經濟部中央標隼局員工消費合作社印裝 460549 A7 B7 五、發明説明（1 ) 〔發明所屬技術領域〕 本發明係有關原子筆、簽字筆、馬克筆、鋼筆等筆具 所適用之水性墨水。 〔習知技術〕 向來，原子筆、簽字筆、馬克筆、鋼筆等一直都使用 低粘度之水性墨水。 〔本發明欲解決之課題〕 然而，一般使用這類水性墨水之水性筆具，其墨水之 流動性容易受到室溫之變化或大氣壓力之變化等影響，致 有墨水自筆尖無端滲出或流出，造成衣物污染之弊發生之 問題。爲防止此問題發生，若提高墨水之表面張力，則有 墨水之流動性變成遲滯之問題發生，尤其是對防水性（斥 水性）樹脂（如：聚丙烯樹脂、聚乙烯樹脂等）製之內徑 在8mm0以下之儲墨管（這是水性墨水筆常用之儲墨管之 管徑）而言，更因水性墨水之高表面張力，以致水性墨水 産生自行保持作用遂有難以順暢流通之問題發生。 此外，水性墨水在紙面上書寫時，亦有墨水容易滲透 進入紙張之纖維組織間，致書寫字跡擴散及透過背面，影 響美觀之問題。 因此，本發明旨在解決上述問題，提供一種改質之水 性墨水，能在不減低表面張力之下，爲達到墨水之流動性 順暢良好，而提高墨水之對儲墨筒或導墨芯筒及墨筆芯等 之潤濕性之同時，亦能有效抑制書寫筆跡之擴散渗透者。 〔解決課題之手段〕 -2 - 本紙張尺度適用中國葶家標準（CNS ) A4規格（210X297公釐） I-------Ί------訂------^ {請先閱讀背面之注意事項再填寫本頁) 460549 A7 B7 五、發明説明（2) 經發明人長期硏究試驗發現，在含有保濕劑之水性溶 媒中溶解或呈懸浮狀分散有色料（顏料）而成之筆具用水 性墨水中，若將由甲基丙烯酸甲酯（methyl methacrylate) '丙烯酸丁酯（butyl acrylic acid }及甲基丙烯酸（ methacrylic acid )之三種單體共聚合而成之三元聚合物 乳化劑成分溶解或分散於上述水性溶媒中，即可獲得能改 善對防水性樹脂之潤濕性，同時能有效抑止書寫筆跡之滲 透擴散之水性墨水，遂完成本發明。 上述甲基丙烯酸甲酯'丙烯酸丁酯及甲基丙烯酸之三 種單體共聚合而成之三元共聚合物以其成分比例而言，以 重量百分比計分別爲：甲基丙烯酸4〇〜50%，丙烯酸乙酯 40〜50%，甲基丙烯酸5 %以下，且分子量約爲250,000〜 350,000，黏度調製爲10,〇〇〇〜12,〇〇〇 CP爲佳。此三元共 聚合物之使用以不揮發成分換算爲0.4%重量百分比以上 ，即可使上述濕潤性獲得顯著之改善，特別是以2.2%〜 2.3%之重量百分比混合分散時，其滲透抑制效果及潤濕 性最適合，惟如超過10.0%重量百分比時，因粘性增加而 會使連續書寫距離（筆跡長度）減短。 經濟部中央梯準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 上述三元共聚合物係將上述甲基丙烯酸、丙烯酸丁酯 及甲基丙烯酸三種單體依前述比例投入反應鍋中，並添加 以過硫酸鹽做爲觸媒（催化劑），一邊攪拌，一邊加熱，而 在約80°C溫度下經過大約1〇小時之加熱聚合後，使反應聚 合物冷卻至常溫即得白色乳化液狀三元聚合物。 藉在上述溶媒中混合以0.4〜10.0%重量百分比之上 本紙張尺度通用中國國家標準（CNS ) A4规格（21〇Χ297公釐} 經滴部中央標準局員工消费合作社印裝 460549 A7 ___— ___B7 五、發明説明（3) 述三元共聚合物乳化液，所得之墨水之表面張力之變化爲 1達因/公分（dyne/cm)以下，粘度之變化爲1.〇 cp(厘 泊）以下。 色料可選用染料及顔料，以在墨水組成分中6〜1〇% 重量百分比之範圍內使用爲宜。 除上述成分之外，視必要尙可添加下列成份在所定範 圍內使用爲宜，即滲透劑〇〜〇.1重量百分比，界面活性劑 0〜0.1重量百分比，防銹劑、防腐劑、防霉劑在〇〜i重 量百分比。爲不使表面張力過於減低，宜僅添加少量之滲 透劑及界面活性劑。 〔實施例說明〕 以下實施例1〜7所用三元共聚合物乳化液，其成分 比以重量百分比而言爲，甲基丙烯酸40〜50%，丙烯酸丁 酯40〜50，甲基丙烯酸5 %以下，並且有黏度在1〇,〇〇〇〜 12,000 CP(厘泊）者。 實施例1 : J|_^_£_ 含量 (重量份) 。水溶性黑色染料（Water Black 100L............... 50.0份 (含水量84重量％ ) 。乙二醇（ethylene glycol)保濕劑）..................30.0份 。SC0UR0L 900(滲透劑）.................................0.1 份 (花王石鹸株式會社出品）聚氧乙烯壬基苯醚) (Polyoxyethylene nonyl phenyl ether) 本紙掁尺度適用中國國家標準（CNS ) A4規格（210X297公釐） --------i------IT-----線 (請先閱讀背面之注意事項再填寫本頁} 460549 A7 五、發明説明（4 ) 。PLYSURF Μ 208 B (界面活性劑）.....................0.1 份 (第一工業製藥株式會社出品）磷酸酯） 。苯并三氮啤（benzotr iazole)(防銹劑）............0.5份 。BIOCIDE .880(防霉劑、防腐劑）.....................0.2份 (Taisho Technos株式會社出品） 。三乙醇胺（triethanolamine)(PH値調整劑）......1.0份 ◎由甲基丙烯酸、丙烯酸丁酯及甲基丙烯酸 之三種單體所形成之三元共聚合物乳化液.........1.0份 (以不揮發分換算含有量爲44.5〜47.5重量分比 ，揮發分（水）含有量爲55.5〜52.5重量百分比） 。水............................................................17.1份 將上述乙二醇、SC0UR0L 900、PLYSURF M208B、苯并 三氮唑' BIOCIDE 880及三乙醇胺混合，並加溫至50〜60°C ，利用攪拌機進行20分鐘之攪拌、混合，隨之，在一邊進 行攪拌，一邊將水溶性黑色染料、水及上述三元共聚合體 乳化液依序加入，經約30分鐘之攪拌之後，加以過濾而獲 經墒部中央標準局員工消f合作社印製 得水性黑色墨水。 實施例2 : J|_座_含量(重量份) 。水溶性黑色染料（Water Black 100L............... 50.0份 (含水量84重量％ ) 。乙二醇（ethylene glycol)保濕劑）..................30.0份 。SC0UR0L 900(渗透劑）.................................0.1 份 ,I裝------訂-----、線 (請先閱讀背面之注意事磺再填寫本頁) 本紙張尺度適用中國國家標準（CMS〉A4規格（210X 297公釐） 經滴部中央標準局貝工消費合作社印製 460549 A7 ______B7__ 五、發明説明（5) (花王石鹸株式會社出品）聚氧乙烯壬基苯醚） (Polyoxyethylene nonyl phenyl ether) 。PLYSURF Μ 208 B (界面活性劑）.....................0.1 份 (第一工業製藥株式會社出品）磷酸酯） 。苯并三氮唑（benzotriazole)(防銹劑）............0.5份 。BIOCIDE 880(防霉劑、防腐劑）.....................0.2份 (Taisho Technos株式會社出品） 。三乙醇胺（triethanolamine)(PH 値調整齊!J)...... 1.0 份 ◎由甲基丙烯酸、丙烯酸丁酲及甲基丙烯酸 之三種單體所形成之三元共聚合物乳化液.........5.0份 (以不揮發分換算其含有量爲44.5〜47.5重量百分 比，揮發分（水）含有量爲55.5〜52.5重量百分比） 。水............................................................13.1份 將上述乙二醇 ' SC0UR0L 900、PLYSURF M208B、苯并 三氮唑、BIOCIDE 880及三乙醇胺混合，並加溫至50〜60eC ，利用攪拌機進行20分鐘之攪拌、混合，隨之，在一邊進 行攪拌，一邊將水溶性黑色染料、水及上述三元共聚合體 乳化液依序加入，經約30分鐘之攪拌之後，加以過濾而獲 得水性黑色墨水。 實施例3 : ^含量 (重量份） 。水溶性黑色染料（Water Black 100L............... 50.0份 (含水量84重量％ ) ^^1 I- - - - - 1» ^々 ^^^1 H— ^^^1 --^ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 460549 A7 B7 經濟部中夾標隼局”身工消贽合竹社印^ 五、發明説明（6) 。乙二醇（ethylene glycol)保濕劑）..................30.0 份 。SC0UR0L 900(滲透劑）.................................〇_1份 (花王石鹸株式會社出品）聚氧乙烯壬基苯醚） (Polyoxyethylene nonyl phenyl ether) 。PLYSURF Μ 208 B (界面活性劑）.....................0.1 份 (第一工業製藥株式會社出品）磷酸酯） 。苯并三氮哗（benzotriazole)(防銹劑）............0.5份 。BIOCIDE 880(防霉劑、防腐劑）.....................0.2份 (Taisho Technos株式會社出品） 。三乙醇胺（triethanolamiiie)(PH値調整劑）......1.0份 ◎由甲基丙烯酸、丙烯酸丁酯及甲基丙烯酸 之三種單體所形成之三元共聚合物乳化液.........10.0份 (以不揮發分換算含有量爲44.5〜47.5重量分比 ，揮發分（水）含有量爲55.5〜52.5重量百分比） 。水......................................................……8.1份 將上述乙二醇、SC0UR0L 900、PLYSURF M208B、苯并 三氮唑、BIOCIDE 880及三乙醇胺混合，並加溫至50〜60°C ，利用攪拌機進行20分鐘之攪拌、混合，隨之，在一邊進 行攪拌，一邊將水溶性黑色染料、水及上述三元共聚合體 乳化液依序加入，經約30分鐘之攪拌之後，加以過濾而獲 得水性黑色墨水。 (請先閱讀背面之注意事項再填寫本頁) -* 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇^97公釐) 460S4i A7 B7五、發明説明（7) 實施例4 : 組成分 含 量(重量份) 。水溶性黑色染料（Water B1 ack 1 ooL............... 50.0份 (含水量84重量％ ) 。乙二醇（ethylene glycol)保濕劑）..................30.0份 。SCOUROL 900(滲透劑）.................................0.1 份 (花王石鹼株式會社出品）聚氧乙烯壬基苯醚） (Polyoxyethylene nony1 phenyl ether) 。苯并三氮唆（匕6112〇1：1^32〇16)(防绣齊丨])............0.5份 。BIOCIDE 880(防霉劑 '防腐劑）.....................0.2份 (Taisho Technos株式會社出品） 。三乙醇胺（tr iethan〇lamine)(PH値調整劑）......1·0份 ◎由甲基丙烯酸、丙烯酸丁酯及甲基丙烯酸 之三種單體所形成之三元共聚合物乳化液.........5.0份 (以不揮發分換算含有量爲44.5〜47.5重量分比 ，揮發分（水）含有量爲55.5〜52.5重量百分比） 。水............................................................13.2份 * . ί ΐ衣 訂 Τ I矣 (請先閱讀背面之注意事項再填寫本頁) 經"-部中央#準局員工消費合作社印製 將上述乙二醇、SC0UR0L 900、苯并三氮唑、BIOCIDE 880及三乙醇胺混合，並加溫至50〜60°C，利用攪拌機進 行20分鐘之攪拌、混合，隨之，在一邊進行攪拌，一邊將 水溶性黑色染料、水及上述三元共聚合體乳化液依序加入 ，經約30分鐘之攪拌之後，加以過濾而獲得水性黑色墨水 本紙張尺度適用中國國家榡隼（CNS Μ4現格（210X297公釐） 460549 A7 B7 經滴部中央標準局員工消費合作社印製 五、發明説明（8) 實施例5 : 組_^含量 " (重量份) 。破黑（Carbon Black)(顔料）...........................8.0份 。J0NCRYL· 62(分散劑）....................................7.4份 (Jonson株式會社出品’丙嫌苯乙嫌系分散劑水溶液） 。乙二醇（ethylene glyco 1)(保濕劑）...............10.0份 。甘油（glycerin)(保濕劑）..............................20·0份 。:NONSOUL 0Κ-1(潤滑劑）.................................1·〇 份 (日本油脂株式會社出品）油酸鉀（Potassium oleate) 。苯并三氮唑（benzotriazoIe)(防銹劑）............0.5份 。BIOCIDE 880(防霉劑、防腐劑）.....................〇.2份 (Taisho Technos株式會社出品） 。三乙醇胺（triethanolamine)(PH値調整劑）……2.0份 ◎由甲基丙烯酸、丙烯酸丁酯及甲基丙烯酸 之三種單體所形成之三元共聚合物乳化液.........1.0份 (以不揮發分換算其含有量爲44.5〜47.5重量百分 比，揮發分（水）含有量爲55.5〜52.5重量百分比） ° 水............................................................49.9份 將上述碳黑，JONCRYL 62、乙二醇及甘油利用攪拌機 進行2小時之預攪拌，隨後，使用砂摩機施以16小時之摩 碎之後，以離心式分離機分離除去粗大粒子，再將此一邊 攪拌，一邊加入N0NS0UL 0K-1、苯并三氮唑、BIOCIDE 880 、三乙醇胺、上述三元共聚合體乳化劑及水中，經2小時 -9 - - __ __ 本紙張尺度適用中國國家標準（CNS) A4規格（2丨0><297公釐） ^U1 nn i^—^ϊ 1^1^1 In— —^n 1^1^1 n^i ^^^^1 ^^^^1 ^^^^1 ^^^^1 (請先閱讀背面之注意事項再填寫本頁) 4 80549 A7 B7 經濟部中次標3?-局員工消贤合作社印奴 五、發明説明（9) 之攪拌混合之後，加以過濾而製得水性黑色墨水。 實施例6 : 組_^含量 (重量份） 。碳黑（Carbon Black)(顏料）...........................8.0份 。J0NCHL 62(分散劑）....................................7.4份 (JonsGn株式會社出品，丙烯苯乙烯系分散劑水溶液） 。乙二醇（ethylene glycol)(保濕劑）...............10.0份 。甘油（glylerin)(保濕劑）..............................20.0 份 。NONSOUL 0K-1(潤滑劑）.................................1,0份 (日本油脂株式會社出品）油酸鉀（？0〖355丨11]110丨63亡6) 。苯并三氮唑（benzotriazoIe)(防銹劑）............0.5份 。BIOCIDE 880(防霉劑 '防腐劑）.....................0.2份 (Taisho Technos株式會社出品） 。三乙醇胺（tr iethanolamine) (PH値調整劑）......2.0份 ◎由甲基丙烯酸、丙烯酸丁酯及甲基丙烯酸 之三種單體所形成之三元共聚合物乳化液.........5.0份 (以不揮發分換算其含有量爲44.5〜47.5重量百分 比，揮發分（水)含有量爲55.5〜52.5重量百分比） 。水......................，.....................................45.9 份 將上述碳黑，J0NCRYL 62、乙二醇及甘油利用攪拌機 行2小時之預攪拌，隨後，使用砂摩機施以16小時之摩碎 之後，以離心式分離機分離除去粗大粒子，再將此一邊攪 拌，一邊加入N0NS0UL 0K-1、苯并三氮唑、BIOCIDE .880、 ^^^1^^國家標準{〔邓）八4規格（2丨(^ 297公釐） --------—裝------訂-----線 {請先閲讀背面之注意事項再填寫本頁) 46054.1 A7 B7 五、發明説明（ίο) 三乙醇胺、上述三元共聚合體乳化劑及水中，經2小時之 攪拌混合之後，加以過濾而製得水性黑色墨水。 經滴部中央標準局員工消費合作社印製 實施例7 : 組 成 分 含量(m&m 。碳黑（Carbon Black)(顏料）...........................8.0份 。J0NCRYL 62(分散劑）....................................7.4份 (Jonson株式會社出品，丙烯苯乙烯系分散劑水溶液） 。乙二醇（ethylene glycol)(保濕劑）...............1〇·〇 份 。甘油（g 1 ycer iη)(保濕劑）..............................20.0份 。:NONSOUL 0K-U潤滑劑）.................................1.0份 (日本油脂株式會社出品）油酸鉀（？〇[&55丨1110〇163七6) 。苯並三氣唯（benzotriazole)(防銹劑）............0.5份 。BIOCIDE 880(防霉劑 '防腐劑）.....................0.2份 (Taisho Technos株式會社出品） 。三乙醇胺（triethanolamineKPH値調整劑）…… 2.0份 ◎由甲基丙烯酸、丙烯酸丁酯及甲基丙烯酸 之三種單體所形成之三元共聚合物乳化液.........10.0份 (以不揮發分換算其含有量爲44.5〜47.5重量百分 比，揮發分（水）含有量爲55.5〜52.5重量百分比） 。水............................................................40.9 份 將上述碳黑，J0NCRYL 62、乙二醇及甘油利用攪拌機 進行2小時之預攪拌，隨後，使用砂摩機施以16小時之摩 碎之後，以離心式分離機分離除去粗大粒子，再將此一邊 -11 - 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2!0Χ 297公釐） --------•-裝-- (請先閲讀背面之注意事項再填寫本頁) Τ 4 60549 A7 B7 經 濟 部 中 央 標 準 局 η 工 消 A 社 印 製 五、發明説明（11) 擅拌’一邊加入NONSOUL 0K-1、苯并三氮哗、BIOCIDE 880 、三乙酵胺、上述三元共聚合體乳化劑及水中，經2小時 之攪拌混合之後，加以過濾而獲得水性黑色墨水。 〔比較例1〕 組____分 含量 T重]份） 。水溶性黑色染料（Water Black 100L............... 50.0份 (含水量84重量％ > 。乙二醇（ethylene glycol)保濕劑）..................30.0份 。SC0UR0L 900(滲透劑）.................................〇_1份 (花王石鹸株式會社出品）聚氧乙烯壬基苯醚） (Polyoxyethylene nonyl phenyl ether) 。本并二氮哗（benzotriazole)(防銹劑）............0.5份 。BIOCIDE 880(防霉劑、防腐劑）.....................〇.2份 (Taisho Technos株式會社出品） 。三乙醇胺（triethanolamine)(PH値調整劑）……1.0份 ..............................................................18.1份 將上述乙二醇、SC0UR0L 900、PLYSURF M208B、苯并 三氮唑、BIOCIDE 880及三乙醇胺混合，並加溫至50〜60°C ，利用攪拌機進行20分鐘之攪拌、混合，隨之，在一邊進 行攪拌，一邊將水溶性黑色染料及水依序加入，經約3〇分 鐘之攪拌之後，加以過濾而獲得水性黑色墨水。 12 本紙張尺度適用中國國家標準{ CNS ) A4規格（210X297公釐） n n n I I f d 冰 (請先閲讀背面之注意事項再填寫本I ) 46〇B4^ A7 B7 經滅部中央標率局只工消费合作社印$* 五、發明説明（12) 〔比較例2〕 組__成 分 含量 1重量份) 。碳黑（Carbon Black)(顏料）...........................8.0份 。J0NCRYL 62(分散劑）....................................7.4份 (Jonson株式會社出品，丙烯苯乙烯系分散劑水溶液） 。乙二醇（ethylene glycol)(保濕劑）...............10.0份 。甘油（glylerin)(保濕劑）..............................20.0份 。NONSOUL 0K-1(潤滑劑）.................................1,0份 (日本油脂株式會社出品）油酸鉀（Potassium oleate) 。苯並三氣唑（benzotr iazole)(防銹劑）............0.5份 。BIOCIDE 8δ0(防霉劑 '防腐劑）.....................0.2份 (Taisho Technos株式會社出品） 。三乙醇胺（triethanolamine)(PH値調整齊U)...... 2.0份 。水............................................................50.9份 將上述碳黑，J0NCRYL 62、乙二醇及甘油利用攪拌機 行2小時之預攪拌，隨後，使用砂摩機施以16小時之摩碎 之後，以離心式分離機分離除去粗大粒子，再將此一邊攪 拌，一邊加入N0NS0UL 0K-1、苯并三氮唑' BIOCIDE 880、 三乙醇胺及水中，經2小時之攪拌混合之後，加以過濾而 製得水性黑色墨水。 將由實施例1至實施例7及比較例1至比較例2所得 水性墨水裝入聚丙烯樹脂製儲墨管內，然後從水性墨水完 全儲存於管之下部呈靜止之狀態下，緩慢倒轉180°並保 -13 - 本紙乐尺度適用中國國家榇隼{ CNS ) A4規格（210X 297公釐） II— II— In..... . - I ^!. \| ^^^1 ^^^1 - - -i n --1! —^^1 一eJI L^i (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印製 460549 A7 B7__ 五、發明说明（13) 持垂直狀，觀察其經過過程之狀態，以觀察其潤濕效果。 結果，實施例1〜實施例7之水性墨水在儲墨管反轉之同 時，即順利循儲墨管內壁迅速從上方往下方流勖，而比較 例1及比較例2則因濶濕性不佳，而經過1小時之後，水 性墨水仍滞留上方不易下降，經左右搖動儲墨管之後，方 得流落至下方。 又，各試樣之璺水中，使用內部裝有實施例1，實施 2及比較例1之水性墨水之儲墨管之相同原子筆，藉專用 機以每秒鐘20公分之書寫速度，將筆尖垂直抵於紙面上連 續書寫，經過10分鐘之後，測量其筆跡之粗細，結果，實 施例2之水性墨水之筆跡粗度設爲「1」時，實施例1之 筆跡粗度爲「1.4」，而比較例1之水性墨水之筆跡粗度 爲「1.8」。又，以比較例2之墨水書寫之筆跡，用肉眼 可觀察出從書寫之直線筆跡有許多垂直方向之細微線條分 岐擴散之現象，而用實施例1及實施例2之墨水書寫之筆 跡，則非常顯明而用肉眼幾乎觀察不到有細微之分岐擴散 線條。 根據以上之說明及觀察，本發明之筆具用水性墨水， 顯然可藉組成分中之甲基丙烯酸，丙烯酸丁酯及甲基丙烯 酸甲酯之三種單體所組成之共聚合物乳化液之作用而改善 斥水性（防水性）樹脂之濕潤性，因此，對於例如「直液式 」水性原子筆，能促使經儲墨管、導墨芯及至筆尖之墨水 之流動性圓滑順暢，故可減少墨水在筆尖端之聚集滯留之 情形；同時，可獲得書寫筆跡殆無擴散滲透之效果之水性 墨水。 -14 - 本紙張尺度適用中國國家標準（CNS ) A4規格（2!0X 297公釐） (請先閱讀背面之注意Ϋ項再填寫本页) 訂Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 460549 A7 B7 V. Description of the Invention (1) [Technical Field to which the Invention belongs] The present invention relates to water-based inks applicable to pens, signature pens, marker pens, fountain pens and other writing instruments. [Knowledge Technology] Low-viscosity water-based inks have always been used for ball pens, signature pens, marker pens, and pens. [Problems to be Solved by the Invention] However, in general, water-based writing instruments using such water-based inks are susceptible to changes in room temperature or changes in atmospheric pressure due to changes in room temperature or atmospheric pressure. Problems that cause contamination of clothing. In order to prevent this problem, if the surface tension of the ink is increased, the problem that the ink's fluidity becomes sluggish will occur, especially for water-resistant (water-repellent) resins (such as polypropylene resin, polyethylene resin, etc.). For ink storage tubes with a diameter of less than 8mm0 (this is the diameter of ink storage tubes commonly used in water-based ink pens), the high surface tension of water-based inks causes the water-based inks to maintain their own functions, which makes it difficult to flow smoothly. . In addition, when writing with water-based ink on paper, there is also the problem that the ink easily penetrates into the fibrous tissue of the paper, causing the writing writing to diffuse and penetrate the back, which affects the appearance. Therefore, the present invention aims to solve the above problems, and provides a modified water-based ink which can improve the fluidity of the ink without reducing the surface tension, and improve the ink on the ink storage tank or the ink guiding cartridge and At the same time as the wettability of ink pen cores, it can also effectively suppress the diffusion and penetration of writing handwriting. [Methods for solving problems] -2-This paper size is applicable to the Chinese Standard (CNS) A4 specification (210X297mm) I ----------------- Order -------- ^ {Please read the precautions on the back before filling this page) 460549 A7 B7 V. Description of the invention (2) After a long-term investigation by the inventor, it was found that the pigment (pigment) was dissolved or suspended in an aqueous solvent containing a humectant. ) In a water-based pen with pen, if the three monomers of methyl methacrylate, butyl acrylic acid and methacrylic acid are copolymerized, a ternary The polymer emulsifier component is dissolved or dispersed in the above-mentioned aqueous solvent to obtain an aqueous ink which can improve the wettability to a water-resistant resin, and at the same time can effectively suppress the penetration and diffusion of writing handwriting, thus completing the present invention. The terpolymer copolymerized by the copolymerization of three monomers of methyl butyl acrylate and methacrylic acid. In terms of their composition ratios, the weight percentages are: 40-50% methacrylic acid, and ethyl acrylate. 40 ~ 50%, A Based on 5% acrylic acid, with a molecular weight of about 250,000 ~ 350,000, the viscosity is preferably adjusted from 10,000 to 12,00 CP. The use of this ternary copolymer is 0.4% by weight based on the non-volatile content. Above, the above-mentioned wettability can be significantly improved, especially when it is mixed and dispersed in a weight percentage of 2.2% to 2.3%, its penetration suppression effect and wettability are most suitable. The increase will reduce the continuous writing distance (handwriting length). It is printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Three monomers: butyl acrylate and methacrylic acid were added to the reaction kettle according to the aforementioned ratio, and persulfate was used as a catalyst (catalyst). While stirring, heating, and passing about 1 ° C at about 80 ° C After heating for 0 hours, the reaction polymer is cooled to normal temperature to obtain a white emulsion liquid terpolymer. By mixing in the above solvent, the content is 0.4 to 10.0% by weight. Paper size General Chinese National Standard (CNS) A4 specification (21〇297mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Printing 460549 A7 ___— ___B7 5. Description of the invention (3) The ternary copolymer emulsion, The change of the surface tension of the obtained ink is less than 1 dyne / cm (dyne / cm), and the change of the viscosity is less than 1.0 cp (centipoise). The pigment can be selected from dyes and pigments to make up 6 It is suitable to use within the range of ~ 10% by weight. In addition to the above ingredients, if necessary, the following ingredients can be added to use within the predetermined range, that is, penetrant 〇 ~ 0.1 weight percent, surfactant 0 ~ 0.1% by weight, rust inhibitor, preservative, and antifungal agent in 0 ~ i weight percentage. In order not to reduce the surface tension too much, it is advisable to add only a small amount of penetrant and surfactant. [Explanation of the Example] The terpolymer copolymer emulsion used in the following Examples 1 to 7 has a composition ratio of 40 to 50% of methacrylic acid, 40 to 50% of butyl acrylate, and 5% of methacrylic acid in terms of weight percentage. Below, there are those with a viscosity of 10,000 to 12,000 CP (centipoise). Example 1: J | _ ^ _ £ _ content (parts by weight). Water-soluble black dye (Water Black 100L ......... 50.0 parts (water content 84% by weight). Ethylene glycol humectant) ... ........... 30.0 servings. SC0UR0L 900 (penetrant) ........ 0.1 parts (produced by Kao Ishiyo Corporation) polyoxygen Polyoxyethylene nonyl phenyl ether (Polyoxyethylene nonyl phenyl ether) The standard of this paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) -------- i ------ IT ----- (Please read the notes on the back before filling this page} 460549 A7 V. Description of the invention (4). PLYSURF Μ 208 B (Interactive agent) ....... .... 0.1 parts (produced by Daiichi Kogyo Pharmaceutical Co., Ltd. phosphate ester). Benzotriazole (rust inhibitor) ... 0.5 parts. BIOCIDE .880 (Fungicide, Preservative) ..... 0.2 parts (by Taisho Technos Co., Ltd.). Triethanolamine (PH 値 adjusting agent) ... 1.0 part ◎ terpolymer copolymer emulsion formed by three monomers of methacrylic acid, butyl acrylate and methacrylic acid ... ..... 1.0 parts (in terms of non-volatile content, the content is 44.5 to 47.5 weight percent, and the content of volatile (water) content is 55.5 to 52.5 weight percent). water................................................. ........... 17.1 parts Mix the above ethylene glycol, SC0UR0L 900, PLYSURF M208B, benzotriazole 'BIOCIDE 880 and triethanolamine, and heat to 50 ~ 60 ° C, using a blender After stirring and mixing for 20 minutes, the water-soluble black dye, water, and the above-mentioned terpolymer emulsion were sequentially added while stirring, and after stirring for about 30 minutes, the mixture was filtered to obtain tritium. The Ministry of Central Standards Bureau employees printed cooperatively produced water-based black ink. Example 2: J | _block_ content (parts by weight). Water-soluble black dye (Water Black 100L ......... 50.0 parts (water content 84% by weight). Ethylene glycol humectant) ... ........... 30.0 servings. SC0UR0L 900 (penetrant) ........ 0.1 parts, I pack --- Order -----, line (please read the notes on the back before filling in this page) This paper size is applicable to Chinese national standards (CMS> A4 size (210X 297 mm)) Printed 460549 A7 ______B7__ 5. Description of the invention (5) (produced by Kao Shijie Co., Ltd.) Polyoxyethylene nonyl phenyl ether). PLYSURF M 208 B (surfactant) .............. 0.1 parts (produced by Daiichi Kogyo Co., Ltd. phosphate). Benzotriazole (rust inhibitor) ... 0.5 parts. BIOCIDE 880 (Fungicide, Preservative) ..... 0.2 parts (by Taisho Technos Corporation). Triethanolamine (PH 値 adjusted! J) ... 1.0 part ◎ terpolymer copolymer emulsion formed by three monomers of methacrylic acid, butyl acrylate and methacrylic acid .. ....... 5.0 parts (converted in non-volatile matter content of 44.5 ~ 47.5 weight percent, volatile matter (water) content of 55.5 ~ 52.5 weight percent). water................................................. ........... 13.1 parts Mix the above-mentioned ethylene glycol 'SC0UR0L 900, PLYSURF M208B, benzotriazole, BIOCIDE 880 and triethanolamine, and heat to 50 ~ 60eC, using a blender for 20 After stirring and mixing for one minute, water-soluble black dye, water, and the above-mentioned terpolymer emulsion were sequentially added while stirring, and after stirring for about 30 minutes, filtration was performed to obtain an aqueous black ink. Example 3: ^ content (parts by weight). Water-soluble black dye (Water Black 100L ......... 50.0 parts (water content 84% by weight) ^^ 1 I-----1 »^ 々 ^^^ 1 H — ^^^ 1-^ (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 460549 A7 B7 The Ministry of Economic Affairs, China工 消 贽 合 竹 社 印 ^ V. Description of the Invention (6). Ethylene glycol humectant .............. 30.0 parts. SC0UR0L 900 ( Penetrant) .............. 1 part (produced by Kao Ishiyo Corporation) polyoxyethylene Polyoxyethylene nonyl phenyl ether). PLYSURF M 208 B (surfactant) ..... 0.1 parts (First Industrial Pharmaceutical Co., Ltd. Produced by the company) Phosphate ester). Benzotriazole (rust inhibitor) ... 0.5 parts. BIOCIDE 880 (Fungicide, Preservative) ... ... 0.2 parts (produced by Taisho Technos Co., Ltd.). Triethanolamiiie (pH adjusting agent) ... 1.0 part ◎ From methacrylic acid , Butyl acrylate and methyl propylene Ternary copolymer emulsion formed by three monomers of acid ... 10.0 parts (the content of non-volatile matter is 44.5 ~ 47.5 by weight, and the content of volatile matter (water) is 55.5 ~ 52.5% by weight) .............................. ............ 8.1 parts Mix the above ethylene glycol, SC0UR0L 900, PLYSURF M208B, benzotriazole, BIOCIDE 880 and triethanolamine, and warm to 50 ~ 60 ° C With a stirrer, stir and mix for 20 minutes. Then, while stirring, add water-soluble black dye, water, and the above-mentioned terpolymer emulsion in order. After stirring for about 30 minutes, filter and Obtain water-based black ink. (Please read the precautions on the back before filling this page)-* This paper size is applicable to China National Standard (CNS) A4 specification (2 丨 〇 ^ 97 mm) 460S4i A7 B7 V. Description of the invention (7 ) Example 4: Component content (parts by weight). Water-soluble black dye (Water B1 ack 1 ooL ............ 50.0 parts (water content 84% by weight). Ethylene glycol humectant) ..... ............. 30.0 servings. SCOUROL 900 (penetrant) ........ 0.1 parts (produced by Kao Shijian Co., Ltd.) Polyoxyethylene nony1 phenyl ether). Benzotriazine (6121〇1: 1 ^ 32〇16) (anti-embroidery together)] ... 0.5 parts. BIOCIDE 880 (Fungicide 'Preservative') .............. 0.2 parts (by Taisho Technos Corporation). Triethanamine (pH 値 adjuster) ... 1 · 0 parts ◎ Emulsion of ternary copolymer formed by three monomers of methacrylic acid, butyl acrylate and methacrylic acid Liquid ......... 5.0 parts (the content of nonvolatile matter is 44.5 ~ 47.5 weight percent, and the content of volatile matter (water) is 55.5 ~ 52.5 weight percent). water................................................. ........... 13.2 copies *. Ί 订 衣 定 Τ I 矣 (Please read the notes on the back before filling out this page) Printed by "-部 中心 # 准 局 Employee Consumer Cooperatives will print The above ethylene glycol, SC0UR0L 900, benzotriazole, BIOCIDE 880, and triethanolamine were mixed and heated to 50 to 60 ° C, and stirred and mixed for 20 minutes using a blender, and then, while stirring, Water-soluble black dye, water and the above-mentioned ternary copolymer emulsion were added sequentially, and after stirring for about 30 minutes, it was filtered to obtain water-based black ink. The paper size is applicable to China National Standard (CNS Μ4) (210X297) (%) 460549 A7 B7 Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Distillation 5. Description of the invention (8) Example 5: Group content ^ (parts by weight). Carbon Black (pigment) ... ........................ 8.0 parts. J0NCRYL · 62 (dispersant) ...... ..... 7.4 parts (aqueous solution of dispersant containing styrene and ethyl acetate produced by Jonson Co., Ltd.). Ethylene glycol (ethylene g lyco 1) (humectant) ............ 10.0 parts. glycerin (humectant) ............ ............. 20 · 0.: NONSOUL 0Κ-1 (Lubricant) ............ ..... 1 (parts from Japan Oil Co., Ltd.) Potassium oleate. BenzotriazoIe (rust inhibitor) ........ ... 0.5 parts. BIOCIDE 880 (Fungicide, Preservative) ..... 0.2 parts (produced by Taisho Technos Co., Ltd.). Triethanolamine (PH 値 regulator) ... 2.0 parts ◎ terpolymer copolymer emulsion formed by three monomers of methacrylic acid, butyl acrylate and methacrylic acid ........ .1.0 parts (the content is 44.5 to 47.5 weight percent in terms of nonvolatile content, and the content of volatile (water) content is 55.5 to 52.5 weight percent) ° Water ............... ........................ 49.9 parts will be carbon Black, JONCRYL 62, ethylene glycol and glycerin are pre-stirred for 2 hours with a mixer, and then crushed with a sander for 16 hours, and then separated by a centrifugal separator Remove coarse particles, and then add this while stirring N0NS0UL 0K-1, benzotriazole, BIOCIDE 880, triethanolamine, the above-mentioned terpolymer copolymer emulsifier and water, after 2 hours -9--__ __ This paper Standards are applicable to China National Standard (CNS) A4 specifications (2 丨 0 > < 297 mm) ^ U1 nn i ^ — ^ ϊ 1 ^ 1 ^ 1 In— — ^ n 1 ^ 1 ^ 1 n ^ i ^^^ ^ 1 ^^^^ 1 ^^^^ 1 ^^^^ 1 (Please read the notes on the back before filling out this page) 4 80549 A7 B7 The Ministry of Economic Affairs won the second bid 3? 2. Description of the invention (9) After stirring and mixing, filtering is performed to obtain water-based black ink. Example 6: Group content (parts by weight). Carbon Black (Pigment) .............. 8.0 parts. J0NCHL 62 (dispersant) ..................... 7.4 parts (produced by JonsGn, Aqueous solution of propylene styrene dispersant). Ethylene glycol (humectant) ......... 10.0 parts. Glycerin (humectant) .............. 20.0 parts. NONSOUL 0K-1 (lubricant) ........ 1 part (Nippon Oil & Fat Co., Ltd. Produced) Potassium oleate (? 0 〖355 丨 11] 110 丨 63 die 6). BenzotriazoIe (rust inhibitor) ... 0.5 parts. BIOCIDE 880 (Fungicide 'Preservative') .............. 0.2 parts (by Taisho Technos Corporation). Tri ethanolamine (PH 値 adjusting agent) ... 2.0 parts ◎ terpolymer copolymer emulsion formed by three monomers of methacrylic acid, butyl acrylate and methacrylic acid ... ... 5.0 parts (the content of nonvolatile matter is 44.5 to 47.5 weight percent, and the content of volatile matter (water) is 55.5 to 52.5 weight percent). water......................,.......................... ........... 45.9 parts of the above carbon black, JONCRYL 62, ethylene glycol and glycerin were pre-stirred for 2 hours with a blender, and then rubbed with a sander for 16 hours. The coarse particles are separated and removed by a centrifugal separator, and while stirring this, N0NS0UL 0K-1, benzotriazole, BIOCIDE .880, ^^^ 1 ^^ National Standard {[邓] 8 4 specifications (2丨 (^ 297mm) ---------- install ------ order ----- line {Please read the precautions on the back before filling this page) 46054.1 A7 B7 V. Description of the invention (Ίο) Triethanolamine, the above-mentioned terpolymer copolymer emulsifier, and water were stirred and mixed for 2 hours, and then filtered to obtain an aqueous black ink. Printed in Example 7 by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Distillation: Component Content (m & m. Carbon Black (Pigment) ........ ......... 8.0 parts. J0NCRYL 62 (dispersant) ..... .... 7.4 parts (produced by Jonson Co., Ltd., aqueous solution of propylene-styrene dispersant). Ethylene glycol (humectant) ............ 1〇 · 〇Parts. Glycerin (g 1 ycer iη) (humectant) .............. 20.0 parts.:NONSOUL 0K -U Lubricant) ........................ 1.0 parts (produced by Japan Oil Co., Ltd.) potassium oleate (? 〇 [& 55 丨 1110〇163VII6). Benzotriazole (rust inhibitor) ... 0.5 parts. BIOCIDE 880 (Fungicide 'Preservative') .............. 0.2 parts (by Taisho Technos Corporation). Triethanolamine (triethanolamine KPH 値 adjusting agent) ... 2.0 parts ◎ terpolymer copolymer emulsion formed by three monomers of methacrylic acid, butyl acrylate and methacrylic acid ... 10.0 parts (The content of nonvolatile matter is 44.5 to 47.5 weight percent, and the content of volatile matter (water) is 55.5 to 52.5 weight percent). water................................................. ........... 40.9 parts of the above-mentioned carbon black, JONCRYL 62, ethylene glycol and glycerin were pre-stirred for 2 hours with a blender, and then rubbed with a sander for 16 hours. Centrifugal separator is used to separate and remove coarse particles, and then this side is -11-This paper size applies Chinese National Standard (CNS) Λ4 specification (2! 0 × 297 mm) -------- • -pack- (Please read the precautions on the back before filling in this page) Τ 4 60549 A7 B7 Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Industrial Consumers A. V. Description of the invention (11) Good at mixing while adding NONSOUL 0K-1, Benzene III Nitrogen purifier, BIOCIDE 880, triethylenylamine, the above-mentioned terpolymer copolymer emulsifier and water were stirred and mixed for 2 hours, and then filtered to obtain an aqueous black ink. [Comparative Example 1] Group ____ points Content T weight] parts). Water-soluble black dye (Water Black 100L ......... 50.0 parts (water content 84% by weight > ethylene glycol moisturizer) ... ...... 30.0 parts. SC0UR0L 900 (penetrant) ............. .... 〇_1 servings (produced by Kao Shijie Co., Ltd.) (Polyoxyethylene nonyl phenyl ether). Benzotriazole (rust inhibitor) ... 0.5 parts. BIOCIDE 880 (Fungicide, Preservative) ..... 2 (by Taisho Technos Corporation). Triethanolamine (pH-adjusting agent) ... 1.0 part ... ........... 18.1 parts of the above-mentioned ethylene glycol, SC0UR0L 900, PLYSURF M208B, benzotriazole, BIOCIDE 880 and Mix triethanolamine and heat to 50 ~ 60 ° C. Stir and mix for 20 minutes with a blender. Then, while stirring, add the water-soluble black dye and water in order. After about 30 minutes After stirring, it was filtered to obtain an aqueous black ink. 12 This paper size applies the Chinese National Standard {CNS) A4 specification (210X297 mm) nnn II fd ice (please read the notes on the back before filling in this I) 46〇B4 ^ A7 B7 Consumption cooperatives printed $ * 5. Description of the invention (12) [Comparative example 2] Group _ ingredient content 1 part by weight). Carbon Black (Pigment) .............. 8.0 parts. J0NCRYL 62 (dispersant) ..................... 7.4 parts (by Jonson Corporation, Aqueous solution of propylene styrene dispersant). Ethylene glycol (humectant) ......... 10.0 parts. Glycerin (humectant) .............. 20.0 parts. NONSOUL 0K-1 (lubricant) ........ 1 part (Nippon Oil & Fat Co., Ltd. (Production) Potassium oleate. Benzotriazole (rust inhibitor) ... 0.5 parts. BIOCIDE 8δ0 (Fungicide 'Preservative') .............. 0.2 parts (by Taisho Technos Co., Ltd.). Triethanolamine (adjusted pH) U 2.0 parts. water................................................. ........... 50.9 parts of the above carbon black, JONCRYL 62, ethylene glycol and glycerin were pre-stirred for 2 hours with a blender, and then rubbed with a sander for 16 hours. Coarse particles are separated and removed by a centrifugal separator, and this is added with stirring while adding NOSNOUL 0K-1, benzotriazole 'BIOCIDE 880, triethanolamine, and water. After 2 hours of stirring and mixing, it is prepared by filtration. Water-based black ink. The water-based inks obtained in Examples 1 to 7 and Comparative Examples 1 to 2 were filled into a polypropylene resin ink storage tube, and then the water-based ink was completely stored under the tube under a static state, and then slowly inverted 180 ° Pingbao-13-This paper scale is applicable to the Chinese national standard {CNS) A4 (210X 297 mm) II— II— In ......-I ^ !. \ | ^^^ 1 ^^^ 1 ---in --1! — ^^ 1 eJI L ^ i (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 460549 A7 B7__ V. Description of Invention (13 ) Hold it vertically and observe the state of the process to observe its wetting effect. As a result, the water-based inks of Examples 1 to 7 flowed smoothly from the top to the bottom of the ink storage tube while the ink storage tube was reversed, while Comparative Examples 1 and 2 were wetted due to wettability. Not good, but after 1 hour, the water-based ink still stays on the top and is not easy to fall. After shaking the ink storage tube from left to right, it has to flow to the bottom. In addition, the same ball pen containing the ink storage tubes of the water-based inks of Examples 1, 2, and Comparative Example 1 was used in the tritium water of each sample, and the pen tip was adjusted by a special machine at a writing speed of 20 cm per second. Writing continuously perpendicular to the paper surface, and after 10 minutes, the thickness of the handwriting was measured. As a result, when the handwriting thickness of the water-based ink of Example 2 was set to "1", the thickness of the handwriting of Example 1 was "1.4". The handwriting thickness of the water-based ink of Comparative Example 1 was "1.8". In addition, the handwriting written in the ink of Comparative Example 2 can be observed with the naked eye from the writing of the linear handwriting. Many vertical lines of fine lines are divided and diffused, while the handwriting written in the inks of Examples 1 and 2 is, It is very obvious and there are almost no subtle diffused lines visible to the naked eye. According to the above explanations and observations, the water-based ink of the pen of the present invention obviously can function as a copolymer emulsion composed of three monomers, namely methacrylic acid, butyl acrylate and methyl methacrylate. And improve the wettability of water-repellent (water-repellent) resin. Therefore, for example, "direct liquid" water-based ball pens can promote the smoothness and smoothness of the ink passing through the ink storage tube, the ink guiding core and the pen tip, so the ink can be reduced In the case where the tip of the pen gathers and stays; at the same time, it is possible to obtain a water-based ink that has no effect of diffusion and penetrating. -14-This paper size is in accordance with Chinese National Standard (CNS) A4 (2! 0X 297 mm) (Please read the note on the back before filling this page) Order