201125938 printing ink for a decorative can, a 3 piece beverage can, a dietary can and the like, and a printed metal plate using the same. The ink composition for metal printing comprises a pigment, an alkyd resin and a hydrocarbon based solvent, wherein a part or all of polyhydric alcohol constituting the alkyd resin is tris(2-hydroxyethyl) isocyanurate, and the printed metal plate is produced using the ink compositions for metal printing. 四、指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明：無。 無。 五、本案若有化科時’請細最能齡發雜_化學式： 六、發明說明： 【發明所屬之技術領域】The ink composition for metal printing includes a pigment, an alkyd resin and a hydrocarbon based solvent, a part or all of polyhydric alcohol constituting the alkyd resin is tris(2-hydroxyethyl) isocyanurate, and the printed metal plate is produced using the ink compositions for metal printing. 4. The designated representative map: (1) The representative representative map of the case is: no. (2) A brief description of the symbol of the representative figure: None. no. 5. If there is a chemical science in this case, please ask the finest age to be mixed. Chemical formula: 6. Invention description: [Technical field of invention]
本發明係關於“一… 用的印刷墨水中， 性的金屬印刷墨水 板0 2 201125938 【先前技術】 目前，金屬印刷大致分成2方式為將金屬加工為圓筒 型後，以凸版膠印（relief 0ffset)方式進行印刷的方法同 以及於片狀金屬板以平版膠印方式進行印刷之後加工為圓 筒狀的方法，美術罐、3件式飲料罐、食品罐等主要是 以平版膠印方式進行印刷。以平版膠印方式所印刷的金= 印刷墨水的硬化方法，雖有利用紫外線照射而硬化與利用 加熱而氧化聚合硬化，但於要求高加工性的用途中:、多數 使用利用乾性油及乾性油脂肪酸而改質的醇酸樹脂的氧化 聚合使其加熱硬化的方法。 此外，已知金屬印刷墨水的加工性，根據醇酸樹脂所 利用的植物油脂肪酸的含量而變化（專利文獻丨）。一般而 言，使用植物油脂肪酸含量大的醇酸樹脂的墨水的加工性 差，使用使用植物油脂肪酸含量小的醇酸樹脂的墨水的加 工性良好。因A ’高加工性型的墨水中，由於使用植物油 脂肪酸含小的醇酸樹脂，樹脂的溶解性或轉移性、機上安 定性之印刷適性，盘倍用始从jα /、便用植物油知肪酸含量大的醇酸樹脂 的墨水相比較為變差。 再者#單位為結合至樣品1Q〇克的埃克數）大的 醇酸樹脂，交聯點間距離變短的樹脂的網眼構造細而成為 缺乏柔权]· 3 t面，碘價小的醇酸樹脂，交聯點間距 離變長的樹脂的網眼構造粗而使柔軟性增加'然而，使用 該等醇k樹I的金屬印刷墨水的加工性，反應於醇酸樹脂 的柔軟性。 201125938 因此，金屬墨水製造商，於加工性非必要的 準備重視印刷適性的—般型，而於加工性為必 中’準備高加工性型的2種類的墨水。然❿，近年^ 為由製罐製造商與金屬印刷製造商人 ’乍 衣以陶σ理化的一環，對於金 屬墨水製造商，期望高加工性血g卩舢唬α 改與印刷適性兩者兼具的 用金屬印刷墨水的開發。 再者，金屬印刷的光澤，影響印刷墨水的塗膜表面的 光滑，亦即影響調平性。截至目前的光澤，無法稱為不充 分但尚有改善的餘地。 【專利文獻1】日本特開第2004-285303號公報 【專利文獻2】日本特開第2〇〇1_31889號公報 【發明内容】 發明欲解決之課題 本發明係為解決上述問題者，其目的係提供具有高光 澤及尚加工性，且印刷適性優異的金屬印刷墨水組成物， 以及使用該組成物所印刷的印刷金屬板。 解決課題之手段 本發明者們，反復致力研究的結果發現，藉由採用以 下的構成’達成上述目的，本發明遂而完成。 亦即本發明係關於一種金屬印刷墨水組成物，在含有 顏料、醇酸樹脂及烴系溶劑的金屬印刷墨水組成物中，構 成醇酸樹脂的植物油脂肪酸的比例為3 5至6 5質量％，且多 元醇成分的15至100莫耳％為三（2-羥基乙基）三聚異氰酸 201125938 酯（THEIC)。 本發明中，醇酸樹脂的碘價較佳為55至】⑽。 再者，本發明亦關於在金屬板上，或金屬板上設置有 底塗層的金屬底板上’具有使用本發明的金屬印刷墨水級 成物所形成的墨水層的印刷金屬板。 發明的效果 根據本發明的墨水組成物，印刷適性優異，且可對於 所印刷的金屬板賦予其来、、要；5古4 萄攸叭卞冋九澤及冋加工性。特別有用於美術 罐、3件式飲料罐、食品罐的印刷墨水。 【實施方式】 以下’更詳細說明本發明的金屬印刷墨水組成物所使 用的各成分。 (醇酸樹脂） 本金明的金屬印刷墨水組成物所使用的醇酸樹脂是以 多元酸（P〇iybasic acid)，與一部分或全部為三（2_經基乙 基)三聚異氰酸酉旨的多元醇的縮合物作為骨架，為經以油或 月曰肪S夂改質的树脂’其製造方法並無特別限制，可利用油 作為原料的S旨交換法、脂肪酸作為原料的脂肪酸法等習知 的方法。 本發明中，構成醇酸樹脂的多元醇成分中所使用的三 (2-羥基乙基）三聚異氰酸酯，具有羥基存在於對稱的三個 方向的,、員構造。多兀酸與三(2_羥基乙基)三聚異氰酸酯 的縮〇物作為月架，經由樹脂的網眼構造的交聯點間距離 201125938 變長而增加自由度，表現柔軟性可實現加工性的提升。士 此-來，經由使用三(2-經基乙基)三聚異氰酸醋可實現: 工性的提升，比至今於具有加工性的墨水中所使用的醇酸 樹脂’可使用植物油脂肪酸含量大的醇酸樹脂，印 改善。 再者，以使用三（2-經基乙基）三聚異氰酸醋的醇酸樹 脂所構成的金屬印刷墨水組成物，高溫時的流動性良好， 塗布後加熱乾燥時的塗膜表面變光滑可得高光澤。 本發明中，構成醇酸樹脂的多元醇成分的15至1〇〇莫 耳％為三（2-羥基乙基）三聚異氰酸醋。未達15%時難以取得 印刷適性與加工性的平衡，再者，無法獲得高光澤。 作為三（2-羥基乙基）三聚異氰酸酯以外的多元醇成 分，可使用乙二醇、丙二醇、L3-丁二醇、匕心丁二醇、 1,5-戊二醇、1，6-己二醇、1，9-壬二醇、2-曱基_1>8_辛二 醇、新戊二醇、二乙二醇、三乙二醇、二丙二醇、三丙二 醇、伸丁 一醇、1，4-環己二醇、1，4-環己二甲醇、氫化雙 酚A、2-丁基-2-乙基-1，3-丙二醇等二元醇；甘油、三羥 曱基丙院、二經甲基乙烧等三元醇；季戍四醇、二甘油、 二-二羥甲基丙烷、二-三羥甲基乙烷等四元醇等，以往醇 酸樹脂所使用的多元醇，並無特別限定。該等可單獨使用 或2種以上併用。 本發明中所使用醇酸樹脂的其他成分的植物油脂肪酸 成分，可列舉亞麻仁油、桐油、脫水蓖麻子油、大豆油、 紅花油、亞麻仁油脂肪酸、桐油脂肪酸、脫水蓖麻子油脂 201125938 肪駄、大且油脂肪酸、紅花油脂肪酸等，或油酸、亞麻油 酸、亞麻仁油、油硬脂酸或蓖麻油酸等不飽和脂肪酸類。 該等可單獨或2種以上併用。考慮價格或塗膜物性，以亞 麻仁油、亞麻仁油酸為較佳。 再者，該等植物油或脂肪酸的一部分亦可變更為脂肪 酉欠以外的一元酸。其他的一元酸，可使用安息香酸、對— 第一丁基女息香酸、松脂酸、氫化松脂酸等。 再者作為多元酸，可列舉苯二甲酸（酐）、 ㈣、對笨二甲酸、2,一酸、間苯二甲酸 等方香族二元酸；四氫笨二甲酸（酐）、六氫笨二曱酸（酐）、 1，4-¾己烷二羧酸等脂環族二元酸；琥珀酸（酐）、烯基琥 拍酸(酐)、富馬酸、馬來酸酐、衣康酸、己二酸、癸二：、 :二酸、海米克酸（hinnc acid)(酐）等脂肪酸二元酸；偏 苯三甲酸(酐)、均苯四甲酸(酐)、甲基環己烷三羧酸(酐）、 二苯基酮四㈣等。該等多元酸可單獨或2種以上併用。 本發明金屬印刷墨水組成物所使用的醇酸樹脂的植物 油脂肪酸的含量為35至65質《。於未達35質量％，作為 多元醇的成分使用三（2-經基乙基）三聚異氰酸酿15至1〇〇 莫耳㈣’墨水的流動性降低’超過65質量%時，加工性或 塗膜硬度差。考慮墨水的流動性、 τ _ , 加工性以及塗膜硬度的 平衡時’再較佳為45至60質量％。 再者’醇酸樹脂的碘價較佳為55 ?丨+ ^ , 勹至13〇。未達55時， 塗膜硬度差，而超過130時，加工性右 性有降低的傾向。考慮 塗膜硬度與加工性的平衡，再較佳為β5至lb。 201125938 進一步地，可將以往所使用的樹脂與本發明的醇酸樹 脂混合使用。換言之，根據印刷適性、塗膜物性等的要求 性能，可將醇酸樹脂與單獨或複數種相容的習知樹脂混合 而使用。具體而言，例如可例示松香改質苯酚樹脂、聚酯 樹脂、石油樹脂、環氧樹脂、酮樹脂、松香改質馬來酸樹 月曰、胺基樹脂、苯胍胺樹脂等。 氧化聚合硬化型印刷墨水中，根據需要，可添加為了 使墨水硬化作為硬化促進劑的印刷墨水用乾燥劑，本發明 中亦可添加印刷墨水用乾燥劑。本發明中可使用的印刷墨 水用乾燥劑，可列舉m鐵、辞等金屬，與辛酸、 環烷酸（naphthenic acid)、新癸酸、桐油脂肪酸、亞麻仁 油脂肪酸、大豆油脂肪酸、樹脂酸等羧酸的鹽，亦即金屬 息。該等可單獨或2種以上組合使用。 (顏料） 本發明中所使用之顏料，可單獨或複數種混合使用印 刷墨水習知的無機或有機顏料而並無特別限制。具體而 言’例如可列舉專利文獻2等所揭示之顏料。 (烴系溶劑） 本發明的墨水組成物中所使用作為金屬印刷墨水用溶 劑的烴系溶劑，可使用沸點範圍為2〇〇至4〇〇。〇左右的一 般作為金屬印刷墨水用所使用的烴系溶劑，並無特別限制。 ^作為烴系溶劑，適宜使用一般的石油系溶劑或烷基笨 系溶劑。作為石油系溶劑，可例示新日本石油公司的AF5、 6、7號溶劑等，烷基苯系溶劑，可例示新曰本石油化學公 8 201125938 BAB等，可 司的阿爾肯（音譯）56N、L、200P或UIC公司的 單獨或複數種混合使用。 刷墨水的TAC 制0 烴系溶劑的使用量，只要可將進行一般印 值可調整為5至4G的㈣即可，並無特別限 (其他成分） 本發明的墨水組成物中，作為其他成分，根據需要可 添加習知的顏料分散劑、蠟、安定劑、酸觸媒等。 再者於不知及本發明目的之範圍，亦可於墨水中添 加微粉末氧化石夕、有機膨潤土等作為助劑，此外，作為印 刷墨水清漆成分，亦可能使用經由使用金屬螯合物或山梨 糖醇等之膠狀清漆。 本發明之金屬印刷墨水組成物，可使用親磨機、球磨 機、珠粒磨機等’經由常法調製。 作為印刷本發明的墨水組成物的金屬板，雖適宜為不 鏽鋼、銘、鑛錫鋼板、無錫鋼板等金屬板，或者於該等金 屬板上設有底塗（底漆）層的金屬底板，但不限定為該等 者。底塗層的形成，例如可使用金屬印刷中一般所使用的 彩印（slze)塗料或白塗覆等基底塗覆用組成物。再者，PET 曝經層合處理者亦無礙。 、於該等金屬板印刷本發明的金屬印刷墨水組成物的方 法’可經由利用濕水的膠印方式、乾膠印方式等一般的印 刷方式而容易地印刷。墨水膜厚雖可為任意者，例如以成 為於〇·1至6/zm的範圍進行。 本發明的金屬印刷墨水組成物的硬化，可使用—般金 9 201125938 屬印刷所使用的烘箱，加熱溫度通常可於120至230°C的 範圍進行。加熱時間只要為3小時以上之任一者即可，通 常於3至30分鐘之間的範圍進行。 由此所得之本發明的印刷金屬板，雖不一定需要套印 (overprint)用的清漆塗裝’但經由使用套印用清漆，可獲 得更良好的塗膜物性。 本發明的印刷金屬板的金屬印刷墨水上塗裝套印用清 漆時’通常使本發明的金屬印刷墨水組成物加熱硬化後進 行為較佳，也可以濕碰濕（wet 〇n wet)方式重疊塗裝後， 同時地使兩者加熱硬化。 本發明的金屬印刷墨水組成物，由於具有優異的印刷 適性’可於金屬板上形成高光澤 '高加工性的墨水塗膜， 可較宜使用作為片狀用金屬印刷墨水。 【實施例】 以下’雖以合成例、實施例為基礎說明本發明，但本 發明不僅限定為該等實施例。又，各例中的份數及％是以質 量為基準者。 合成例1 於具備攪拌機、水分離器、冷凝器、氮導入管、溫度 計的反應裝置中，加入亞麻仁油脂肪酸45份、笨二甲酸野 25. 4份、THE 1C 26· 3份、甘油9. 3份，於氮氣存在下一邊 回流二甲苯，一邊於22 0至23(TC反應至酸價為1〇以下後， 蒸餾分離二甲笨而獲得液狀的樹脂（1)。又，脫水量為6. 〇 份。再者’樹脂（1)的碘價為86(碘價的測定，係根據 10 201125938 JISK0070進行。以下相同）。 合成例2 與合成例1同樣的反應裝置中’加入亞麻仁油脂肪酸 50份、苯二甲酸酐20. 9份、THEIC23. 〇份、三羥曱基丙烧 11.8份，於氮氣存在下一邊回流二甲笨，一邊於220至230 °C反應至酸價為1 〇以下後，蒸餾分離二曱苯而獲得液狀的 樹脂（2 )。又，脫水量為5. 7份。再者，樹脂（2 )的碘價為 93 ° 合成例3 與合成例1同樣的反應裝置中，加入亞麻仁油脂肪酸 50份、間苯二曱酸21.1份、THEIC32.4份、季戊四醇4 2 份’於氮氣存在下一邊回流二曱苯，一邊於220至230。(： 反應至酸價為10以下後，蒸餾分離二曱苯而獲得液狀的樹 脂（3)。又，脫水量為7.7份。再者，樹脂（3)的蛾價為95。 合成例4 與合成例1同樣的反應裝置中，加入脫水蓖麻子油脂 肪酸40份、笨二曱酸酐25.6份、THEIC26.5份、三經甲 基丙烷13·6份，於氮氣存在下一邊回流二甲苯，一邊於 220至230°C反應至酸價為1〇以下後，蒸餾分離二甲苯而 獲得液狀的樹脂（4)。又，脫水量為5. 7份。再者，樹脂（4) 的碘價為60。 合成例5 與合成例1同樣的反應裝置中，加入亞麻仁油脂肪酸 45份、間苯二甲酸30. 7份、THEIC11. 1份、三羥曱基丙烷 11 201125938 22.7份，於氮氣存在下一邊回流二曱苯，一邊於220至230 。(：反應至酸價為1 〇以下後’蒸館分離二甲笨而獲得液狀的 樹脂（5 )。又’脫水量為9. 5份。再者’樹脂（5 )的碘價為 87 〇 合成例6 與合成例1同樣的反應裝置中，加入亞麻仁油脂肪酸 5 5份、間笨二曱酸14. 6份、THE IC3 7. 1份’於氮氣存在下 一邊回流二甲苯，一邊於220至230°C反應至酸價為10以 下後，蒸德分離二甲苯而獲得液狀的樹脂（6)。又’脫水量 為6. 7份。再者，樹脂（6)的碘價為106。 合成例7 與合成例1同樣的反應裝置中，加入亞麻仁油脂肪酸 30份、苯二曱酸酐30. 0份、THEIC30. 1份、三羥甲基丙院 15.4份’於氮氣存在下一邊回流二甲苯，一邊於220至230 °C反應至酸價為1 0以下後，蒸餾分離二曱苯而獲得液狀的 樹脂（7)。又’脫水量為5. 5份。再者，樹脂（7)的碘價為 56 〇 合成例8 與合成例1同樣的反應裝置中，加入脫水蓖麻子油脂 肪酸70份、苯二甲酸酐6. 5份、THEIC23. 6份、三羥甲基 丙炫 5. 2份，於氮氣存在下一邊回流二甲苯，一邊於22〇 至230°C反應至酸價為丨0以下後，蒸餾分離二曱笨而獲得 液狀的樹脂（8)。又’脫水量為5.3份。再者，樹脂（8)的 碘價為11 0。 12 201125938 合成例9 與合成例1同樣的反應裝置中，加入亞麻彳二 ~ /由脂肪駿 40份、苯二甲酸酐31. 9份、三羥甲基丙烷34 5外 , .切，於氣 氣存在下一邊回流二甲苯，一邊於220至230& 久應至酸 價為1 0以下後，蒸餾分離二曱苯而獲得液狀的樹^ 又，脫水量為6.4份。再者，樹脂（9)的峨價為 合成例1 0 與合成例1同樣的反應裝置中，加入亞麻k —'由脂肪峻 60份、間苯二甲酸21_ 8份、THEIC4. 8份、：r敍m 一鉍曱基丙浐 22. 0份，於氮氣存在下一邊回流二曱苯，一邊於9〇n ^ 20 至 230 °C反應至酸價為1 〇以下後，蒸餾分離二曱苯而獾β 復件液狀的 樹脂（1 0)。又’脫水量為8 · 6份。再者，樹脂（1 〇、 為 115。 ^ 合成例1至1 〇中各別獲得的醇酸樹脂的組成及 r生狀示 於表1。 [表1]The present invention relates to a printing ink for "...", a metallic printing ink plate 0 2 201125938 [Prior Art] At present, metal printing is roughly divided into two ways: after processing metal into a cylindrical shape, relief printing (relief 0ffset) The method of printing is the same as the method of processing the sheet metal plate by lithographic offset printing and then processing into a cylindrical shape. The art can, the three-piece beverage can, the food can, etc. are mainly printed by lithographic offset printing. Gold printed by lithographic offset printing method: The method of curing printing ink is oxidatively polymerized and cured by irradiation with ultraviolet rays, but it is used for applications requiring high processability: most of them use dry oil and dry oil fatty acid. A method of oxidatively polymerizing a modified alkyd resin to heat-harden it. Further, it is known that the processability of a metal printing ink varies depending on the content of a vegetable oil fatty acid used in an alkyd resin (Patent Document No.). Ink using an alkyd resin with a high fatty acid content in vegetable oils has poor processability and uses vegetable oil fat. The ink of the alkyd resin having a small content is excellent in workability. In the A' high-process type ink, the solubility of the resin, the transferability, and the stability of the on-board stability are improved by using an alkyd resin having a small vegetable oil fatty acid. The disk is used in comparison with the ink of the alkyd resin which is rich in fatty acid content from the vegetable oil, and the alkyd resin which is large in the unit of the sample 1Q. The resin having a short distance between the cross-linking points has a fine mesh structure and lacks a soft weight. The 3 t-face, an alkyd resin having a small iodine value, has a coarse mesh structure of a resin having a long distance between cross-linking points. Increased softness' However, the processability of the metal printing ink using the alcohol k-tree I is reflected in the flexibility of the alkyd resin. 201125938 Therefore, the metal ink manufacturer pays attention to the printability in the non-essential preparation of the processability- The general type, and the processability is a must-prepare for the preparation of two types of inks of high processing type. Then, in recent years, it is a part of the chemistry and chemistry of the can manufacturer and the metal printing manufacturer. manufacturer, The development of metal printing inks, which combines high processing blood g卩舢唬α and printability. Furthermore, the gloss of metal printing affects the smoothness of the surface of the coating film of printing ink, that is, it affects the leveling property. In the past, the gloss is not sufficient, and there is still room for improvement. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-285303 [Patent Document 2] Japanese Patent Laid-Open No. Hei. OBJECTS TO BE SOLVED BY THE INVENTION The present invention has been made to solve the above problems, and an object thereof is to provide a metal printing ink composition having high gloss and processability and excellent printability, and a printed metal sheet printed using the composition. Means for Solving the Problems As a result of repeated efforts, the present inventors have found that the present invention has been achieved by adopting the following configuration 'to achieve the above object. That is, the present invention relates to a metal printing ink composition in which a ratio of vegetable oil fatty acid constituting an alkyd resin is 35 to 65 mass% in a metal printing ink composition containing a pigment, an alkyd resin, and a hydrocarbon solvent. And 15 to 100 mol% of the polyol component is tris(2-hydroxyethyl)trimeric isocyanate 201125938 ester (THEIC). In the present invention, the iodine value of the alkyd resin is preferably from 55 to (10). Further, the present invention relates to a printed metal sheet having an ink layer formed using the metal printing ink composition of the present invention on a metal plate or a metal substrate provided with an undercoat layer on a metal plate. EFFECTS OF THE INVENTION According to the ink composition of the present invention, it is excellent in printability, and it can be imparted to the printed metal sheet, and it is required to be processed. In particular, there are printing inks for art cans, 3-piece beverage cans, and food cans. [Embodiment] Hereinafter, each component used in the metal printing ink composition of the present invention will be described in more detail. (Alkyd resin) The alkyd resin used in the metal printing ink composition of the present invention is a polybasic acid (P〇iybasic acid), and a part or all of tris(2-hydroxyethyl)trimeric isocyanuric acid. The condensate of the polyol is used as a skeleton, and the method of producing a resin modified with oil or sorghum S is not particularly limited, and a fatty acid method using an oil as a raw material and a fatty acid as a raw material can be used. And other known methods. In the present invention, the tris(2-hydroxyethyl)trimeric isocyanate used in the polyol component constituting the alkyd resin has a hydroxyl group in three directions of symmetry, and has a member structure. The polycondensate of polydecanoic acid and tris(2-hydroxyethyl)trimeric isocyanate acts as a lunar frame, and the degree of freedom is increased by the distance between the cross-linking points of the resin mesh structure, which is longer than 201125938, and the flexibility is achieved. Improvement. Hereby, it can be achieved by using tris(2-transethylethyl)trimeric isocyanuric acid: an increase in workability, which can be used as an alkyd resin used in inks which have been processed to date. The alkyd resin with a large content is improved. Further, a metal printing ink composition comprising an alkyd resin using tris(2-transethylethyl)trimeric isocyanuric acid has good fluidity at a high temperature, and the surface of the coating film is heated and dried after coating. Smooth and high gloss. In the present invention, 15 to 1 mol% of the polyol component constituting the alkyd resin is tris(2-hydroxyethyl)trimeric isocyanuric acid. When it is less than 15%, it is difficult to obtain a balance between printability and workability, and further, high gloss cannot be obtained. As the polyol component other than tris(2-hydroxyethyl)trimeric isocyanate, ethylene glycol, propylene glycol, L3-butanediol, rhodium butylene glycol, 1,5-pentanediol, 1,6- can be used. Hexanediol, 1,9-nonanediol, 2-mercapto_1>8-octanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butanol , 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 2-butyl-2-ethyl-1,3-propanediol, etc.; glycerol, trishydroxyl a trihydric alcohol such as propylamine or dimethyl ketone; a tetrahydric alcohol such as quaternary tetraol, diglycerin, di-dimethylolpropane or di-trimethylolethane; used in the past alkyd resin The polyol is not particularly limited. These may be used alone or in combination of two or more. The vegetable oil fatty acid component of the other components of the alkyd resin used in the present invention may, for example, be linseed oil, tung oil, dehydrated castor oil, soybean oil, safflower oil, linseed oil fatty acid, tung oil fatty acid, dehydrated castor bean oil 201125938 Large and oil fatty acids, safflower oil fatty acids, etc., or unsaturated fatty acids such as oleic acid, linoleic acid, linseed oil, oil stearic acid or ricinoleic acid. These may be used alone or in combination of two or more. Considering the price or the physical properties of the film, it is preferred to use linseed oil and linseed oleic acid. Further, a part of the vegetable oil or fatty acid may be changed to a monobasic acid other than the fat stagnation. As the other monobasic acid, benzoic acid, p-first butyl benzoic acid, rosin acid, hydrogenated rosin acid, or the like can be used. Further, examples of the polybasic acid include phthalic acid (anhydride), (IV), a succinyl dibasic acid such as p-dicarboxylic acid, 2, monoacid, and isophthalic acid; tetrahydro succinic acid (anhydride) and hexahydrogen. An alicyclic dibasic acid such as stearic acid (anhydride) or 1,4-3⁄4 hexane dicarboxylic acid; succinic acid (anhydride), alkenyl succinic acid (anhydride), fumaric acid, maleic anhydride, clothing Butic acid, adipic acid, bismuth:: fatty acid dibasic acid such as diacid, hinnc acid (anhydride); trimellitic acid (anhydride), pyromellitic acid (anhydride), methyl Cyclohexane tricarboxylic acid (anhydride), diphenyl ketone tetra (tetra), and the like. These polybasic acids may be used alone or in combination of two or more. The alkyd resin used in the metal printing ink composition of the present invention has a vegetable oil fatty acid content of 35 to 65. When it is less than 35% by mass, it is used as a component of a polyol, and tris(2-p-ethylethyl) isocyanuric acid is used to make 15 to 1 Torr (4) 'the flowability of the ink is lowered'. When it exceeds 65 mass%, processing is performed. Sex or film hardness is poor. It is more preferably 45 to 60% by mass in consideration of the fluidity of the ink, τ _ , workability, and balance of the hardness of the coating film. Further, the iodine value of the 'alkyd resin is preferably 55 ? 丨 + ^ and 勹 to 13 〇. When it is less than 55, the coating film hardness is poor, and when it exceeds 130, the workability right tends to decrease. Considering the balance between the hardness of the coating film and the workability, it is preferably from β5 to lb. Further, the resin used in the past can be used in combination with the alkyd resin of the present invention. In other words, the alkyd resin can be used in combination with a conventional resin which is compatible with a plurality of types, depending on the desired properties such as printability and film properties. Specifically, for example, a rosin-modified phenol resin, a polyester resin, a petroleum resin, an epoxy resin, a ketone resin, a rosin-modified maleic acid tree, an amine resin, a benzoguanamine resin, or the like can be exemplified. In the oxidative polymerization hardening type printing ink, a drying agent for printing ink for curing the ink as a curing accelerator may be added as needed, and a drying agent for printing ink may be added in the present invention. The desiccant for printing ink which can be used in the present invention may, for example, be a metal such as m iron or rhodium, and octanoic acid, naphthenic acid, neodecanoic acid, tung oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, and resin acid. A salt of a carboxylic acid, that is, a metal. These may be used alone or in combination of two or more. (Pigment) The pigment used in the present invention may be used alone or in combination of inorganic or organic pigments which are conventionally used for printing inks, and is not particularly limited. Specifically, for example, a pigment disclosed in Patent Document 2 or the like can be cited. (Hydrocarbon solvent) The hydrocarbon solvent used as the solvent for the metal printing ink used in the ink composition of the present invention can be used in a boiling point range of 2 Å to 4 Å. The hydrocarbon solvent to be used for the metal printing ink is not particularly limited. ^ As the hydrocarbon solvent, a general petroleum solvent or an alkyl solvent is suitably used. Examples of the petroleum-based solvent include solvents such as AF5, No. 6, and No. 7 of Nippon Oil Co., Ltd., and alkylbenzene-based solvents, which can be exemplified by Shinkoku Petrochemical Co., Ltd. 8, 201125938 BAB, etc., Alken (transliteration) 56N, L, 200P or UIC companies are used alone or in combination. The amount of the TAC-based 0 hydrocarbon-based solvent to be used for the ink is not particularly limited as long as the general printing value can be adjusted to 5 to 4 G (other components), and the ink composition of the present invention is used as the other component. A conventional pigment dispersant, a wax, a stabilizer, an acid catalyst, or the like may be added as needed. Further, without knowing the scope of the object of the present invention, it is also possible to add fine powder of oxidized stone, organic bentonite or the like as an auxiliary agent to the ink, and further, as a printing ink varnish component, it is also possible to use a metal chelate or sorbose. A gelatinous varnish such as an alcohol. The metal printing ink composition of the present invention can be prepared by a conventional method using a grinder, a ball mill, a bead mill or the like. The metal plate for printing the ink composition of the present invention is preferably a metal plate such as stainless steel, ingot, tin-plated steel or tin-free steel, or a metal substrate having a primer (primer) layer on the metal plate. Not limited to these. For the formation of the undercoat layer, for example, a substrate coating composition such as a slze paint or a white coat which is generally used in metal printing can be used. Furthermore, PET exposure laminates are also not harmful. The method of printing the metal printing ink composition of the present invention on these metal plates can be easily printed by a general printing method such as an offset printing method using wet water or a dry offset printing method. The ink film thickness may be any, for example, in the range of 〇·1 to 6/zm. The hardening of the metal printing ink composition of the present invention can be carried out using an oven of the type of gold, which is usually used in the range of 120 to 230 °C. The heating time may be any one of 3 hours or longer, and is usually carried out in the range of 3 to 30 minutes. The thus obtained printed metal sheet of the present invention does not necessarily require varnish coating for overprinting. However, by using an overprint varnish, better coating film properties can be obtained. When the overprint varnish is applied to the metal printing ink of the printed metal sheet of the present invention, it is preferable to carry out the heat treatment of the metal printing ink composition of the present invention, and it is also possible to carry out the coating by wet 碰n wet. After that, both heat-harden at the same time. The metal printing ink composition of the present invention can be used as a sheet-like metal printing ink because it has excellent printing suitability to form a high-gloss 'high-strength ink coating film on a metal plate. [Examples] Hereinafter, the present invention will be described based on Synthesis Examples and Examples, but the present invention is not limited to the examples. Further, the number of copies and % in each case are based on the mass. Synthesis Example 1 In a reaction apparatus equipped with a stirrer, a water separator, a condenser, a nitrogen introduction tube, and a thermometer, 45 parts of linseed oil fatty acid, 5.2 parts of stearic acid, and 1 part of THE 1C 26·3 parts, glycerin 9 were added. 3 parts, refluxing xylene in the presence of nitrogen, and after 22 to 23 (TC reaction to an acid value of 1 Torr or less, distilling and separating the dimethyl group to obtain a liquid resin (1). In addition, the iodine value of the resin (1) is 86 (the measurement of the iodine value is carried out according to 10 201125938 JISK0070. The same applies hereinafter.) Synthesis Example 2 In the same reaction apparatus as in Synthesis Example 1, "adding flax" 50 parts of lipoic acid fatty acid, 20.1 parts of phthalic anhydride, THEIC 23. 〇 part, 13.1 parts of trishydroxyl-propyl propylene, refluxing in the presence of nitrogen, and reacting at 220 to 230 ° C to acid value After being 1 Torr or less, diphenylbenzene was distilled off to obtain a liquid resin (2). Further, the amount of dehydration was 5.7 parts. Further, the iodine value of the resin (2) was 93 °. Synthesis Example 3 and Synthesis Example 1 In the same reaction apparatus, 50 parts of linseed oil fatty acid, 21.1 parts of isophthalic acid, and THEIC 32.4 were added. And 4 parts of pentaerythritol are refluxed with diphenylbenzene in the presence of nitrogen at 220 to 230. (: After the reaction to an acid value of 10 or less, diphenylbenzene is distilled off to obtain a liquid resin (3). The amount of dehydration was 7.7 parts. Further, the moth of the resin (3) was 95. Synthesis Example 4 In the same reaction apparatus as in Synthesis Example 1, 40 parts of dehydrated castor oil fatty acid and 25.6 parts of stupid anhydride were added to THEIC26. .5 parts, 13 parts of trimethyl propylene oxide, refluxing xylene in the presence of nitrogen, and reacting at 220 to 230 ° C until the acid value is 1 Torr or less, and then separating xylene to obtain a liquid resin. (4) Further, the amount of dehydration was 5.7. Further, the iodine value of the resin (4) was 60. Synthesis Example 5 In the same reaction apparatus as in Synthesis Example 1, 45 parts of linseed oil fatty acid and m-benzene were added. 30 parts of dicarboxylic acid, 1 part of THEIC, 1 part, and 12.7 parts of trihydrocarbyl propane 11 201125938, refluxing diphenylbenzene in the presence of nitrogen, and 220 to 230. (: After reacting to an acid value of 1 〇 or less) 5份。再的的树。 The steaming hall to separate the dimethyl benzene to obtain a liquid resin (5). (5) The iodine value is 87 〇 Synthesis Example 6 In the same reaction apparatus as in Synthesis Example 1, 55 parts of linseed oil fatty acid, 14.6 parts of stearic acid, and 14.1 part of 'the IC3' were added to nitrogen. And the amount of dehydration is 6.7. Further, the amount of dehydration is 6.7. The iodine value of the resin (6) was 106. Synthesis Example 7 In the same reaction apparatus as in Synthesis Example 1, 30 parts of linseed oil fatty acid, 30.1 parts of benzoic anhydride, 3 parts of THEIC, and 15.4 parts of trimethylol propyl group were added and refluxed in the presence of nitrogen. Xylene is reacted at 220 to 230 ° C until the acid value is 10 or less, and then diphenylbenzene is distilled off to obtain a liquid resin (7). 5份。 The amount of dehydration was 5. 5 parts. Further, the resin (7) has an iodine value of 56 〇. In the same reaction apparatus as in Synthesis Example 1, 70 parts of dehydrated castor oil fatty acid, phthalic anhydride 6. 5 parts, THEIC 23.6 parts, and three were added. 5 parts of methylol propyl sulfonate, refluxing xylene in the presence of nitrogen, and reacting at 22 Torr to 230 ° C until the acid value is 丨0 or less, and then distilling off the hydrazine to obtain a liquid resin (8) ). Also, the amount of dehydration was 5.3 parts. Further, the iodine value of the resin (8) was 110. 12 201125938 Synthesis Example 9 In the same reaction apparatus as in Synthesis Example 1, flaxseed II / / 40 parts by fat, 31.9 parts of phthalic anhydride, and 34 parts of trimethylolpropane were added, and the gas was cut. In the presence of gas, while returning xylene, the divalent benzene was distilled off to obtain a liquid-like tree at 220 to 230 & after the acid value was 10 or less, and the amount of dehydration was 6.4 parts. Further, the valence of the resin (9) is the same as in the synthesis example of the synthesis example 10, and the addition of flax k-' is 60 parts by weight of fat, 21_8 parts of isophthalic acid, and 8 parts of THEIC. r 。 m 铋曱 铋曱 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐 浐And 獾β complex liquid resin (10). Also, the amount of dehydration was 8.6 parts. Further, the resin (1 〇, 115.) The composition and r-form of the alkyd resin obtained in each of Synthesis Examples 1 to 1 are shown in Table 1. [Table 1]
實施例1 將作為顏料之Lionol Blue-FG-7351 (東洋墨水公司製 13 201125938 造）15份、醇酸樹脂（1)60份、環烷酸錳1份 177作為烴系溶 劑之烧基笨（UIC製造。BAB)25份’使用3根輥磨機混練， 獲得藍色墨水（1)。 使用所得藍色墨水（1)於金屬板印刷，關於硬化性、光 澤、加工性及印刷適性，根據以下的方法評估。結果示於 表2 〇 〈硬化性試驗〉 墨水0.3mL，以RI Tester(明製作所製造）之分開的2 個輥，印刷於電鍍錫鋼板（錫板）上之印刷板於電烘箱中， 於1 50°C加熱10分鐘。加熱乾燥後，將板溫冷卻至室溫， 根據JIS K 5 4 0 0測定印刷表面的鉛筆硬度。 評估基準 〇：印刷的墨水面無HB錯筆的刮傷。 △:印刷的墨水面有HB鉛筆的刮傷但無B鉛筆的到傷。 X :印刷的墨水面又B鉛筆的刮傷。 〈光澤試驗〉 則述硬化性試驗中所加熱硬化的印刷板的墨水面的照 相/·生，亦即以目視觀察投影至墨水面的螢光燈影像的鮮明 度。 〇：螢光燈的影像鮮明者。 △:螢光燈的影像為中等程度者。 X :螢光燈的影像不鮮明者。 〈加工性試驗> 前述硬化性試驗中所製作的印刷板，使用東洋墨水製 14 201125938 造公司：造的金屬片用透明塗料，以塗膜量為6〇m— 、 裝於電烘箱中以1 6 0。(3施行加熱硬化丨〇分鐘。 將該印刷塗奘如认h 土屐板於至溫下，以壓印機加工為角型罐（深度 20mm ’各角落部分的 h工克為4 b 8、l〇min)，以目視觀察 各角落部分。 ” 〇：未見塗膜的剝離者。 X :可見塗膜的剝離者。 〈印刷適性試驗> 乂鬲速印刷適性试驗機（Smt公司製造之pMg〇4pT)，以 墨水被膜厚度成為1/zm方式之試驗用橡膠輥採取墨水一 邊以2m/S的速度在電鍍錫鋼板移動，一邊將墨水由輥印刷 至電鍍錫鋼板，加熱硬化後，觀察墨水的移動狀態。墨水 的塗膜消耗完成良好平滑者評估為：〇，中等程度者評估 為：△’消耗差而可見底部者評估為：χ。 實施例2至6及比較例1至4 除了使用合成例2至1 0各別合成的樹脂（2)至（1 〇)作 為醇酸樹脂，以示於表2的調配比例外，與實施例丨同樣 的方式而調製墨水（2)至（1 0)’評估各特性。結果示於表2。 201125938 [表2] 醇酸樹脂 烴系溶劑 種類（份） 顏料 種類(份） 特性 種類 THEIC含量 (莫耳％) 碘價 份 硬化性 光澤 加工性 印刷適性 實施例1 樹脂（1) 50 86 60 BAB(25) FG-735K15) 〇 〇 〇 〇 實施例2 樹脂（2) 50 93 65 BAB(20) FG-7351C15) 〇 〇 〇 〇 實施例3 樹脂（3) 80 95 65 BAB(20) FG-735K15) 〇 〇 〇 〇 實施例4 樹脂（4) 50 60 60 BAB(25) FG-7351C15) 〇 〇 〇 〇 實施例5 樹脂（5) 20 87 60 BAB(25) FG-735K15) 〇 〇 〇 〇 實施例6 樹脂（6) 100 106 70 BAB(15) FG-735K15) 〇 〇 〇 〇 比較例1 樹脂（7) 50 56 50 BAB(35) FG-735K15) X 〇 〇 X 比較例2 樹脂（8) 70 110 75 BAB(10) FG-735K15) 〇 〇 X 〇 比較例3 樹脂（9) 0 75 55 BABOO) FG-7351C15) Δ X 〇 X 比較例4 樹脂（10) 10 115 70 BAB(15) FG-735K15) 〇 Δ X 〇 由表2可知，使用多元醇成分中的一部分或全部使用 三（2 -羥基乙基）三聚異氰酸酯，且植物油脂肪酸的含量係 於特定範圍的醇酸樹脂之金屬印刷墨水，可使至今仍無法 之印刷適性與加工性的兼具為可行，再者，可表現高光澤 性。 【圖式簡單說明】 無0 【主要元件符號說明】 無。 16Example 1 15 parts of Lionol Blue-FG-7351 (manufactured by Toyo Ink Co., Ltd., manufactured by Toyo Ink Co., Ltd.), 60 parts of alkyd resin (1), and 1 part of 177 naphthenate as a hydrocarbon solvent were used as a hydrocarbon solvent. UIC manufacturing. BAB) 25 parts 'mixed with 3 roll mills to obtain blue ink (1). Using the obtained blue ink (1) for printing on a metal plate, the hardenability, gloss, workability, and printability were evaluated by the following methods. The results are shown in Table 2 〇 <hardenability test> 0.3 mL of ink, separated by RI Tester (manufactured by Ming Manufacturing Co., Ltd.), printed on an electroplated tin plate (tin plate) in an electric oven, at 1 Heat at 50 ° C for 10 minutes. After heating and drying, the plate temperature was cooled to room temperature, and the pencil hardness of the printed surface was measured in accordance with JIS K 5 400. Evaluation Criteria 〇: The printed ink surface is free from scratches caused by HB pens. △: The printed ink surface was scratched by an HB pencil but not by a B pencil. X: The printed ink surface is scratched by a pencil. <Gloss Test> The photograph of the ink surface of the printed board which is heat-cured in the hardenability test is described, that is, the brightness of the fluorescent light image projected onto the ink surface is visually observed. 〇: The image of the fluorescent light is clear. △: The image of the fluorescent lamp is moderate. X: The image of the fluorescent lamp is not clear. <Processability Test> The printing plate produced in the above-mentioned hardenability test was made of a transparent paint for metal sheets manufactured by Toyo Ink Co., Ltd., manufactured by Toyo Ink, with a coating amount of 6 μm, and was placed in an electric oven. 1 6 0. (3) Perform heat hardening for 丨〇 minutes. Apply the printing to the temperature of the plate, and machine it into an angular can with an imprinting machine (depth 20mm 'h corner of each corner is 4 b 8 , L〇min), visually observing the corners of each corner. ” 〇: No peeling of the coating film was observed. X: The peeling of the coating film was observed. <Printability test> 乂鬲 Speed printing suitability test machine (manufactured by Smt Corporation) pMg〇4pT), the test rubber roller having the ink film thickness of 1/zm was moved to the tin-plated steel sheet at a speed of 2 m/s while the ink was applied, and the ink was printed by a roll to a tin-plated steel sheet, and then heat-hardened. The movement state of the ink was observed. The film finish consumption of the ink was evaluated as follows: 〇, moderately evaluated as: △ 'poor consumption and visible bottom is evaluated as: χ. Examples 2 to 6 and Comparative Examples 1 to 4 The ink (2) was prepared in the same manner as in Example 除了 except that the resins (2) to (1 〇) synthesized in Synthesis Examples 2 to 10 were used as the alkyd resin, and the compounding ratios shown in Table 2 were used. (1 0) 'Evaluate each characteristic. The results are shown in Table 2. 201125938 [Table 2] Alkyd resin hydrocarbon solvent type (part) Pigment type (part) Characteristic type THEIC content (mol%) Iodine valence hardening gloss processability Printing suitability Example 1 Resin (1) 50 86 60 BAB ( 25) FG-735K15) 〇〇〇〇 Example 2 Resin (2) 50 93 65 BAB (20) FG-7351C15) 〇〇〇〇 Example 3 Resin (3) 80 95 65 BAB (20) FG-735K15) 〇〇〇〇 Example 4 Resin (4) 50 60 60 BAB (25) FG-7351C15) 〇〇〇〇 Example 5 Resin (5) 20 87 60 BAB (25) FG-735K15) 〇〇〇〇Example 6 Resin (6) 100 106 70 BAB (15) FG-735K15) 〇〇〇〇Comparative Example 1 Resin (7) 50 56 50 BAB(35) FG-735K15) X 〇〇X Comparative Example 2 Resin (8) 70 110 75 BAB(10) FG-735K15) 〇〇X 〇Comparative Example 3 Resin (9) 0 75 55 BABOO) FG-7351C15) Δ X 〇X Comparative Example 4 Resin (10) 10 115 70 BAB(15) FG- 735K15) 〇Δ X 〇 It can be seen from Table 2 that some or all of the polyol components use tris(2-hydroxyethyl)trimeric isocyanate, and the content of vegetable oil fatty acid is in a specific range of alcohol. The metal printing ink of the acid resin makes it possible to print both the suitability and the processability, and further, it can exhibit high gloss. [Simple description of the diagram] No 0 [Description of main component symbols] None. 16