196它，再利用 樹脂低溫下之脆性加以粉碎，可以微粉碎成5〇〇#m以下。 同時，低溫冷凍粉碎後再經分級機適當地依粒徑分級，去 除粗大粒子後再進行後續之濕式粉碎時可提高其粉碎效 率〇 濕式粉碎步驟中，濕式粉碎機可以粉碎至所欲之粒裎 範圍。本發明中所可使用之濕式粉碎機可例舉如超微粉碎 315086 15 1283791 機、輾輪式混砂機、戴諾磨（dynomill)、球磨機、強力亞培 司磨機、脈衝磨機、可波磨（CoBall-Mill)、細鑽砂磨機、 DCP磨機、OB磨機等介質型濕式粉碎機，或均質機、微 粒均質機、三角形研磨機（Trigonal)、刀型磨（Slasher)、膠 體磨機、超音波研磨機（Cavitron)、哥拉特磨（Golatlu)、吉 納斯磨（Genus)、克來爾混碎機（Clear Mix)等非介質型濕式 粉碎機。 將本發明電泳顯示裝置用顯示液包於微膠囊内之電 泳顯示裝置用顯示微粒所使用之微膠囊，可以原位 (in-situ) 法、界面t合法、凝聚法等調製，此時微膠囊之囊壁材料 可例舉如聚脲烧、聚尿素、聚尿素_聚脲烧、尿素_甲酸樹 脂、二聚氰胺-甲醛樹脂、聚醯胺、聚酯、聚磺醯胺、聚碳 酸酯、聚亞磺酸酯、環氧樹脂、丙烯酸酯、甲基丙烯酸酯、 乙酸乙酯、明膠等。本發明電泳顯示裝置用顯示微粒中所 使用U膠囊之大小以〇·5至5〇〇 “ m程度為宜，^ 〇至1〇〇 /z m程度更佳。 使用本電泳顯示裝置用顯示液之電泳顯示裝置之一 例可列舉如下之形態。 ,(1)將具有於一對玻璃基板等透明基材之一方，形成所 A ut明電極’介由間隔板相向配置並形成空間，再 將本發明顯示液充填入該空間中。 (2)在整面為電極之基# μ _ , 板上’介由複數間隔片形成絕緣 勝相向之不連續空間，再將 冉將本發明顯示液充填入該空間 315086 16 1283791 (3) 在將具有於一對玻璃基板等透明基材之一方形成 所欲圖樣之透明電極，彳由間隔片相向配置並形成空間， 再將含本發明顯示液之微膠囊充填入該空間中。在本例中 亦可存在黏合劑而取代間隔片。 (4) 在整面為電極之基板上，介由複數間隔片形成絕緣 膜相向之不連續空間，再將含本發明顯示液之微膠囊充填 入該空間中。在本例中亦可存在黏合劑而取代間隔片。 (5) 在整面為電極之基板上，同時以含本發明顯示液之 微膠囊及黏合劑塗布。 依據本發明可提供一種利用不易凝聚且電泳速度快 之微粒的電泳顯示裝置用顯示液。 實施例 以下即以實施例詳細說明本發明，但本發明並不限定 於以下之實施例。在實施例中，其中之”份”指，，重量份,，， ”％’’指”重量％π。 (實施例1) γ正電彳放粒液之调製：將1〇〇份之氧化鈦（Ti_puRE R101 :杜邦（DuPont)公司製造）、72份之聚異丁烯琥珀酸 亞胺、328份之艾索貝-L(EX〇N化學公司製造）攪拌均勻， 再經GenUS(GENUS PY，吉納斯公司製造）以i 〇〇Mpa壓力處 理10次，即得表1所示平均粒徑（MS2000 : Sysmex公 司製造）之帶電微粒母液。該液再經艾索貝_L調整為顏料 成份10重量％，即得帶正電微粒液a。該微粒有良好之帶 正電性。帶負電微粒液之調製：將210份之著色劑pH7 0 315086 17 1283791 碳黑與378份之樹脂MFR5〇之芳環稀金屬pE，以雙_ 壓機加熱混拌後粗粉碎為丨至1〇mm粗片，得到著色片。 八人再面以/夜悲氮冷卻一面以棒磨機（pinmill)粉碎（冷 凍粉碎）’並經150/z m網目之篩網分級，即得粒徑分布為龠口々 ^ ^ ’ is sold by Adelaide to ACLYI. ^ There is a Ca salt, and Man 1 has a pigment dispersion yarn. The acid value of the acid is considered to be better than the affinity of the resin, and the cost is preferably less than or equal to 60 mgK〇H/g. More preferably, the weight average molecular weight is preferably a low molecular weight ionomer. The compound using a charged agent and the calixarene compound in the charged particles of the _G range can be exemplified by an iron metal soap, and then combined with a resin, a 315086 12 1283791 coloring agent, an electrically insulating solvent, and an additive to make it positive. Or a negative charge. The p compound can be freely selected from the first to fourth grades, and can be selected from the group consisting of ammonium compounds, deuterated materials, and cation compounds. Substituents bonded to nitrogen, sulfur or phosphorus atoms are, for example, alkyl groups and aryl groups. In general, a salt may be present, and a halogen group or a hydroxyl group or a tick acid group represented by chlorine may be used, but it is not limited thereto. Among them, an amine salt of 1 to 3 grade or an ammonium salt of 4 grade is particularly preferable. Further, a pyridylamine black derivative charged dye or an amine resin may be used. The ratio of the shortest diameter to the longest diameter of the charged particles of the present invention is from 1:〗 to ι·· 5〇. Preferably, since it is non-spherical, it has the advantages of being able to exhibit steric hindrance and having a large surface area, so that the maximum effect of the charged agent existing on the surface can be exerted, and the ratio is preferably in the range of 1 ·· 1.5 to 1:20. The average particle size of charged particles is preferably 20 # m, When the electrophoresis and dispersion stability are better, the ratio is preferably in the range of 丨 to 1 〇//m. When the dispersion stability is insufficient, a dispersing agent such as a commonly known surfactant may be added. The alkenyl succinic anhydride, ester or imine, decane compound, etc. may be added to hinder the electrical insulating property thereof. The alkenyl succinic anhydride, ester or imide may, for example, be polyisobutylene succinic anhydride, polyisobutylene succinate or polyisobutylene. Succinic acid imide, etc. The amount of such dispersing stabilizer added is preferably in the range of 〇〇1 to 1〇 when the weight of the charged particles treated is i. The electrically insulating solvent used in the present invention may A dielectric constant of 3 〇 or less and a grain resistivity of 100 Å·cm or more are used. For example, Essobe-GHLm·, Aisol 〇3〇, D40, and D80 manufactured by EXON Chemical Co., Ltd. , D 11〇, D 13〇, Sirso 13 315086 1283791 (Shellsol) A, AB 'Sakamoto Oil Co., Ltd. manufactured by SheU Co., Ltd., Nafford rubber l, μ, pj and toluene, xylene. The substituent of toluene may be any of ortho, meta and para, and It is a mixture of any combination. For the electrically insulating solvent, the weight ratio of the total charged particles is preferably in the range of 1 to 50% by weight. In the display liquid for the class 1 electric permanent display device, the dye can be dissolved in the electrical insulation. A colored electrical insulating solvent made in a solvent. It can be used as an oil-soluble dye, such as alcohol-soluble black ($B, ss BB, AB), aniline black background (sa, SAP, SAPL, EE, EEL, EX, EXBP, EB), oil soluble yellow (105, 107, 129, 3G, ggs), oil soluble orange (2〇1, PS, PR), acid orange, oil soluble red (5B, rr, 〇G ), oil soluble scarlet, oil pink 312, oil soluble purple #730, micronaire blue RR, smectre green G, oil soluble brown (GR, 416), Sudan black X60, oil soluble green (5 〇 2, BG), oil soluble blue (613, 2N, BOS), oil soluble black (HBB, 860, BS), Paris acid yellow (1101, 11〇5, 31〇8, 412〇), Paris acid orange (32 〇9 321〇), Paris acid red (1306, 1355, 2303, 3304, 3306, 3320), Baqin acid pink 23 10N, Paris acid brown (24〇2, 34〇5), Paris acid monitor (3405, 1501 1,603,16 05, 1607, 2606, 2610), Paris 酉夂 备, (1701, 1702), Paris acid black (18 〇 2, 18 〇 7, 38 〇 4, 381 〇, 3820, 3830) and so on. The method for producing a display liquid for an electrophoretic display device according to the present invention comprises the step of pulverizing a mixture of a resin synthesized by an aromatic-dilute metal catalyst and a coloring agent. Hereinafter, a flow of a method for producing a display liquid for an electrophoretic display device of the present invention will be described as an example of a flow chart 14 315086 1283791. The first coupon θ is scattered in the tree wax. If necessary, the mixing step is to completely separate the pigment (colorant) and then the resulting mixture is mixed with LI; It can be followed. Also #田 π碎. The pulverization step may be performed once or twice, or may be pre-pulverized by using several kinds of pulverization too 4, and then 捍m, for example, first, dry pulverization, smashing, and smashing. In this case, the last wet pulverization step r 2 electric and wide dielectric insulating solvent and charged to make the particles functional. The machine is wet pulverized 22 and is non-spherical. It is especially suitable for the formation of non-spherical shape. ..., in this mixing step, 'the resin and the coloring agent can be appropriately blended and dispersed t' and then mixed with a Han-Su mixer, a cooling mixer, a Nauta mixer, a drum: a combiner, a sander, etc. The Banbury mixing machine, the smothering machine and the μ machine, the biaxial grinding machine, the triaxial grinding machine, the single shaft extruder, the two-axis masking machine, etc., the coloring agent is heated and mixed with the resin. After the heating and mixing step The mixed mixture containing the colorant and the resin may also be coarsely pulverized. The dry pulverization step is preferably carried out by low-temperature cold pulverization. Hereinafter, the low-temperature cold used in the present invention; the east pulverization will be described. The granulated thermoplastic resin is not easy to be used. Crushing at room temperature, but mixing and mixing the resin and coloring agent The pulverizer such as a turbopulverizer is cooled to _196 with liquid nitrogen, and then pulverized by the brittleness of the resin at a low temperature, and can be finely pulverized into 5 〇〇 #m or less. At the same time, it is chilled and pulverized at a low temperature and then appropriately classified by a classifier. According to the particle size classification, the coarse particles can be removed and the subsequent wet pulverization can be used to improve the pulverization efficiency. In the wet pulverization step, the wet pulverizer can be pulverized to the desired granule size. It can be used in the present invention. The wet pulverizer can be exemplified by ultrafine pulverization 315086 15 1283791 machine, 辗 wheel type sand mixer, dynomill, ball mill, powerful sub-peel mill, pulse mill, and wave mill (CoBall-Mill) ), fine-drill sand mill, DCP mill, OB mill and other medium-type wet pulverizer, or homogenizer, particle homogenizer, triangular grinder (Trigonal), knife-type mill (Slasher), colloid mill, super A non-media type wet pulverizer such as a Cavitron, a Golatlu, a Genus, or a Clear Mix. The display of the electrophoretic display device of the present invention is used. Electrophoresis of liquid in microcapsules The microcapsules used for displaying the microparticles in the device can be prepared by in-situ method, interface t-method, coacervation method, etc., and the material of the microcapsule wall can be exemplified by polyurea, polyurea, polyurea. _ Polyurea, urea-formic acid resin, melamine-formaldehyde resin, polyamide, polyester, polysulfonamide, polycarbonate, polysulfinate, epoxy resin, acrylate, methacrylic acid Ester, ethyl acetate, gelatin, etc. The size of the U capsule used in the display microparticles of the electrophoretic display device of the present invention is preferably from 5 to 5 Å, preferably from about 1 to about 3 Å. An example of the electrophoretic display device using the display liquid for the electrophoretic display device is as follows. (1) The anode electrode is formed on one of the transparent substrates such as a pair of glass substrates to form a space, and the spacers are arranged to face each other to form a space, and the display liquid of the present invention is filled in the space. (2) The entire surface is the base of the electrode # μ _ , and the plate is formed by a plurality of spacers to form a discontinuous space in which the insulating phase is opposite to each other, and then the display liquid of the present invention is filled into the space 315086 16 1283791 (3) A transparent electrode having a desired pattern formed on one of a pair of transparent substrates such as a pair of glass substrates is disposed so as to be opposed to each other by a spacer to form a space, and the microcapsule containing the display liquid of the present invention is filled in the space. In this case, a binder may also be present instead of the spacer. (4) A micro-capsule containing the display liquid of the present invention is filled into the space by forming a discontinuous space in which the insulating film faces in the substrate on the entire surface of the electrode. In this case, a binder may also be present instead of the spacer. (5) On the substrate having the entire surface as an electrode, the microcapsules containing the display liquid of the present invention and a binder are simultaneously coated. According to the present invention, it is possible to provide a display liquid for an electrophoretic display device which utilizes particles which are less likely to aggregate and have a fast electrophoresis speed. EXAMPLES Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited. In the examples, "parts" means, parts by weight, and "%" means "% by weight". (Example 1) Preparation of γ-positive ruthenium granulating liquid: 1 part of titanium oxide (Ti_puRE R101: manufactured by DuPont), 72 parts of polyisobutylene succinate, 328 parts of AI Sobe-L (manufactured by EX〇N Chemical Co., Ltd.) was stirred uniformly, and then treated with GenUS (GENUS PY, manufactured by Guinness) at i 〇〇Mpa pressure for 10 times to obtain the average particle diameter shown in Table 1 (MS2000: Charged particle mother liquor manufactured by Sysmex. The liquid was further adjusted to 10% by weight of the pigment component by Essobe_L to obtain positively charged particulate liquid a. The particles have good positive chargeability. Modulation with negatively charged particulate liquid: 210 parts of coloring agent pH7 0 315086 17 1283791 carbon black and 378 parts of resin MFR5 芳 aromatic ring thin metal pE, mixed by double _ press, coarsely pulverized to 〇 to 1〇 Mm thick to obtain a colored sheet. The eight people were again smashed (cold pulverized) with a pinmill by a nighttime cold nitrogen cooling and classified by a 150/z m mesh screen to obtain a particle size distribution.
平均粒徑48/zm(SA_CP3L，島津製作所製離心沉降式粒度 分布測定機）之粉碎物。 X DCP粉碎機粉碎··將12〇份之上述粉碎物、份之 艾索貝_L、10份之崩特隆（B〇netr〇n)p_5l (4級銨鹽：〇士加 化學工業株式會社製造）於6〇分鐘内粉碎，即得表工所示 平均粒徑（MS2000: Sysmex公司製造）之帶電微粒母液。該 液再經艾索貝-L調整為不揮發成分4 〇 %，即得帶負電微 粒液b。該微粒有良好之帶負電性。 混：液之調製··將上述帶正電微粒液a及帶負電微粒 液b等量混合，即得電泳顯示裝置用顯示液〇。 〈評估方法〉 各評估方法及評定標準如下，其評估結果如表丨所 示電冰性.在下側電極為不銹鋼、上側電極為IT〇蒸鍍 玻璃板構成之電極間之100 # m槽中注滿樣品液，再以 + 30V及-30V電Μ、以之間隔交互施加電壓，其帶 負電微粒液b之微粒即向正極側、帶正電微粒液&之微粒 即向負極側移動、附著。就此狀態自上端之玻璃面輸入影 像並觀察影像，其色交換若平穩則為〇、色交換不完全則 為△、色交換若無法明確觀察則為X。 分散安定性··分別將帶正電微粒液a及帶負電微粒液 315086 18 1283791 b注入i〇ml用之附刻度試管中為樣品，再於i日後、】週 後觀察其上清液之容量。 微粒之污損： 在下側電極為不銹鋼、上側電極為IT〇蒸鍍玻璃板構 成之電極間之100"爪槽中注滿樣品液，再測定藉外加電 壓使其附著ΙΤΟ蒸鍍玻璃板之反射強度（ph〇tai mcpd_ 1000 :大塚電子公司製造），由其與標準板之比例算出其反 射率。在白色之場合以高者為佳，在黑色之場合則以低者 為佳。 (實施例2) 帶正電微粒液之調製：將300份之氧化鈦（Ti_PURE _ :杜邦公司製造）、3 〇 0份之樹脂乙稀_甲基丙稀酸共 聚物N1525(三井•杜邦化學公司製造）經雙軸親塵機加熱混 拌後粗=碎為粗片，得到著色片。其次，再一 面以液態氮冷卻-面以棒磨機粉碎（冷㈣碎），並經"Ο 口網目之篩網分級，即得粒徑分布為平均粒徑45 # m(SA-CP3L ’胃津製作所製離心沉降式粒度分布測定機） — 粉碎機粉碎：將120份之上述粉碎物、52〇份 乂索貝、L 1〇伤之崩特隆Ρ·51(4級銨鹽：Orient化學工 株式會社製造）於6〇分鐘内粉碎，即得表丨所示平均粒 a : Sysmex公司製造）之帶電微粒母液。言亥液再經 索貝-L凋整為不揮發成分1〇%，即得帶 微粒有良好之帶正電性。 夜 315086 19 1283791 帶負電微粒液之調製··以與實施例1相同操作得到帶 負電微粒液b。 混合液之調製：將上述帶正電微粒液a及帶負電微粒 液b等量混合，即得電泳顯示裝置用顯示液〇。 (實施例3) 帶正電微粒液之調製：除以MFR5〇之芳環稀金屬pE 取代乙烯-甲基丙烯酸共聚物N1 525之外，以相同之處方 與貫施例2相同操作，即得帶正電微粒液a。 帶負電微粒液之調製：將128份之著色劑碳黑 (ELFTEX415R:嘉寶德公司製造）與46〇份之樹脂乙烯_甲 基丙烯酸共聚物Nl 525(三井•杜邦化學公司製造）、及12 份之顏料分散劑低分子離子鍵聚合物ACLYN246a(阿萊德 公司製造），經雙軸輥壓機加熱混拌後粗粉碎為丨至i〇mm 粗片’付到著色片。其次，# 一面以液態氮冷卻一面以棒 磨機粕碎（冷凍粉碎），並經！ 5〇 # m網目之篩網分級，即得 粒徑分布為平均粒徑心m(SA_cp3L，島津製作所離心沉 降式粒度分布測定機）之粉碎物。 斗 ----a不刀砰物、520佚 乂^貝乙1〇份之崩特隆E_89(杯芳烴：〇rient化學工 株式會社製造）於6G分鐘内粉碎，即得表丨所示平均相 (MS2〇〇〇 : Sysmex公司製造)之帶電杈粒 l ^ f冤认拉母液。該液再慈 :驗右：揮發成分4·〇% ’即得帶負電微粒液b 该楗粒有良好之帶負電性。 犯合液之調製：將上述帶正電微粒液a及帶負電德 315086 20 1283791 液b等量混合，即得電泳顯示裝置用顯示液e。 (實施例4) 除以Finess Red F2B(東洋油墨製造株式會社製造）取 代碳黑之外，與實施例3相同操作，製成樣品供評估。 (實施例5) 帶正電微粒液之調製：將210份之著色劑pH8 5碳里 與378份之樹月旨MFR5〇之芳環烯金| pE，以雙轴概壓機 加熱混拌後粗粉碎為丨至1〇mm粗片，得到著色片。其次， 再一面以液態氮冷卻一面以棒磨機粉碎（冷凍粉碎），並經 150私〇網目之篩網分級，即得粒徑分布為平均粒徑a# m(SA-CP3L，島津製作所離心沉降式粒度分布測定機）之粉 碎物。 “ DCP粉碎機粉碎：將12〇份之上述粉碎物、52〇份之 艾索貝-L、1〇份之崩特隆卜51(4級銨鹽：〇七加化學工業 株式會社製造）於60分鐘内粉碎，即得表1所示平均粒徑 ( 〇 Sysmex公司製造）之帶電微粒母液。該液再經艾 索貝-L調整為不揮發成分4 () %，即得帶正電微粒液&。 該微粒有良好之帶正電性。 帶負電微粒液之調製··將100份之氧化鈦（Ti-PURE Rl 4 DuPont公司製造）、72份之聚異丁烯琥珀酸酐、328 伤之艾索貝-L(EX〇N化學公司製造）攪拌均勻，再經吉納 斯（GENUSPY，吉納斯公司製造）以1〇〇Mpa壓力處理ι〇 -人，即侍表1所示平均粒徑（MS2〇〇〇 : 公司製造） 之絜電微粒母液。該液再經艾索貝_L調整為顏料成分丄〇 21 315086 1283791 重1 % ’即得帶負電微粒液b。該微粒有良好之帶負電性。 混合液之調製：將上述帶正電微粒液a及帶負電微粒 液b等量混合，即得電泳顯示裝置用顯示液〇。 (實施例6 ) 帶正電微粒液之調製：將1 〇〇份之鈦黑、72份之聚異 丁烯琥珀酸亞胺、328份之艾索貝_l(ex〇N化學公司製造） 攪拌均勻，再經吉納斯（GENUS PY，吉納斯公司製造）以 lOOMPa壓力處理1〇次’即得表i所示平均粒徑（mS2〇〇〇 :A ground product having an average particle diameter of 48/zm (SA_CP3L, a centrifugal sedimentation type particle size distribution measuring machine manufactured by Shimadzu Corporation). X DCP pulverizer pulverized · 12 parts of the above pulverized material, part of Aisop _L, 10 parts of 崩特特隆 (B〇netr〇n) p_5l (4 grade ammonium salt: Gentleman Chemical Industry Co., Ltd. Produced by the company) pulverized in 6 minutes, that is, the charged particle mother liquid of the average particle diameter (MS2000: manufactured by Sysmex Co., Ltd.) shown by the watch. The liquid is then adjusted to a non-volatile content of 4 〇% by Essobe-L, which results in a negatively charged microparticle b. The particles are well negatively charged. Mixing: Liquid preparation · The above-mentioned positively charged fine particle liquid a and negatively charged fine particle liquid b are mixed in equal amounts to obtain a display liquid helium for an electrophoretic display device. <Evaluation method> The evaluation methods and evaluation criteria are as follows. The evaluation results are shown in the table below. The electric ice is shown in the table. The bottom electrode is stainless steel, and the upper electrode is the 100# m slot between the electrodes of the IT/vapor-deposited glass plate. Full sample liquid, and then apply voltage at intervals of +30V and -30V, and the particles with negatively charged particle liquid b are moved to the positive electrode side, and the particles with positively charged particle liquid & . In this state, an image is input from the upper glass surface and the image is observed. If the color exchange is smooth, the color is 〇, the color exchange is incomplete, and Δ, and the color exchange is X if it is not clearly observed. Dispersion stability··Inject the positively charged particulate liquid a and the negatively charged particulate liquid 315086 18 1283791 b into the graduated test tube for i〇ml as the sample, and observe the volume of the supernatant after the day after i . Particle fouling: The sample is filled in the 100" claw groove between the electrode with the lower electrode and the upper electrode for the IT〇 vapor-deposited glass plate, and then the reflection is applied to the vapor-deposited glass plate by the applied voltage. The strength (ph〇tai mcpd_1000: manufactured by Otsuka Electronics Co., Ltd.) was calculated from the ratio of the ratio to the standard plate. In the case of white, the upper one is better, and in the case of black, the lower one is preferable. (Example 2) Preparation of positively charged fine particle liquid: 300 parts of titanium oxide (Ti_PURE _: manufactured by DuPont), 3 parts by weight of resin ethylene-methyl acrylate copolymer N1525 (Mitsui DuPont Chemical Co., Ltd.) The company's manufacturing) is heated by a two-axis dusting machine and then coarsely crushed into coarse pieces to obtain a colored sheet. Secondly, the surface is cooled by liquid nitrogen and pulverized by a rod mill (cold (four) crushed), and classified by a sieve mesh of the mesh of the mouth, and the particle size distribution is an average particle size of 45 # m (SA-CP3L ' Centrifugal sedimentation type particle size distribution measuring machine manufactured by Weijin Co., Ltd.) - Crusher pulverization: 120 parts of the above pulverized material, 52 parts of cockroach, and L 1 之 崩 特 Ρ 51 51 51 (4 grade ammonium salt: Orient Chemicals Co., Ltd.) is pulverized in 6 minutes, that is, the charged particle mother liquid of the average particle a: manufactured by Sysmex Co., Ltd.). Yanhai liquid is then immersed in Sobe-L to a non-volatile content of 1%, which means that the particles have a good positive charge. Night 315086 19 1283791 Modulation with negatively charged fine particle liquid · The negatively charged fine particle liquid b was obtained in the same manner as in Example 1. Modulation of the mixed solution: The positively charged fine particle liquid a and the negatively charged fine particle liquid b are mixed in equal amounts to obtain a display liquid for the electrophoretic display device. (Example 3) Modulation of positively charged fine particle liquid: Except that the aromatic ring rare metal pE of MFR5 is substituted for the ethylene-methacrylic acid copolymer N1 525, the same operation as in the case of Example 2 is obtained in the same manner. With positively charged particulate liquid a. Modulation with negatively charged particulate liquid: 128 parts of coloring agent carbon black (ELFTEX415R: manufactured by Jiabaode) and 46 parts of resin ethylene_methacrylic acid copolymer Nl 525 (manufactured by Mitsui & DuPont Chemical Co., Ltd.), and 12 Part of the pigment dispersant low molecular weight ionomer ACLYN246a (manufactured by Arad), which is heated and mixed by a double-axis roller press and then coarsely pulverized into 〇 to i〇mm thick sheet 'paid to the colored sheet. Secondly, # one side is cooled with liquid nitrogen and crushed with a rod mill (freezing and crushing), and passed! 5 〇 # m mesh screen grading, that is, the pulverized material having a particle size distribution of an average particle diameter m (SA_cp3L, Shimadzu Corporation centrifugal sedimentation particle size distribution measuring machine).斗----a knives, 520 佚乂 贝 贝 〇 〇 〇 〇 E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E Phase (MS2〇〇〇: manufactured by Sysmex) charged granules l ^ f 冤 pull mother liquid. The liquid is reciprocal: the right is tested: the volatile component is 4·〇% ‘that is, the negatively charged particulate liquid b is obtained. The granule has good negative chargeability. Modulation of the liquid mixture: The above positively charged fine particle liquid a and negatively charged 315086 20 1283791 liquid b are mixed in equal amounts to obtain the display liquid e for the electrophoretic display device. (Example 4) A sample was prepared for evaluation in the same manner as in Example 3 except that Finess Red F2B (manufactured by Toyo Ink Co., Ltd.) was used instead of carbon black. (Example 5) Preparation of positively charged fine particle liquid: 210 parts of the coloring agent pH 8 5 carbon and 378 parts of the tree MFR 5 芳 环 烯 烯 | | p | , , , , , , The coarse pulverization was carried out to a coarse sheet of 1 mm to obtain a colored sheet. Secondly, the surface is cooled by liquid nitrogen and pulverized by a rod mill (frozen pulverization), and classified by a sieve of 150 private mesh, and the particle size distribution is average particle size a# m (SA-CP3L, centrifugally sedimentation of Shimadzu Corporation) The pulverized material of the particle size distribution measuring machine. "DCP pulverizer pulverization: 12 parts of the above-mentioned pulverized material, 52 parts of Aesop-L, and 1 part of Truffled 51 (4th-order ammonium salt: manufactured by 〇7-Chem Chemical Co., Ltd.) After pulverizing in 60 minutes, the charged particle mother liquid of the average particle diameter (manufactured by 〇Sysmex Co., Ltd.) shown in Table 1 was obtained, and the liquid was further adjusted to a non-volatile content of 4 (%) by Essobe-L, that is, positively charged particles were obtained. Liquid & The fine particles have good positive charge. Preparation of negatively charged fine particle liquid · 100 parts of titanium oxide (Ti-PURE Rl 4 DuPont), 72 parts of polyisobutylene succinic anhydride, 328 Aisop-L (manufactured by EX〇N Chemical Co., Ltd.) is stirred evenly, and then treated by Genus (manufactured by Genus PY, manufactured by Guinness) at a pressure of 1 〇〇Mpa, which is the average particle shown in Table 1.絜 (MS2〇〇〇: manufactured by the company) 絜 絜 微粒 微粒 。 。 。 公司 公司 公司 公司 公司 公司 公司 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Negatively charged. Modulation of mixed solution: mixing the positively charged particulate liquid a and the negatively charged particulate liquid b in the same amount The liquid display device used to display liquid helium. (Example 6) Preparation of positively charged fine particle liquid: 1 part of titanium black, 72 parts of polyisobutylene succinate, 328 parts of essobe _l (ex 〇N Chemical Co., Ltd.) Stir well, and then treated by Genus PY (manufactured by Guinness) at 100 MPa pressure to obtain the average particle size shown in Table i (mS2〇〇〇:
Sysmex公司製造）之帶電微粒母液。該液再經艾索貝彳調 整為顏料成分10重量％，即得帶正電微粒液a。該微粒有 良好之帶正電性。Charged particle mother liquor manufactured by Sysmex. The solution was further adjusted to 10% by weight of the pigment component by Essobe, that is, positively charged microparticles a. The particles are well positively charged.
帶負電微粒液之調製：將300份之氧化鈦（Ti_puRE R104 .杜邦公司製造）、3〇〇份之樹脂之芳環稀金 屬PEj以雙軸輥壓機加熱混拌後粗粉碎為丨至i〇mm粗 片’侍到者色片。其次，再一面以液態氮冷卻一面以棒磨 機粉碎（冷絲碎），並經15G"m網目之_分級，即得粒 ^分布為平均粒徑45 " m(SA_CP3L，島津製作所離心沉降 式粒度分布測定機）之粉碎物。 DCP粉碎機粉碎··们2〇份之上述粉碎物、別份之 又索貝-L、1 〇份夕山 株式會社製造)於6:八Ε:(杯芳：：0_化學工業 (MS2_:Sysmex八^内粉碎，即得表1所示平均粒徑 索貝-L調整為不揮；^造）之帶電微粒母液。該液再經艾 微粒有良好之帶負電1〇%，即得帶負電微粒液b。該 315086 22 1283791 合液之調製：將上述帶正電微粒液& 液b等量混合，即得電泳顯示裝置用顯示液V、電U粒 (實施例7) e。 帶正電微粒液之調製：以與實施例3 得帶正電微粒液a。 目同操作，即 帶負電微粒液之調製：將21〇份 與-份之樹脂峨30之芳環稀金屬p:色二飢5碳黑 離子鍵聚合物ACLYN246A(阿萊德公司製造)，二：= 機加熱混拌後粗粉碎為1至10顏粗片，得到著=1 次’再-面以液態氮冷卻一面以棒磨機粉 /、 並經150 // m網目夕r w h東叔碎）， 4S,m(SA-CP^^ 之粉碎物。作㈣心沉降式粒度分布測定機） DCP粉碎機粉碎：冑㈣份之上述粉碎物、咖份之 乂索貝:卜10份之崩特隆Ε·89(杯芳烴：㈤叫匕 株式會社製造）於6〇分鐘内粉碎’即得表i所示平沖 (购_ ·· Sysmex公司製造）之帶電微粒母液。該液再^ =調整為不揮發成分儀，即得帶負電微粒液二 微粒有良好之帶負電性。 ^ ΓI液之'周製··將上述帶正電微粒液a及帶負電微粒 ’文：篁混合’即得電泳顯示裝置用顯示液C。 (比較例1) ^ W包微粒液之調製··以與實施例2之相同操作，即 得帶正電微粒液a。 23 315086 1283791 帶負電微粒液之調製··以與實施例3之 得帶負電微粒液b。 α木’即 混合液之調製··將上述帶正電微粒液 饬h笙旦、曰人 bd ^ f負電微粒 液b寻里此a ，即侍電泳顯示裝置用顯示液e。 (比較例2) 帶正電微粒液之調製：以與實施例2之相同择 得帶正電微粒液a。 /、卜’即 帶負電微粒液之調製：除以MFR50之芳環烯金屬PE 取^乙烯·甲基丙烯酸共聚物N1 525之外，與實施例3相 同操作，即得帶負電微粒液b。Modulation with negatively charged particulate liquid: 300 parts of titanium oxide (Ti_puRE R104. manufactured by DuPont), 3 parts of resin, aromatic ring rare metal PEj, heated and mixed by a double-axis roller press, and then coarsely pulverized into 丨 to i 〇mm thick film 'waiter color film. Secondly, the surface is cooled by liquid nitrogen and pulverized by a rod mill (cold wire), and classified by 15G"m mesh, the particle size distribution is average particle size 45 " m (SA_CP3L, Shimadzu Seisakusho The pulverized material of the particle size distribution measuring machine. The DCP pulverizer pulverizes the above-mentioned pulverized material, and the other parts of the smashed material, and the other parts are also produced by Sobe-L, 1 〇 夕 夕 株式会社 于 于 at 6: gossip: (Cup Fang:: 0_Chemical Industry (MS2_) :Sysmex smashed within 8^, that is, the average particle size of Sobe-L shown in Table 1 is adjusted to be non-volatility; the liquid carrier liquid of the charged particles. The liquid has a good negative charge of 1% by the AI particles. The negatively charged fine particle liquid b. The 315086 22 1283791 preparation of the liquid mixture: the positively charged fine particle liquid & liquid b is mixed in equal amounts to obtain the display liquid V and the electric U particles (Example 7) e of the electrophoretic display device. Modulation with positively charged particulate liquid: with positively charged particulate liquid a as in Example 3. The same operation, that is, modulation with negatively charged particulate liquid: 21 parts and parts of resin 峨 30 of aromatic ring rare metal p : Color two hunger 5 carbon black ion bond polymer ACLYN246A (made by Arad), two: = machine heated mixed with coarse pulverization to 1 to 10 fat, get = 1 're-face to liquid nitrogen Cool one side with a rod mill powder /, and pass 150 / m m mesh eve rwh East uncle broken), 4S, m (SA-CP ^ ^ pulverized material. For (four) heart sedimentation particle size distribution measuring machine) DCP pulverizer Broken: 胄 (4) parts of the above-mentioned pulverized material, 咖 乂 乂 : : : : : : : : : : : : : : : : : : : : 89 89 89 89 89 89 89 89 89 89 89 89 89 89 89 89 89 89 89 89 89 89 The charged particle mother liquor of Siping Chong (purchased by _··Sysmex). The liquid is further adjusted to a non-volatile composition meter, that is, the negatively charged particulate liquid has a good negative charge. ^ ΓI liquid 'week system · The above-mentioned positively charged fine particle liquid a and negatively charged particles 'text: 篁 mixed' is the display liquid C for electrophoretic display devices. (Comparative Example 1) ^ Modulation of W-packed fine particle liquid · In the same operation as in Example 2, positively charged fine particle liquid a was obtained. 23 315086 1283791 Modulation with negatively charged particulate liquid · With negatively charged particulate liquid b as in Example 3. α木', ie, the preparation of the mixed liquid, the above-mentioned positively charged fine particle liquid 曰h笙, 曰人 bd ^ f negative electric particle liquid b find this a, that is, the display liquid e for the electrophoretic display device. (Comparative Example 2) Modulation with positively charged fine particle liquid: The positively charged fine particle liquid a was selected in the same manner as in Example 2. The preparation of the negatively charged fine particle liquid is carried out in the same manner as in the third embodiment except that the aromatic ring-containing metal PE of the MFR 50 is taken as the ethylene/methacrylic acid copolymer N1 525.
DCP粉碎機粉碎：將60份之帶正電微粒、12〇份之嫌 負電微粒分開各別處理。 T 此口液之調製：與實施例1相同操作，即得電泳 裝置用顯示液c。 y' 315086 24 1283791 表1DCP pulverizer pulverization: 60 parts of the positively charged particles and 12 parts of the negatively charged particles were separately treated. T Modulation of the liquid: In the same manner as in Example 1, the display liquid c for the electrophoresis device was obtained. y' 315086 24 1283791 Table 1
粒徑 電泳性 分散安定性 反射率 (u m) 1曰 1週 (%) (m I ) 實施例1 微粒液a 0.3 〇 0 0 50 微粒液b I 1.5 0.1 0.3 4 實施例2 微粒液a _ 8.5 2.9 4 40 微粒液b 1.5 U 0.1 0.3 4 實施例3 徴粒液a 1.8 0.6 0.8 45 微粒液b 4.1 2 2·5 10 實施例4 微粒液a 1.8 r\ 0.6 0.8 45 微粒液b 2.6 0.5 0.8 10 實施例5 微粒液a 1.6 〇 0.7 1 5 微粒液b 0 0 48 實施例6 微粒液a 0.05 〇 0 0 5 微粒液b 1.4 0.2 0.5 52 實施例7 All# 微粒液a 1.8 0.6 0.8 45 微粒液b 2.4 0.8 3.5 5 比較例1 微粒液a 8.5 X 2.9 4 w — ——« 40 微粒液b 4.1 2 2.5 10 比較例2 微粒液a 8.5 X 2.9 4 40 微粒液b —1.3 0.5 1 1 1 II 脂 凝 脂 液 在實施例1至7中，含以芳環烯金屬催化劑合成之 及著色劑之帶電微粒，其粒徑小、製成之帶 j 聚、分散性佳。同時，含芳 屬 Λ : /文/ s以方ί衣烯金屬催化齊 及著色劑之帶電微粒製成之第2類電泳顯示;:成。 ，電泳性優良、反射率之比大、視認性佳。置用顯; 315086 25Particle size electrophoretic dispersion stability reflectance (um) 1曰1 week (%) (m I ) Example 1 Particulate liquid a 0.3 〇0 0 50 Particulate liquid b I 1.5 0.1 0.3 4 Example 2 Particulate liquid a _ 8.5 2.9 4 40 Particulate liquid b 1.5 U 0.1 0.3 4 Example 3 徴 granule liquid a 1.8 0.6 0.8 45 Particulate liquid b 4.1 2 2·5 10 Example 4 Particulate liquid a 1.8 r\ 0.6 0.8 45 Particulate liquid b 2.6 0.5 0.8 10 Example 5 Particulate liquid a 1.6 〇0.7 1 5 Particulate liquid b 0 0 48 Example 6 Particulate liquid a 0.05 〇0 0 5 Particulate liquid b 1.4 0.2 0.5 52 Example 7 All# Particulate liquid a 1.8 0.6 0.8 45 Particulate liquid b 2.4 0.8 3.5 5 Comparative Example 1 Particulate liquid a 8.5 X 2.9 4 w — —— « 40 Particulate liquid b 4.1 2 2.5 10 Comparative example 2 Particulate liquid a 8.5 X 2.9 4 40 Particulate liquid b — 1.3 0.5 1 1 1 II Grease In the examples 1 to 7, the charged fine particles containing the coloring agent synthesized by the aromatic cycloolefin metal catalyst have a small particle size, and the resulting ribbon is excellent in dispersibility. At the same time, the second type electrophoretic display made of aromatic Λ: / text / s with charged particles of the metal and the charged particles of the coloring agent; Excellent electrophoresis, large reflectance ratio, and good visibility. Use the display; 315086 25