588095 A7 _ B7_ 五、發明說明（/ ) 發明的背景 發明領域 本發明係關於一種可適用於原子筆之亮性水性墨水組 成物。 習知技術的說明 以往，爲了獲得金色 '銀色等之金屬光澤色的筆跡’ 乃提供一種採用亮性顏料之水性墨水組成物。例如’曰本 專利特開平8- 151547號爲一種使用經硬脂酸表面處理所 得之鋁粉顏料的水性墨水組成物。特開平7- 1 18592號爲 一種使用珍珠顏料之水性墨水組成物。 然而，就以往使用鋁粉顏料或珍珠顏料之水性墨水組 成物而言，很難獲得具強烈光亮感之筆跡。 本發明的目的在於提供一種用於原子筆等的亮性水性 墨水組成物，其與過去使用鋁粉顏料或珍珠顏料之水性墨 水相比較，可獲得具強烈光亮感之筆跡。 發明的槪要 爲了達成上述目的而專心一意地進行檢討的結果，就 使用油酸作爲粉碎助劑而被粉粹處理之鋁粉顏料（此顏料 之中値粒徑爲15 // m以上，以30〜60// m較佳）而言，若 將同時含有此鋁粉顏料、水溶性樹脂、水溶性有機溶劑及 水之水性墨水組成物使用於原子筆等之書寫文具中，則在 其墨水的筆跡上展現出強烈的光亮感。 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） * * w m -------------------訂·-------- (請先閱讀背面之注意事項再填寫本頁) 588095 ____B7 ___ 五、發明說明（r ) 又，就使用硬脂酸作爲粉碎助劑而被粉粹處理之鋁粉 顏料（此顏料之中値粒徑爲15//m以上，以30〜60/zm較 佳）而言，若將同時含有此鋁粉顏料、水溶性樹脂、水溶 性有機溶劑及水之水性墨水組成·物使用於原子筆等之書寫 文具中，則在其墨水的筆跡上亦同樣地展現出強烈的光亮 感。 如上所述，若使用本發明的水性墨水組成物於原子筆 等之書寫文具中，則在其筆跡上將展現出強烈的光亮感。 較佳態樣之說明 (鋁粉顏料） 在本發明中所使用的鋁粉顏料，係例如石油溶劑同時 與作爲粉碎助劑之油酸或硬脂酸配合，再將其分散後，藉 由使用球磨機進行粉粹，即可以鋁糊的形式來得到。又例 如，最好能使用更進一步讓此鋁糊（餅）在混合機內同時 添加無機磷酸、脂肪族化合物、表面活性劑、水、水合性 醇及烴類油，然後混煉等所得之耐水型的鱗片狀鋁糊（耐 水型鋁粉顏料或耐水型鱗片狀鋁顏料組成物）。總而言之 ，只要是使用油酸或硬脂酸作爲粉碎助劑而被粉粹處理之 鋁粉顏料，無論何者皆可使用。 若爲使用此油酸作爲粉碎助劑而被粉粹處理之鋁粉顏 料者，因對鋁粉顏料之粒子表面的油酸吸附變稀疏，且極 性亦大，故變成非飄浮型之筆跡或塗膜，而且因在筆跡或 塗膜中具有鋁粉顏料，故各鋁粉顏料以各式各樣的角度配 5 ΐ紙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) 588095 A7 ____B7____ 五、發明說明（今） 向而存在。另一方面，若爲使用硬脂酸來取代油酸作爲粉 碎助劑而被粉粹處理之鋁粉顏料者，因對鋁粉顏料之粒子 表面的硬脂酸吸附變密，且極性低，故變成飄浮型之筆跡 或塗膜。在如此情況下，因鋁粉顏料聚集於筆跡或塗膜的 表面，故各鋁粉的顏料粒子大致與筆跡或塗膜呈平行定向 。然而，在含有具極性之樹脂（淸漆）的情況下，與使用 油酸作爲粉碎助劑而被粉粹處理之鋁粉顏料相同，變成非 飄浮型之筆跡或塗膜，且因在筆跡或塗膜中具有鋁粉顏料 ，故使各鋁粉顏料變成以各式各樣的角度定向而存在。亦 即，就使用硬脂酸作爲粉碎助劑而被粉粹處理之鋁粉顏料 而言，最重要的是含有使鋁粉顏料非飄浮化之極性或高氧 化的樹脂。作爲這些樹脂，可舉出例如藉由使用鹼性中和 劑之電解、羥基或醚基的導入等來進行羥化之醇酸樹脂、 三聚氰胺樹脂等的水溶性樹脂。 又，在本發明中，爲了在原子筆等的筆跡上展現高度 光亮感，最重要的是，更進一步地使其顏料粒子的中値粒 徑變爲15//m以上，最好是30〜60/zm之大粒徑的鋁粉顏 料。若上記鋁粉顏料的中値粒徑未滿15/zm，則即使在筆 跡或塗膜上使鋁粉顏料定向成非飄浮，然而因作爲原子筆 等之筆跡的鱗片狀粒子太小故亮性差。相對於此，若上記 鋁粉顏料的中値粒徑超過60# m，則即使調節上記鋁粉顏 料的含有量或筆珠徑，然而在作爲原子筆墨水來使用時， 墨水很難由筆尖流出，故不佳。此外，若上記大粒徑鋁粉 顏料的粒子徑爲30 // m或超過30 /i m，則在筆跡上將展現 6 裝--------訂--------- (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（210 X 297公釐） 588095 A7 ______B7 五、發明說明（斗） 出更高度的光亮感。 作爲如此的鋁粉顏料，可舉出例如旭化成公司製之商 品名「AW7000R」（中値粒徑：15//m)、東洋鋁業公司 製之商品名「WXM 764〇」（中値粒徑：17# m)、同公司 製之商品名「WXM 5422」（中値粒徑：19#m)、同公司 製之商品名「WXMl44〇」（中値粒徑：30#m)、同公司 製之商品名「WXM1415」（中値粒徑：51//m)、同公司 製之商品名「WXM 7493」（中値粒徑：60/zm)。這些中 値粒徑相異之鋁粉顏料，可1種或混合至少2種來使用。 此外，在本發明中所謂「中値粒徑」係指使用藉由雷 射繞射式粒度分佈計所測得之D5Q値來特定的直徑。 如此大粒徑的鋁粉顏料，以在墨水組成物全量中含有 〇.〇1〜20重量％者爲宜。上述鋁粉顏料，若在墨水組成物 全量中未滿0.01重量％，則在亮性上不充分。若上述銘粉 顏料在墨水組成物全量中超過20重量％，做爲墨水之黏度 會過度上升，流動性降低，書寫性降低。此外，在作爲原 子筆用墨水來使用的情況下，若考慮亮性與墨水流出性（ 在筆珠與保持此筆珠之孔間的墨水流出性）兩者，則如此 大粒徑鋁粉顏料的最適配合量爲〇·〇5〜10重量％。 (水溶性樹脂） 作爲水溶性樹脂，最重要的是，以使用能調整墨水的 黏度，同時亦能謀求大粒徑的鋁粉顏料與著色劑之分散及 防止沉澱的水溶性增稠樹脂，特別是使用給予墨水假塑性 流動特性（觸變性，thixotropy)之水溶性樹脂。若舉一例 7 ---------------訂·-------- (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（210 X 297公釐） 588095 A7 ____B7 五、發明說明（< ) 來說，能使用微生物產系多糖類及其衍生物。例如，可舉 出黏稠性多糖（pullulan )、咕噸（xanthane)膠、韋蘭 (welan)膠、拉母山(rhamsan)膠、琥珀葡聚糖、葡聚糖等。 又，能使用水溶性植物系多糖類及其衍生物。例如，可舉 例出西黃蓍膠（tragcanth)、瓜爾豆（guar)膠、雲實屬 (tara)膠、次槐豆（locust beam)膠、卡丁佳(caatinga)膠、阿 拉伯糖半乳聚糖（arabinogalactan)膠、阿拉伯膠、溫桴子 (quince seeds)膠、果膠、澱粉、歐車前子(pSylliuin seeds) 膠、角叉藻膠、褐藻酸、瓊脂(agar)等。又，能使用水溶性 動物系多糖類及其衍生物。例如，可舉例出明膠、酪素、 淸蛋白（albumin)等。又，作爲增稠樹脂，可使用N—乙烯 基乙醯胺樹脂、交聯之N-乙烯基乙酸醯胺樹脂等之N-乙烯基乙酸醯胺系樹脂。 就本發明而言，上述水溶性樹脂中尤可適當地使用微 生物產系多糖類及其衍生物。又，上述水溶性樹脂可使用 1種或將至少2種混合使用。 這些水溶性樹脂在墨水組成物全量中以含有〇.〇1〜40 重量％者爲宜。若上述水溶性樹脂在墨水組成物全量中未 滿0.01重量％時，大粒徑的鋁粉顏料的沉澱防止效果不充 分。若水溶性樹脂在墨水組成物全量中超過40重量％時， 作爲墨水之黏度會過度上升，而降低流動性。水溶性樹脂 之最佳配合量，雖依水溶性樹脂之種類而略有不同，然一 般爲0.05〜20重量％。 此外，在上記的水溶性樹脂中，特別是相對於中値粒 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 588095 A7 _____B7___ 五、發明說明（6 ) 徑15//m以上，最好是30〜60# m之大粒徑的鋁粉顏料， 以韋蘭膠、拉母山膠、琥珀葡聚糖在墨水中之分散安定性 良好，且相對於含有大粒徑鋁粉顏料之墨水，其亦可給予 良好的假塑性流動特性（觸變性）。 (水溶性有機溶劑） 水溶性有機溶劑以使用能謀求防止筆尖之乾燥與防止 墨水之凍結之物爲宜。例如可舉出乙二醇、二乙二醇、三 乙二醇、丙二醇、聚乙二醇等二元醇類，甘油等之多元醇 類，乙二醇單甲醚、二乙二醇單甲醚、二丙二醇單甲醚、 二丙二醇單丙醚等之乙二醇醚類。這些有機溶劑可採用1 種或將至少2種混合使用。 水溶性有機溶劑，在墨水組成物全量中以含有1〜40重 量％者爲宜。上述水溶性有機溶劑，若在墨水組成物全量 中未滿1重量％，則筆尖容易乾燥，又墨水容易凍結。若 水溶性有機溶劑在墨水組成物全量中超過40重量％，不但 會影響上述水溶性樹脂之溶解性，同時筆跡不易乾燥。故 水溶性有機溶劑之最佳配合量，雖依水溶性有機溶劑之種 類略有不同，但以5〜20重量％者爲佳。 (著色劑） 作爲著色劑，採用不與上述大粒徑的鋁粉顏料反應， 以及不致影響該鋁粉顏料的光亮感之物爲佳。具體而言， 可舉出除酸性染料、直接染料、鹼性染料等的水溶性染料 ，尙有碳黑等的無機顏料，銅肽菁(phthalocyanine)系顏料 、替(threne)系顏料、偶氮系顏料、喹D丫酮(quinacridone)系 9 ___ 本紙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) 588095 A7 ___B7__ 五、發明說明（？） 顏料、憩·〇η1:1ΐΓ&ςιΗηοη6)系顏料、二卩惡院系顏料、館藍系 顏料、硫靛系顏料、北醌系顏料、北（perylene)系顏料、 吲哚醌系顏料、甲亞胺(azomethine)系顏料等之有機顏料， 以及螢光顏料、著色樹脂乳液等。又，該等物質可作爲顏 料分散體來使用。又，在本發明中可混合1種或至少2種 顏料來使用。又，可混合本發明的大粒徑鋁粉顏料與珍珠 顏料等之亮性顏料來使用。又，亦可混合使用具遮蓋性的 氧化鈦、烷撐雙三聚氰胺衍生物、球狀·扁平狀等之各種 形狀的塑膠顏料（合成樹脂粒子顏料）等之各種的無機或 有機白色顏料之遮蓋性顏料。又，亦可同時使用鋁粉顏料 與金屬被覆無機顏料。 在本發明的水性墨水組成物中，即使未含有著色劑亦 可。不含著色劑而含有鋁粉顏料之水性墨水組成物，亦可 給予筆跡高度光亮感。然而含有著色劑之上述水性墨水組 成物，因可藉由著色劑的色調等而賦予對應於該色調等之 高度光亮感於筆跡上，故乃特別所希望者。 又，著色劑在墨水組成物全量中以含有0.05〜15重量 %者爲宜。若上述著色劑在墨水組成物全量中未滿0.05重 量％時’很難以視覺辨認該著色劑的著色。若著色劑在墨 水組成物全量中超過15重量％，作爲墨水之黏度會過度上 升’而降低流動性。著色劑之最佳配合量，雖依著色劑之 種類而略有不同，但一般爲1〜10重量％。 (合成樹脂乳液） 如上所述，本發明者爲了得到具有高度光亮感的筆跡 10 本紙週用中國國家標準（CNS)A4規格（210 X 297公爱—)一'" " 裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 588095 A7 __B7_ ___ 五、發明說明（f ) ，發現可在含有水溶性增稠樹脂、水溶性有機樹脂、與水 之墨水組成物中，適當地使用以油酸或硬脂酸作爲粉碎助 劑來進行粉粹處理所得之大粒徑鋁粉顏料。相較於以往使 用其他脂肪酸或無機酸作爲粉碎助劑來進行粉碎處理所得 之小粒徑的鋁粉顏料與珍珠顏料，若使用此大粒徑鋁粉顏 料，則能賦予筆跡更高度的光亮感。 然而，就含有水溶性樹脂，特別是水溶性增稠樹脂之 亮性水性墨水組成物而言，雖可藉由該水溶性增稠樹脂將 上記大粒徑鋁粉顏料的固著性昇高至某一程度，惟發現因 上記大粒徑鋁粉顏料的形狀太大，故以水溶性增稠樹脂很 難使大粒徑鋁粉顏料強力地固著於基材。因此，就含有上 記大粒徑鋁粉顏料之水性墨水組成物而言，於書寫後，受 到摩擦等作用造成上記大粒徑鋁粉顏料容易剝落，所以很 難持續地將高度光亮感賦予至筆跡，具有光亮感的筆跡或 塗膜之耐久性乃低。 由於上述緣故，提供一種不會降低墨水特性或書寫性 能，且不會因爲配合上記大粒徑鋁粉顏料而阻礙高度光亮 感之效果，並且能夠提升對基材之上記大粒徑鋁粉顏料的 固著性，而且能持續地將更高度的光亮感賦予筆跡之水性 墨水組成物，特別是在書寫用具中原子筆用之亮性水性墨 水組成物，爲本發明之重要課題。 爲了達成上述課題，經努力硏究的結果，發現若含有 作爲必須成分之上記大粒徑鋁粉顏料、水溶性樹脂、水溶 性有機溶劑及水，且進一步地含有可將上記大粒徑鋁粉顏 11 本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公爱)一 一 ------ C請先53讀背面之注意事項再填寫本頁) Μ*·I ·111111 I — — — — — — — . 588095 A7 _ B7 五、發明說明（1 ) 料強力地固著於例如書寫用紙等之紙等的被塗佈物、被複 印物等之基材上的結合劑成分（固著樹脂成分）之亮性水 性墨水組成物，將能夠解決上述的課題。 另一方面，爲將此種上記大粒徑鋁粉顏料強力地固著 於被塗佈物、被複印物等之基材上，可考慮使用作爲結合 劑成分之水溶性合成樹脂。但是爲了強力固著大粒徑鋁粉 顏料，而依據使用之水溶性合成樹脂的種類來提高含量時 ，有時會對於增稠樹脂的溶解性、著色劑的分散性造成不 良影響。又，有時墨水的黏彈性會大大地降低，導致書寫 性能之下降。又，縱使能發揮對於被塗佈物、被複印物等 之基材的固著性，仍必須避免成爲上記大粒徑鋁粉顏料之 局度光売感在該筆跡中降低之水性墨水組成物。 本發明者更努力硏究的結果，發現若使用合成樹脂乳 液作爲使上記大粒徑鋁粉顏料固著於被塗佈物、被複印物 等之基材上之結合劑成分，不僅不會失去亮性，亦可提高 上記大粒徑鋁粉顏料對書寫用紙等之紙等的基材之固著性 ，進而完成本發明。 因此’將含有上記大粒徑鋁粉顏料之本發明的水性墨 水組成物書寫或塗佈或複印於紙、金屬、塑膠、纖維製品 等之被塗佈物、被複印物等的基材上時，能提高上記大粒 徑鋁粉顏料對於被塗佈物、被複印物等之基材的固著性， 並使其能成爲具耐久性之筆跡，且對於該筆跡亦能持續地 賦予更高度的光亮感。這是因爲合成樹脂乳液的成膜性對 具有大的鱗片形狀之上記大粒徑鋁粉顏料爲適合的、不致 12 本紙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) 588095 A7 ______— _B7 _ 五、發明說明（ί。） 妨礙由於上記大粒徑鋁粉顏料的配合所產生的高度光亮感 之效果、並能夠強力地固著於被塗佈物、被複印物等之基 材上之故。 而且’因本發明的結合劑成分（固著樹脂成分）並非 水溶性合成樹脂而爲合成樹脂乳液之故，故對同時所配合 之水溶性增稠樹脂的溶解性、著色劑的分散性、以及墨水 的黏彈性等之特性上鮮會造成不良影響。因此，本發明的 墨水組成物不會對墨水的黏度、書寫性能以及筆跡的顏色 造成影響，而能提升上記大粒徑鋁粉顏料的固著性。 由上述結果可知，本發明之含上記大粒徑鋁粉顏料的 亮性水性墨水組成物，不致降低墨水特性和書寫性能等， 且不妨礙玻璃所具有之高表面平滑性，相較於使用以往之 鋁粉顏料、珍珠顏料等之亮性顏料的水性墨水組成物，可 持續地賦予筆跡更高度的光亮感。 作爲本發明的合成樹脂乳液者並無特別的限定，只要 是具水分散性的合成樹脂乳液即可使用。但若考慮墨水特 性及書寫性能時，使用不致影響水溶性增稠樹脂的溶解性 或墨水的黏度、著色劑的分散性、以及墨水的顯色係重要 的。此外，不致妨礙由於上記大粒徑鋁粉顏料的配合所產 生的高度光亮感之效果亦爲重要的。 又，合成樹脂乳液的最低成膜溫度以20°C以下爲佳。 若合成樹脂乳液的最低成膜溫度爲20°C以下，特別是〇t： 以下時，不僅在常溫（25°C )下、即使在寒冷地帶亦能皮 膜化，且能提高對於基材之筆跡的固著性。 13 本紙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) 588095 A7 _______Β7 五、發明說明（U ) 又，合成樹脂乳液亦能適宜地使用具陰離子性或非離 子性的物質。具陰離子性或非離子性的合成樹脂乳液，例 如可由陰離子性或非離子性的單體來製作合成樹脂，或可 藉由使用陰離子性或非離子性乳化劑來獲得。若合成樹脂 乳液具有陰離子性或非離子性，即可提高墨水組成物的安 定性。 又合成樹脂乳液，以墨水的pH爲6以上時，不致影 響著色劑的分散性或水溶性增稠樹脂的溶解性之物爲佳。 由此觀點看來，作爲合成樹脂乳液，例如可使用丙烯 酸系合成樹脂乳液、苯乙烯-丙烯酸系合成樹脂乳液、乙 酸乙烯系合成樹脂乳液。又，作爲丙烯酸系合成樹脂乳液 ，例如以丙烯酸酯共聚物合成樹脂乳液爲佳。作爲苯乙烯 -丙烯酸系合成樹脂乳液，例如以苯乙烯-丙烯酸酯共聚 物合成樹脂乳液爲佳。又在乙酸乙烯系合成樹脂乳液方面 ，例如可適宜地使用乙酸乙烯合成樹脂乳液、乙酸乙烯-丙烯酸酯共聚物合成樹脂乳液。合成樹脂乳液可使用該等 合成樹脂的1種或混合至少2種來使用。 具體而言，作爲丙烯酸系合成樹脂乳液，可舉出例如 商品名「尼卡索魯FX336」（日本電石（Carbide)工業股 份有限公司製、最低成膜溫度<0°C、pH 7.5、200mPa · s )、商品名「尼卡索魯A - 02」（日本電石工業股份有限 公司製、最低成膜溫度<0°C、pH 7.0、500mPa · s)、商 品名「尼卡索魯FH—011A」（日本電石工業股份有限公 司製、最低成膜溫度<0°C、pH 7.0、150mPa · s)，又， 14 本紙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) 588095 A7 __B7 五、發明說明（、> ) 作爲乙酸乙烯系合成樹脂乳液，可舉出例如商品名「摩必 尼魯231」（庫拉里安德聚合物股份有限公司製、最低成 膜溫度< 〇°C、pH 4.0、黏度500〜1500mPa · S)等。此外 ，此黏度測定係使用25°C的B型黏度計所測得之數値。 合成樹脂乳液的含有量並無特別地限定，例如相對於 墨水組成物全量以固形分〇· 1〜40重量％爲適宜範圍。若 合成樹脂乳液的含有量相對於墨水組成物全量在固形分未 達〇· 1重量％時，將使相對於基材之上記大粒徑鋁粉顏料 的固著性降低。另一方面，若合成樹脂乳液的含有量相對 於墨水組成物全量在固形分超過40重量％時，固形分變多 ，於筆尖處的塗膜化等將使書寫性能降低。此外，筆跡容 易白色化。爲使對於基材之上記大粒徑鋁粉顏料的固著性 更爲優異，合成樹脂乳液的含有量以相對於墨水組成物全 量在固形分上至少0.3重量％爲最適宜。又，爲使書寫性 能更爲優異，合成樹脂乳液的含有量以相對於墨水組成物 全量在固形分上20重量％者爲最適宜。亦即，合成樹脂乳 液的最佳含有量爲0.3〜20重量％。 由上述可知，作爲有關本發明實施形態之亮性水性墨 水組成物，最佳者係如申請專利範圍1所記載者，其相對 於墨水全量，含有以下成分a〜e且黏度爲1，〇〇〇〜 10,000mPa · s (ELD 型黏度計：3。R14 圓錐體、〇.5rpm、 2〇°C )之亮性水性墨水組成物。 a·使用油酸或硬脂酸作爲粉碎助劑來進行粉粹處理而 得之中値粒徑15//m以上的鋁粉顏料0.01〜20重量％ , 15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） * > I — I— · - I-----·111111 I I (請先閱讀背面之注意事項再填寫本頁) 588095 A7 ___B7 五、發明說明（〇 ) b. 擇自丙烯酸系合成樹脂乳液、苯乙烯-丙烯酸系合 成樹脂乳液及乙酸乙烯系合成樹脂乳液之合成樹脂乳液0·1 〜40重量％ (固形分）， c. 擇自韋蘭膠、琥珀葡聚糖及拉母山膠之多糖類0.01 〜40重量％， d. 水溶性有機溶劑1〜40重量％， e. 著色顏料〇.〇5〜15重量％ (其他的添加物） 此外，在本發明中，依其他之需要，可添加聚環氧乙 烷鹼金屬鹽，二羧酸醯胺、磷酸酯、N-油烯基肌氨酸鹽 等之潤滑劑，苯并三唑、甲苯基三氮雜茂二環己基硝酸銨 等之防銹劑，苯并異噻唑啉系、五氯苯酚系、甲酚等之防 腐防黴劑，以及相對於上記大粒徑鋁粉顏料之各種表面活 性劑等。 此外，本發明之墨水組成物的最佳黏度範圍爲1，〇〇〇〜 10,000mPa · s。本發明的墨水組成物被調整至如此的黏度 範圍。此外，此黏度係ELD型黏度計（3° R14圓錐體、 OApm、20°C )之測定値。 (墨水的製作方法） 雖可採用以往眾所周知的分散方法、消泡方法、過濟 等來製作墨水，然而作爲投入方法，最好使用以下的方法 。亦即，在溫室中藉由溶解等使水、水溶性有機溶劑、声 性鋁粉顏料、著色劑分散後，投入水溶性樹脂、固著樹月^ ，再依必要性而添加各種添加劑及調整pH値，然後藉由 16 (請先閱讀背面之注意事項再填寫本頁) — I----訂--------- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 588095 A7 B7 五、發明說明（哼） 加壓過濾等來過濾此混合液後，再進行消泡即可獲得亮性 墨水組成物。 實施例 依表1所示的組成及配合量（重量％)，依上記製造 方法，混合攪拌水、水溶性有機溶劑、既定的大粒徑鋁粉 顏料、及著色劑乃至顏料基劑等之各成分使分散後，投入 水溶性樹脂，然後將其過濾後消泡，即可獲得實施例的亮 性水性墨水組成物。如表2所示般，爲了比較，混合攪拌 水、水溶性有機溶劑、小粒徑的鋁粉顏料及珍珠顏料等之 各成分使分散後，投入水溶性樹脂，然後將其過濾後消泡 ，即可獲得比較例的水性墨水組成物。無論在實施例及比 較例方面，分散方法、消泡方法、過濾等皆採用以往眾所 周知的方法。 表1 (重量％ ) 實施例 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 I 4.0 4.0 4.0 4.0 Π 4.0 4.0 4.0 4.0 鋁粉顏料 m 4.0 4.0 4.0 4.0 IV V 4.0 4.0 4.0 珍珠顏料 水溶性樹脂 I 0.3 0.3 0.3 0.3 0.4 0.4 0.4 17 本紙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) 588095 A7B7 五、發明說明（6) Π 0.4 0.4 0.4 0.4 瓜 0.3 0.3 0.3 0.3 IV 3.0 3.0 3.0 固著樹脂 I 15 15 15 15 15 15 15 15 15 Π 12 12 12 水溶性有機 溶劑 I 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 Π 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 著色劑 I 2.0 2.0 2.0 2.0 2.0 Π 0.8 0.8 0.8 0.8 0.8 防腐防黴劑 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 防銹劑 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 潤滑劑 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 亮性顏料分散劑 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 水 56.4 54.4 55.6 54.3 55.5 56.3 55.6 56.4 54.4 56.4 54.3 55.6 71.3 69.3 70.5 合計 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 光亮感 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 比較例 1 2 3 4 5 6 7 8 9 10 11 12 I Π 鋁粉顏料 m IV 4.0 4.0 4.0 4.0 V 8.0 8.0 8.0 4.0 18 本紙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) 588095 A7 B7 五、發明說明（^)588095 A7 _ B7_ V. Description of the invention (/) Background of the invention Field of the invention The present invention relates to a bright water-based ink composition applicable to ball pens. Description of Conventional Technology Conventionally, a water-based ink composition using a bright pigment has been provided in order to obtain a golden 'silver color metallic handwriting'. For example, Japanese Patent Laid-Open No. 8-151547 is an aqueous ink composition using an aluminum powder pigment obtained by stearic acid surface treatment. Japanese Patent Laid-Open No. 7-1 18592 is a water-based ink composition using a pearl pigment. However, it has been difficult to obtain a handwriting with a strong luster for an aqueous ink composition using an aluminum powder pigment or a pearl pigment in the past. An object of the present invention is to provide a bright water-based ink composition for ball-point pens and the like, which can obtain a handwriting with a strong luster compared with water-based inks using aluminum powder pigments or pearl pigments in the past. In order to achieve the above-mentioned purpose, the invented 槪 will focus on the results of an intensive review, using an oleic acid as a pulverization aid and an aluminum powder pigment (the 値 particle size of this pigment is 15 // m or more. 30 ~ 60 // m is preferred), if an aqueous ink composition containing both the aluminum powder pigment, water-soluble resin, water-soluble organic solvent, and water is used in a writing stationery such as a ball pen, the ink The handwriting showed a strong sense of brightness. 4 This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) * * wm ------------------- Order · ------ -(Please read the precautions on the back before filling this page) 588095 ____B7 ___ V. Description of the invention (r) In addition, the aluminum powder pigments (in this pigment) that have been treated with stearic acid as a grinding aid (in this pigment)値 The particle diameter is 15 // m or more, preferably 30 ~ 60 / zm.) If an aqueous ink composition and material containing both the aluminum powder pigment, water-soluble resin, water-soluble organic solvent, and water is used, In writing stationery such as pens, the ink handwriting also exhibits a strong light feeling. As described above, if the water-based ink composition of the present invention is used in a writing stationery such as a ball pen, the handwriting will show a strong luster. Explanation of the preferred aspect (aluminum powder pigment) The aluminum powder pigment used in the present invention is, for example, a petroleum solvent mixed with oleic acid or stearic acid as a pulverization aid at the same time, and then dispersed, and then used The ball mill is powdered, that is, it can be obtained in the form of aluminum paste. For another example, it is better to use the water resistance obtained by further adding this aluminum paste (cake) to the inorganic phosphoric acid, aliphatic compound, surfactant, water, hydratable alcohol and hydrocarbon oil in the mixer, and then mixing Type scaly aluminum paste (water-resistant aluminum powder pigment or water-resistant scaly aluminum pigment composition). In short, as long as it is an aluminum powder pigment that has been treated with oleic acid or stearic acid as a pulverizing aid, any one can be used. For those who use this oleic acid as a pulverizing aid and have been treated with aluminum powder pigments, because the oleic acid adsorption on the surface of the aluminum powder pigments becomes thinner and the polarity is large, it becomes a non-floating handwriting or coating. Film, and because it has aluminum powder pigment in handwriting or coating film, each aluminum powder pigment is matched with 5 at various angles. Ϊ́Paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) '- ------------ ^ -------- ^ ------ (Please read the notes on the back before filling out this page) 588095 A7 ____B7____ 5. Description of the invention ( Today) exists forever. On the other hand, if it is an aluminum powder pigment that is treated with stearic acid instead of oleic acid as a pulverizing aid, it will have a denser stearic acid adsorption on the surface of the particles of the aluminum powder pigment, and its polarity is low. It becomes a floating handwriting or coating. In this case, since the aluminum powder pigment is collected on the surface of the handwriting or the coating film, the pigment particles of each aluminum powder are oriented substantially parallel to the handwriting or the coating film. However, in the case of containing polar resin (paint), it is the same as the aluminum powder pigment treated with oleic acid as a grinding aid, and becomes a non-floating handwriting or coating film. Since the coating film has an aluminum powder pigment, each of the aluminum powder pigments is oriented at various angles and exists. That is, in the case of aluminum powder pigments that have been processed with stearic acid as a pulverizing aid, it is most important to contain a polar or highly oxidized resin that makes the aluminum powder pigment non-floating. Examples of these resins include water-soluble resins such as alkyd resins and melamine resins which are hydroxylated by electrolysis using a basic neutralizing agent, introduction of a hydroxyl group or an ether group, and the like. In addition, in the present invention, in order to exhibit a high-gloss feeling on a handwriting such as a ball pen, it is most important to further increase the median particle size of the pigment particles to 15 // m or more, preferably 30 to 60 / zm aluminum powder pigment with large particle size. If the median particle size of the aluminum powder pigment is less than 15 / zm, even if the aluminum powder pigment is oriented non-floating on the handwriting or coating film, the scale-like particles used as the handwriting of the ballpoint pen are too small and the brightness is poor. . In contrast, if the medium particle size of the above aluminum powder pigment exceeds 60 # m, even if the content of the aluminum powder pigment or the pen diameter is adjusted, it is difficult for the ink to flow out from the pen tip when it is used as a ballpoint ink. So bad. In addition, if the particle diameter of the large-size aluminum powder pigment is 30 // m or more than 30 / im, the 6 pieces will be displayed on the handwriting .-------- Order --------- (Please read the precautions on the back before filling in this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 588095 A7 ______B7 5. Description of the invention (bucket) For a higher degree of brightness. Examples of such aluminum powder pigments include, for example, the trade name "AW7000R" (Medium particle size: 15 // m) manufactured by Asahi Kasei Corporation, and the trade name "WXM 764〇" (Medium particle size) : 17 # m), the same company's product name "WXM 5422" (medium size: 19 # m), the same company's product name "WXMl44〇" (medium size: 30 # m), the same company The product name "WXM1415" (medium particle size: 51 // m), and the product name "WXM 7493" (medium particle size: 60 / zm) manufactured by the same company. These aluminum powder pigments having different medium 中 particle sizes may be used singly or in combination of at least two kinds. In addition, in the present invention, the "medium」 particle size "refers to a specific diameter using D5Q 测 measured by a laser diffraction particle size distribution meter. The aluminum powder pigment having such a large particle diameter preferably has a content of 0.001 to 20% by weight in the entire ink composition. When the aluminum powder pigment is less than 0.01% by weight in the total amount of the ink composition, the brightness is insufficient. If the above-mentioned powder powder pigment exceeds 20% by weight in the total amount of the ink composition, the viscosity of the ink will increase excessively, the fluidity will decrease, and the writing performance will decrease. In addition, when using as a ballpoint ink, considering the brightness and ink outflow (the ink outflow between the ball and the hole holding the ball), such a large particle size aluminum powder pigment The optimum blending amount of O is 0.05 to 10% by weight. (Water-soluble resin) As a water-soluble resin, the most important thing is to use a water-soluble thickening resin that can adjust the viscosity of the ink, and also can disperse aluminum powder pigments and colorants with a large particle size and prevent precipitation, especially It is a water-soluble resin that imparts pseudoplastic flow characteristics (thixotropy) to the ink. If you give an example 7 --------------- Order · -------- (Please read the precautions on the back before filling this page) This paper size applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) 588095 A7 ____B7 5. In the description of the invention (<), polysaccharides derived from microorganisms and their derivatives can be used. For example, pullulan, xanthane gum, welan gum, rhamsan gum, succinodextran, dextran and the like can be mentioned. In addition, water-soluble plant polysaccharides and derivatives thereof can be used. For example, tragacanth, guar gum, tara gum, locust beam gum, caatinga gum, arabinose galactose can be exemplified. Arabinogalactan gum, acacia gum, quince seeds gum, pectin, starch, pSylliuin seeds gum, carrageenan, alginic acid, agar, and the like. In addition, water-soluble animal polysaccharides and their derivatives can be used. For example, gelatin, casein, albumin and the like can be exemplified. Further, as the thickening resin, N-vinylacetamide resin, N-vinylacetamide resin, and the like can be used. In the present invention, among the above-mentioned water-soluble resins, microbiological polysaccharides and their derivatives can be suitably used. Moreover, the said water-soluble resin can be used individually by 1 type or in mixture of 2 or more types. These water-soluble resins are preferably contained in an amount of 0.01 to 40% by weight in the entire ink composition. If the water-soluble resin is less than 0.01% by weight in the total amount of the ink composition, the effect of preventing precipitation of the aluminum powder pigment with a large particle diameter is insufficient. When the water-soluble resin exceeds 40% by weight in the total amount of the ink composition, the viscosity as an ink will increase excessively, and the fluidity will be reduced. Although the optimum blending amount of the water-soluble resin varies slightly depending on the type of the water-soluble resin, it is generally 0.05 to 20% by weight. In addition, among the above-mentioned water-soluble resins, especially the paper size of 8 papers is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- pack- ------- Order --------- (Please read the precautions on the back before filling this page) 588095 A7 _____B7___ V. Description of the invention (6) diameter 15 // m or more, preferably Aluminum powder pigments with a large particle size of 30 ~ 60 # m have good dispersion stability in inks such as wellan gum, ram rubber, and succindextran, and compared with inks containing large particle aluminum powder pigments, It can also give good pseudoplastic flow properties (thixotropy). (Water-soluble organic solvent) The water-soluble organic solvent is preferably a substance that can prevent the pen tip from drying out and the ink from freezing. Examples include glycols such as glycol, diethylene glycol, triethylene glycol, propylene glycol, and polyethylene glycol; polyhydric alcohols such as glycerin; glycol monomethyl ether and diethylene glycol monomethyl. Glycol ethers such as ether, dipropylene glycol monomethyl ether, and dipropylene glycol monopropyl ether. These organic solvents may be used singly or in combination of at least two kinds. The water-soluble organic solvent preferably contains 1 to 40% by weight of the entire ink composition. When the water-soluble organic solvent is less than 1% by weight in the total amount of the ink composition, the pen tip is liable to dry and the ink is liable to freeze. If the water-soluble organic solvent exceeds 40% by weight in the total amount of the ink composition, not only the solubility of the above water-soluble resin will be affected, but also the handwriting will not be easily dried. Therefore, the optimal blending amount of the water-soluble organic solvent is slightly different depending on the type of the water-soluble organic solvent, but it is preferably 5 to 20% by weight. (Colorant) As the colorant, it is preferable to use a substance that does not react with the above-mentioned aluminum powder pigment having a large particle size and does not affect the brightness of the aluminum powder pigment. Specific examples include water-soluble dyes other than acid dyes, direct dyes, and basic dyes; inorganic pigments such as carbon black; copper peptides (threne) pigments; azo pigments; and azo pigments. Series pigments, quinacridone series 9 ___ This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) ----------- ^ ------ -^ --------- (Please read the notes on the back before filling out this page) 588095 A7 ___B7__ V. Description of the invention (?) Pigments, rest · 〇η1: 1ΐΓ & ςΗηοη6) Series pigments, two Organic pigments, such as sassafras pigments, museum blue pigments, thioindigo pigments, northern quinone pigments, perylene pigments, indoloquinone pigments, azomethine pigments, and fluorescent Pigments, colored resin emulsions, etc. These materials can be used as pigment dispersions. In the present invention, one kind or at least two kinds of pigments can be mixed and used. In addition, bright pigments such as the large particle size aluminum powder pigments and pearl pigments of the present invention can be used in combination. It is also possible to mix the hiding properties of various inorganic or organic white pigments such as hiding titanium oxide, alkylene melamine derivatives, plastic pigments (synthetic resin particle pigments) in various shapes such as spherical and flat shapes. pigment. Alternatively, an aluminum powder pigment and a metal-coated inorganic pigment may be used simultaneously. The water-based ink composition of the present invention may not contain a colorant. The water-based ink composition containing no colorant and containing aluminum powder pigments can also give a highly shiny handwriting. However, the above-mentioned aqueous ink composition containing a colorant is particularly desirable because it can impart a high degree of luster to the handwriting according to the color tone of the colorant or the like. The colorant is preferably contained in an amount of 0.05 to 15% by weight in the entire ink composition. If the colorant is less than 0.05% by weight in the total amount of the ink composition, it is difficult to visually recognize the coloring of the colorant. If the colorant exceeds 15% by weight in the total amount of the ink composition, the viscosity as an ink will be excessively increased 'and the fluidity will be lowered. Although the optimum blending amount of the colorant varies slightly depending on the type of the colorant, it is generally 1 to 10% by weight. (Synthetic resin emulsion) As described above, in order to obtain handwriting with a high degree of gloss, the present inventor used 10 national paper (CNS) A4 specifications (210 X 297 public love —) a week '" " ----- Order --------- (Please read the notes on the back before filling out this page) 588095 A7 __B7_ ___ V. Description of the Invention (f), it is found that In the water-soluble organic resin and the ink composition with water, a large-particle-size aluminum powder pigment obtained by powder treatment using oleic acid or stearic acid as a pulverization aid is suitably used. Compared with the small-particle size aluminum powder pigments and pearl pigments obtained by using other fatty acids or inorganic acids as the pulverization treatment in the past, if the large-particle size aluminum powder pigments are used, the handwriting can be given a higher degree of brightness. . However, in the case of a bright water-based ink composition containing a water-soluble resin, especially a water-soluble thickening resin, the water-soluble thickening resin can improve the fixing property of the large-particle-size aluminum powder pigment described above to To some extent, it was found that the shape of the large-particle-size aluminum powder pigment is too large, so it is difficult to strongly fix the large-particle-size aluminum powder pigment to the substrate with a water-soluble thickening resin. Therefore, for an aqueous ink composition containing the large-size aluminum powder pigment described above, after writing, the large-size aluminum powder pigment described above is easily peeled off due to friction and the like, so it is difficult to continuously impart a high gloss to handwriting. , The durability of the bright handwriting or coating film is low. Due to the foregoing, it is possible to provide an effect that does not degrade ink characteristics or writing performance, and does not hinder a high-brightness effect by adding the large-size aluminum powder pigment described above, and can improve the performance of the large-size aluminum powder pigment on the substrate. A water-based ink composition capable of continuously imparting a higher degree of gloss to handwriting, particularly a bright water-based ink composition for ball pens in writing instruments, is an important subject of the present invention. In order to achieve the above-mentioned problem, as a result of diligent research, it was found that if it contains a large particle size aluminum powder pigment, water-soluble resin, water-soluble organic solvent, and water as essential components, and further contains the above-mentioned large particle size aluminum powder Yan 11 This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 public love) ----- C Please read the notes on the back before filling this page) Μ * · I · 111111 I — — — — — — —. 588095 A7 _ B7 V. Description of the invention (1) The binder component is strongly fixed on the substrate such as writing paper and other substrates, such as paper, etc. The bright water-based ink composition (fixed resin component) can solve the above-mentioned problems. On the other hand, in order to strongly fix such a large-particle-size aluminum powder pigment to a substrate such as an object to be coated, an object to be copied, etc., it is considered to use a water-soluble synthetic resin as a binder component. However, in order to strongly fix a large particle size aluminum powder pigment, increasing the content depending on the type of water-soluble synthetic resin used may adversely affect the solubility of the thickening resin and the dispersibility of the colorant. In addition, the viscoelasticity of the ink may be greatly reduced, resulting in a decrease in writing performance. In addition, even if the adhesiveness to the substrate of the object to be coated, the object to be copied, etc. can be exerted, it is still necessary to avoid the water-based ink composition in which the local lightness of the large particle size aluminum powder pigment described above is reduced in the handwriting. . As a result of further research, the inventors have found that if a synthetic resin emulsion is used as a binder component for fixing the above-mentioned large-particle-size aluminum powder pigment to a substrate such as a coated object or a copied object, it will not only be lost. Brightness can also improve the fixation of the above-mentioned large particle size aluminum powder pigments to substrates such as writing paper and the like, and complete the present invention. Therefore, 'when writing or coating or copying the aqueous ink composition of the present invention containing the large particle size aluminum powder pigment described above on a substrate such as paper, metal, plastic, fiber products, etc. It can improve the fixation of the large particle size aluminum powder pigment on the substrate of the object to be coated, the object to be copied, etc., and make it a durable handwriting, and it can continue to give a higher height to the handwriting. The sense of brightness. This is because the film-forming properties of synthetic resin emulsions are suitable for large-scale aluminum powder pigments with a large scale shape. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm)- ------------------ ^ --------- (Please read the notes on the back before filling out this page) 588095 A7 ______— _B7 _ V. Invention Explanation (ί.) It hinders the effect of high brightness caused by the combination of the large particle size aluminum powder pigments mentioned above, and it can be firmly fixed to the substrate such as the coated object and the copied object. In addition, since the binder component (fixing resin component) of the present invention is not a water-soluble synthetic resin but a synthetic resin emulsion, the solubility of the water-soluble thickening resin, the dispersibility of the colorant, and The ink's viscoelasticity and other characteristics will cause adverse effects. Therefore, the ink composition of the present invention does not affect the viscosity of the ink, the writing performance, and the color of handwriting, and can improve the fixation of the large-particle-size aluminum powder pigment described above. From the above results, it can be seen that the bright water-based ink composition containing the above-mentioned large-particle-size aluminum powder pigment of the present invention does not reduce ink characteristics and writing performance, and does not hinder the high surface smoothness of glass. The water-based ink composition of bright pigments such as aluminum powder pigments and pearl pigments can continuously give the handwriting a higher degree of brightness. The synthetic resin emulsion of the present invention is not particularly limited, and it can be used as long as it is a water-dispersible synthetic resin emulsion. However, when considering ink characteristics and writing performance, it is important to use inks that do not affect the solubility of the water-soluble thickening resin or the viscosity of the ink, the dispersibility of the colorant, and the color development of the ink. In addition, it is important not to hinder the high-gloss effect caused by the mixing of the large particle size aluminum powder pigments mentioned above. The minimum film-forming temperature of the synthetic resin emulsion is preferably 20 ° C or lower. If the minimum film-forming temperature of the synthetic resin emulsion is 20 ° C or less, especially 0t: When it is below, it can be filmed not only at normal temperature (25 ° C), even in cold areas, but also improve the handwriting of the substrate. Of the fixation. 13 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ^ -------- ^ --------- (Please read the precautions on the back before filling in this Page) 588095 A7 _______B7 5. Description of the invention (U) In addition, synthetic resin emulsions can also suitably use anionic or nonionic substances. An anionic or non-ionic synthetic resin emulsion can be made, for example, from an anionic or non-ionic monomer, or can be obtained by using an anionic or non-ionic emulsifier. If the synthetic resin emulsion is anionic or nonionic, the stability of the ink composition can be improved. Further, it is preferable that the synthetic resin emulsion does not affect the dispersibility of the colorant or the solubility of the water-soluble thickening resin when the pH of the ink is 6 or more. From this viewpoint, as the synthetic resin emulsion, for example, an acrylic synthetic resin emulsion, a styrene-acrylic synthetic resin emulsion, or an ethyl acetate synthetic resin emulsion can be used. As the acrylic synthetic resin emulsion, for example, an acrylate copolymer synthetic resin emulsion is preferred. As the styrene-acrylic synthetic resin emulsion, for example, a styrene-acrylate copolymer synthetic resin emulsion is preferred. As for the vinyl acetate-based synthetic resin emulsion, for example, a vinyl acetate synthetic resin emulsion and a vinyl acetate-acrylate copolymer synthetic resin emulsion can be suitably used. The synthetic resin emulsion can be used singly or as a mixture of at least two of them. Specifically, examples of the acrylic synthetic resin emulsion include, for example, the trade name "Nicassolo FX336" (manufactured by Carbide Industries, Ltd., minimum film forming temperature < 0 ° C, pH 7.5, 200 mPa). · S), trade name "Nicassolu A-02" (manufactured by Japan's calcium carbide industry, minimum film formation temperature < 0 ° C, pH 7.0, 500mPa · s), trade name "Nicassour FH —011A ”(manufactured by Japan Carbide Industry Co., Ltd., minimum film formation temperature < 0 ° C, pH 7.0, 150mPa · s), 14 paper sizes are applicable to China National Standard (CNS) A4 (210 X 297) Li) -------- ^ --------- (Please read the notes on the back before filling this page) 588095 A7 __B7 V. Description of the invention (, >) Synthesized as vinyl acetate Resin emulsions include, for example, the trade name "Mobiniru 231" (manufactured by Clarion Polymer Co., Ltd., minimum film forming temperature < 0 ° C, pH 4.0, viscosity 500 to 1500 mPa · S), etc. . In addition, this viscosity is measured using a type B viscometer at 25 ° C. The content of the synthetic resin emulsion is not particularly limited, and for example, a solid content of 0.1 to 40% by weight relative to the total amount of the ink composition is a suitable range. If the content of the synthetic resin emulsion is less than 0.1% by weight relative to the total amount of the ink composition, the fixability of the aluminum powder pigment having a large particle size on the substrate will be reduced. On the other hand, if the content of the synthetic resin emulsion is more than 40% by weight relative to the total amount of the ink composition, the solid content will increase, and the coating film at the pen tip will reduce writing performance. In addition, handwriting is easily whitened. In order to improve the fixation of the aluminum powder pigment having a large particle diameter on the substrate, the content of the synthetic resin emulsion is preferably at least 0.3% by weight based on the solid content of the entire ink composition. In order to further improve writing performance, the content of the synthetic resin emulsion is preferably 20% by weight based on the solid content relative to the total amount of the ink composition. That is, the optimum content of the synthetic resin emulsion is 0.3 to 20% by weight. From the above, it can be seen that, as the bright water-based ink composition related to the embodiment of the present invention, the best is the one described in the patent application scope 1, which contains the following components a to e and the viscosity is 1.00 with respect to the total amount of the ink. 〇 ~ 10,000mPa · s (ELD type viscometer: 3. R14 cone, 0.5rpm, 20 ° C) bright aqueous ink composition. a · Using oleic acid or stearic acid as a pulverizing aid for powder treatment to obtain an aluminum powder pigment with a particle size of 15 // m or more 0.01 to 20% by weight, 15 This paper is applicable to Chinese national standards (CNS ) A4 specification (210 X 297 mm) * > I — I— ·-I ----- · 111111 II (Please read the notes on the back before filling out this page) 588095 A7 ___B7 5. Description of the invention (〇 ) b. selected from acrylic synthetic resin emulsion, styrene-acrylic synthetic resin emulsion, and vinyl acetate synthetic resin emulsion, synthetic resin emulsion 0.1 to 40% by weight (solid content), c. selected from Welan gum, Polysaccharides of succindextran and gum lam, 0.01 to 40% by weight, d. Water-soluble organic solvents 1 to 40% by weight, e. Color pigments 0.05 to 15% by weight (other additives), In the present invention, according to other needs, lubricants such as polyethylene oxide alkali metal salts, diammonium dicarboxylate, phosphate, N-olenyl sarcosinate, benzotriazole, and toluene may be added. Based rust inhibitors such as triazocene dicyclohexyl ammonium nitrate, benzoisothiazoline, pentachlorophenol, Etc. preservative antifungal agent, and relative to mind various large particle aluminum pigments of the active agent surface. In addition, the optimum viscosity range of the ink composition of the present invention is from 1,000 to 10,000 mPa · s. The ink composition of the present invention is adjusted to such a viscosity range. In addition, this viscosity is measured by ELD viscometer (3 ° R14 cone, OApm, 20 ° C). (Ink production method) Although a conventionally well-known dispersion method, defoaming method, economical method, and the like can be used to make the ink, the following method is preferably used as the input method. That is, after dispersing water, a water-soluble organic solvent, an acoustic aluminum powder pigment, and a colorant in a greenhouse by dissolving, etc., a water-soluble resin and a fixing tree are added, and various additives are added and adjusted as necessary. pH 値, then by 16 (Please read the precautions on the back before filling this page) — I ---- Order --------- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 588095 A7 B7 V. Description of the invention (hum) After filtering the mixed solution by pressure filtration, etc., and then defoaming, a bright ink composition can be obtained. Examples According to the composition and blending amount (% by weight) shown in Table 1, according to the manufacturing method described above, each of the mixed and stirred water, a water-soluble organic solvent, a predetermined large particle size aluminum powder pigment, and a coloring agent or a pigment base agent is mixed. After dispersing the components, a water-soluble resin is added, and after filtering, the foam is defoamed to obtain the bright aqueous ink composition of the example. As shown in Table 2, for comparison, after mixing and stirring the components such as water, water-soluble organic solvents, aluminum powder pigments and pearl pigments of small particle size, dispersing them, adding water-soluble resins, filtering them to defoam, A water-based ink composition of a comparative example was obtained. Regardless of the examples and comparative examples, the dispersion method, the defoaming method, and the filtration method are all known in the past. Table 1 (% by weight) Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 I 4.0 4.0 4.0 4.0 Π 4.0 4.0 4.0 4.0 Aluminum powder pigment m 4.0 4.0 4.0 4.0 IV V 4.0 4.0 4.0 Pearl pigment water solubility Resin I 0.3 0.3 0.3 0.3 0.4 0.4 0.4 17 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ^ -------- ^ --------- (Please Read the precautions on the back before filling this page) 588095 A7B7 V. Description of the invention (6) Π 0.4 0.4 0.4 0.4 Melon 0.3 0.3 0.3 0.3 IV 3.0 3.0 3.0 Fixing resin I 15 15 15 15 15 15 15 15 15 Π 12 12 12 Water-soluble organic solvent I 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 Π 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 Colorant I 2.0 2.0 2.0 2.0 2.0 Π 0.8 0.8 0.8 0.8 0.8 Anticorrosive and mold inhibitor 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Antirust agent 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Lubricant 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Bright pigment dispersant 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Water 56.4 54.4 55.6 54.3 55.5 56.3 55.6 56.4 54.4 56.4 54.3 55.6 71.3 69.3 70.5 Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Brightness 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 I Π Aluminum powder pigment m IV 4.0 4.0 4.0 4.0 V 8.0 8.0 8.0 4.0 18 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------- ^- ------- (Please read the notes on the back before filling this page) 588095 A7 B7 V. Description of the invention (^)
珍珠顏料 8.0 8.0 8.0 8.0 水溶性樹脂 I 0.3 0.3 0.3 0.4 0.4 0.5 Π 0.4 0.4 0.4 m 0.3 0.3 0.3 IV 3.0 固著樹脂 I 15 15 15 15 15 15 π 15 15 12 水溶性有機 溶劑 I 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 π 15 15 15 15 15 15 15 15 15 15 15 15 著色劑 I 2.0 2.0 2.0 2.0 π 0.8 0.8 0.8 0.8 防腐防黴劑 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 防銹劑 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 潤滑劑 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0·1 亮性顏料分散劑 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 水 56.4 54.3 55.6 52.4 50.3 51.6 52.4 50.3 51.6 71.3 69.3 66.4 合計 100 100 100 100 100 100 100 100 100 100 100 100 光亮感 X X X X X X X X X X X X 裝--------訂---------. (請先閱讀背面之注意事項再填寫本頁) 在表中之各原料的組成係如下所述。 (鋁粉顏料） I :油酸處理鋁粉顏料、商品名「WXM5422」，東洋 隹呂業股份有限公司製造，中値粒徑19/zm Π :油酸處理鋁粉顏料、商品名「WXM1440」，東洋 鋁業股份有限公司製造，中値粒徑30#m 瓜··油酸處理鋁粉顏料、商品名「WXM1415」，東洋 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 588095 A7 ________B7___ 五、發明說明（1) 鋁業股份有限公司製造，中値粒徑51/zm IV :硬脂酸處理鋁粉顏料、商品名「WXM0630」，東 洋鋁業股份有限公司製造，中値粒徑7/zm V :硬脂酸處理鋁粉顏料、商品名「1110W」，昭和 鋁業股份有限公司製造，中値粒徑15/zm (珍珠顏料） 商品名「Iriodin32」，美魯克日本股份有限公司製造 ，粒徑約爲5〜20 # m (水溶性樹脂） I :韋蘭樹膠、商品名「K1C376」，三晶股份有限公 司製造 Π :琥珀葡聚糖、商品名「雷歐杉」，三晶股份有限 公司製造 m :拉母山膠、商品名「K7C233」，三晶股份有限公 司製造 IV :胺中和型醇酸樹脂、商品名「Watersol S-311」 ，大日本墨水化學工業公司製造 (水溶性有機溶劑） I :甘油 Π :丙二醇 (固著樹脂） I :丙烯酸系合成樹脂乳液（商品名「尼卡索魯FH — 011A」（日本電石工業股份有限公司製、最低成膜溫度< 〇°C、pH 7.0、150mPa · s (在25°C的B型黏度計測定値） 20 本紙張尺度適用中國國家標準（CNS)A4規格（21Q X 297公爱) " -- --------訂·-------1 (請先閱讀背面之注意事項再填寫本頁) 588095 A7 __B7 五、發明說明（β ) )) Π :丙烯酸系合成樹脂乳液（商品名「尼卡索魯 FX336」（日本電石工業股份有限公司製、最低成膜溫度 <.0°C、pH 7·5、200mPa · s (在25°C的B型黏度計測定値 ))) (著色劑） I:藍色顏料基劑 藍色顏料基劑的顏料分散体，爲將下述藍色顏料和下 述顏料分散用樹脂以下列的比例混合，再加入三乙胺並使 其溶解，然後於球磨機進行分散，所獲得之平均粒徑〇·〇8 μ m、固形分濃度10重量％之顏料水分散體。又，作爲藍 色顏料係使用銅tt菁藍（商品名「第一更布魯TGR」，大 曰本墨水化學工業公司製造），而作爲顏料分散用樹脂係 使用苯乙烯一丙烯酸共聚物（商品名「強克里魯J683」， 強森聚合物公司製造，重量平均分子量：8000)。 銅菁藍 5重量份 顏料分散用樹脂 1重量份 Π ··紅色染料（酸性紅色289、商品名「Chugai Aminol Pink R」、中外化成股份有限公司製造） (防腐防黴劑） 1，2—苯并異噻唑咐—3-酮（商品名「普洛克塞爾 GXL」，赫希斯特合成股份有限公司製造） (防銹劑） 苯并三唑 21 本紙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 —0 ^---- -項再填寫本頁) I M ϋ n —^1 一 _ n I ϋ— ·ϋ ϋ Hi i^i I · 588095 A7 ___B7 五、發明說明（1) (潤滑劑） POE烷基醚磷酸酯（磷酸酯系活性劑、商品名「佛斯 法羅魯PE-510」，東邦化學工業公司製造） (鋁粉顏料等之亮性顏料分散劑） POE壬基苯基醚（非離子系表面活性劑、HLB : 13.2 、商品名「黑麻魯更PI — 20T」，花王公司製造） (試驗樣品之製作） 其次，將示於表中的實施例及比較例之各墨水組成物 ，塡充於在一端連接設置有不銹鋼製的原子筆尖（筆珠材 質；碳化矽）之聚丙烯製的中空軸筒所構成之墨水收容部 中，製成裝塡此墨水收容部之各試驗樣品的原子筆。 (評價試驗） 使用這些原子筆於市售之活頁用紙上書寫，然後分別 就表1的實施例及比較例之各墨水組成物的光亮感進行評 價。 光亮感係以目視觀察書寫狀態來進行，而將光亮感強 者評價爲〇，光亮感低或無光亮感者評價爲X。 由表可知，實施例1、6、8、10及13皆得到展現出如 寶石的鑽石般印象之亮性的筆跡。實施例2、4、9、11及 14皆得到展現出如寶石的海藍寶石般印象之亮性的筆跡。 實施例3、5、7、12及15皆得到展現出如寶石的粉紅珍珠 般印象之亮性的筆跡。相對於此，比較例皆變成白色度強 之筆跡，且不顯現出亮性。特別是將實施例的墨水組成物 與含珍珠顏料之比較例7、10、11及12相比較，實施例的 22 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） f > I i -----------------I I ^ --------I (請先閱讀背面之注意事項再填寫本頁) 588095 A7 _____ B7____ 五、發明說明) 墨水組成物無論是否含有固著樹脂，皆可得到散佈著閃爍 強而亮之光亮點的筆跡。 此外，雖上記實施例皆爲適用作爲原子筆用墨水組成 物者，但是若其爲含有以油酸或硬脂酸作爲粉碎助劑來進 行粉粹處理而得之中値粒徑15/zm以上的鋁粉顏料之本發 明的亮性墨水組成物，則其亦可使用於其他的書寫用具上 。又，若爲含有以油酸或硬脂酸作爲粉碎助劑來進行粉碎 處理而得之中値粒徑15//m以上的鋁粉顏料之本發明的亮 性墨水組成物，其亦可使用於有關臉部美容品、手指甲油 、腳指甲油、指甲磨光劑、染睫毛油、眼線膏、眼影、口 紅、粉底等的化粧品、毛髮化粧品等各種用途之化粧品領 域等。 因本發明係至少含有以油酸或硬脂酸作爲粉碎助劑來 進行粉粹處理而得之中値粒徑15/zm以上、最好是30〜60 //m的鋁粉顏料、與水溶性樹脂、水溶性有機溶劑以及水 之亮性水性墨水組成物，故與使用以往亮性顏料之水性墨 水組成物相比較，能獲得過去未有、具更高度光亮感之獨 特的筆跡。特別是在同時含有鋁粉顏料與著色劑之上記亮 性水性墨水組成物的情況下，能賦予對應於該著色劑色調 等之高度光亮感於筆跡上。 23 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） #1 W· -------------------^--------- (請先閱讀背面之注意事項再填寫本頁)Pearl pigment 8.0 8.0 8.0 8.0 Water-soluble resin I 0.3 0.3 0.3 0.4 0.4 0.5 Π 0.4 0.4 0.4 m 0.3 0.3 0.3 IV 3.0 Fixing resin I 15 15 15 15 15 15 π 15 15 12 Water-soluble organic solvent I 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 π 15 15 15 15 15 15 15 15 15 15 15 15 15 Colorant I 2.0 2.0 2.0 2.0 π 0.8 0.8 0.8 0.8 Anti-corrosion and anti-mold agent 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Lubricant 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Bright pigment dispersant 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Water 56.4 54.3 55.6 52.4 50.3 51.6 52.4 50.3 51.6 71.3 69.3 66.4 Total 100 100 100 100 100 100 100 100 100 100 100 100 100 Brightness XXXXXXXXXXXX Installation -------- Order ---------. (Read the back first (Notes on this page, please fill out this page) The composition of each raw material in the table is as follows. (Aluminum powder pigment) I: Oleic acid-treated aluminum powder pigment, trade name "WXM5422", manufactured by Toyo Sumi Industry Co., Ltd., with a particle size of 19 / zm Π: oleic acid-treated aluminum powder pigment, trade name "WXM1440" , Manufactured by Toyo Aluminium Co., Ltd., with a particle size of 30 # m, melons, oleic acid-treated aluminum powder pigment, trade name "WXM1415", Toyo's paper size applies Chinese National Standard (CNS) A4 (210 X 297) (%) 588095 A7 ________B7___ V. Description of the invention (1) Manufactured by Aluminum Industry Co., Ltd., with a particle size of 51 / zm. IV: Stearic acid treated aluminum powder pigment, trade name "WXM0630", manufactured by Toyo Aluminum Co., Ltd., Medium particle size 7 / zm V: Stearic acid-treated aluminum powder pigment, trade name "1110W", manufactured by Showa Aluminum Co., Ltd. Medium particle size 15 / zm (pearl pigment), trade name "Iriodin32", Meru Manufactured by Gram Japan Co., Ltd., particle size is about 5 to 20 # m (water-soluble resin) I: Wellan gum, trade name "K1C376", manufactured by Sanjing Co., Ltd. Π: succindextran, trade name "Ray "Ocean", made by Sanjing Co., Ltd. m: ram rubber, trade name "K7C233", manufactured by Sanjing Co., Ltd. IV: amine neutralized alkyd resin, trade name "Watersol S-311", manufactured by Dainippon Ink Chemical Industry Co., Ltd. (water-soluble organic solvent ) I: Glycerin Π: Propylene Glycol (Fixed Resin) I: Acrylic Synthetic Resin Emulsion (trade name "Nicassol FH — 011A" (manufactured by Japan's calcium carbide industry, minimum film forming temperature < 〇 ° C, pH 7.0, 150mPa · s (determined by a B-type viscometer at 25 ° C) 20 This paper size applies to China National Standard (CNS) A4 (21Q X 297 public love) "--------- Order · ------- 1 (Please read the precautions on the back before filling in this page) 588095 A7 __B7 V. Description of the Invention (β))) Π: Acrylic synthetic resin emulsion (brand name "Nicassolu FX336 "(manufactured by Japan Carbide Industry Co., Ltd., minimum film formation temperature < .0 ° C, pH 7.5, 200mPa · s (measured at 25 ° C with a B-type viscometer))) (colorant) I: Blue pigment base The pigment dispersion of the blue pigment base is prepared by dispersing the following blue pigment and the following pigment dispersion resin The following proportions were mixed, triethylamine was added and dissolved, and then dispersed in a ball mill. The obtained pigment aqueous dispersion having an average particle diameter of 0.08 μm and a solid content concentration of 10% by weight was obtained. In addition, as the blue pigment system, copper tt cyanine blue (trade name “First Guru Blue TGR”, manufactured by Daiichi Ink Chemical Industry Co., Ltd.) was used, and as the pigment dispersion resin system, styrene-acrylic acid copolymer (commercial product The name is "Strong Creole J683", manufactured by Johnson Polymers, weight average molecular weight: 8000). 5 parts by weight of copper cyanine blue and 1 part by weight of a resin for pigment dispersion Π ·· red dye (acid red 289, trade name "Chugai Aminol Pink R", manufactured by Sinowai Chemical Co., Ltd.) (preservative and mildew inhibitor) 1, 2-benzene Benzisothiazol—3-ketone (brand name “Proxell GXL”, manufactured by Hearst Synthesis Co., Ltd.) (rust inhibitor) Benzotriazole 21 This paper is in accordance with China National Standard (CNS) A4 Specifications (210 x 297 mm) (Please read the notes on the back-0 ^ -----item before filling out this page) IM ϋ n — ^ 1 一 _ n I ϋ— · ϋ ϋ Hi i ^ i I · 588095 A7 ___B7 V. Description of the invention (1) (Lubricant) POE alkyl ether phosphate ester (phosphate ester active agent, trade name "Fos Farolu PE-510", manufactured by Toho Chemical Industry Co., Ltd.) (aluminum powder Bright pigment dispersant for pigments, etc.) POE nonylphenyl ether (nonionic surfactant, HLB: 13.2, trade name "Kuromaru PI-20T", manufactured by Kao Corporation) (production of test samples) Next Each of the ink compositions of the examples and comparative examples shown in the table was filled at one end. A ball-point pen containing each test sample in the ink receiving portion was formed in an ink containing portion made of a hollow shaft made of polypropylene, provided with a stainless steel ballpoint pen tip (pen bead material; silicon carbide). (Evaluation test) These ballpoint pens were used to write on a commercially available loose-leaf sheet, and then the brightness of each ink composition in the examples and comparative examples in Table 1 was evaluated. The glossiness was evaluated by visually observing the writing state, and those with strong glossiness were evaluated as 0, and those with low glossiness or no glossiness were evaluated as X. As can be seen from the table, Examples 1, 6, 8, 10, and 13 all obtained handwritings that exhibited the brightness of a diamond-like impression. Examples 2, 4, 9, 11, and 14 all obtained handwritings exhibiting the brightness of aquamarine-like impressions of gems. Examples 3, 5, 7, 12, and 15 all obtained handwritings showing the brightness of the impression like pink pearls of precious stones. On the other hand, the comparative examples were all handwritings with strong whiteness and did not show brightness. In particular, the ink composition of the example is compared with Comparative Examples 7, 10, 11, and 12 containing a pearl pigment. The paper size of Example 22 is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) f > I i ----------------- II ^ -------- I (Please read the notes on the back before filling this page) 588095 A7 _____ B7____ 5 (Explanation of the invention) Regardless of whether or not the ink composition contains a fixing resin, a handwriting strewn with bright and bright light spots can be obtained. In addition, although the examples described above are all suitable for use as ink compositions for ball pens, if they contain powders treated with oleic acid or stearic acid as a grinding aid, the median particle size is 15 / zm or more. The bright ink composition of the present invention, which is an aluminum powder pigment, can also be used in other writing instruments. In addition, if the bright ink composition of the present invention contains an aluminum powder pigment having an intermediate particle size of 15 // m or more obtained by pulverizing treatment using oleic acid or stearic acid as a pulverizing aid, it can also be used. In the field of cosmetics for various applications such as facial beauty products, hand nail polish, toenail polish, nail polish, mascara, eyeliner, eye shadow, lipstick, foundation, etc., and hair cosmetics. Since the present invention contains at least an aluminum powder pigment having a particle size of 15 / zm or more, preferably 30 to 60 // m, which is obtained by powder processing using oleic acid or stearic acid as a pulverization aid, and is soluble in water Compared with water-based ink compositions using conventional bright pigments, it is possible to obtain unique handwriting with a higher degree of gloss than conventional water-based organic inks and water-based bright ink compositions. In particular, when a bright water-based ink composition containing both an aluminum powder pigment and a coloring agent is contained, it is possible to impart a high degree of gloss to the handwriting corresponding to the hue of the colorant. 23 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) # 1 W · ------------------- ^ ------ --- (Please read the notes on the back before filling this page)