200403316 玫、費明說明 ， (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明） ㈠【發明所屬之技術領域】 本發明係相關於氧化聚合乾燥型印刷油墨用乾燥劑及 含該乾燥劑之印刷油墨。 ㈡【先前技術】 爲要促進平版膠版印刷油墨等氧化聚合乾燥型油墨印 刷後之乾燥而添加乾燥劑。通常這類的乾燥劑係單獨使用 或倂用脂肪酸的錳鹽及脂肪酸的鈷鹽。 鲁 鈷屬於重金屬，從表1毒性評估的數據亦可得知鈷並非 爲無害之金屬。平版膠版印刷油墨的成分中含有對環境造 成負擔之成分。因此，爲要開發一種對環境無負擔且儘量 不含有害成分之平版膠版印刷油墨，期望能不使用鈷成 分。惟，若單獨使用對環境負荷更低、對健康的不良影響 小之脂肪酸鈣鹽和鐵鹽時，幾乎不具有乾燥劑之效果。因 不易找到其他替代品，故皆使用含錳或鈷之乾燥劑。 又，比較鈷和錳的毒性之數據如表1所示。從表中可得 鲁 知鈷的毒性較大。 200403316 表1鈷和錳的毒性比較 (資料來源爲 REGISTRY OF TOXIC EFFECTS OF CHEMICAL SUBSTANCES) LD50 (老鼠經嘴） 鈷金屬 6.17g/ kg 錳金屬 9.0g/ kg 環烷酸鈷（一般的乾燥劑） 3.9g/kg 環烷酸鑑（一般的乾燥劑） 6.0g/ kg 又因近年來對環境問題的意識高漲，故使用植物油作爲 原料之油墨的用量增加。自古常用的石油類溶劑係印刷油 墨用溶劑，爲代表性的揮發性有機化合物（又稱爲V〇C )， 以植物油取代此有機化合物，減少其用量。又，依據w Η〇 (世界保健機構）的定義，本發明中的V 0 C係指沸點範圍 約爲50〜25 0°C範圍內之有機化合物。例如苯、甲苯、二甲 苯等。 例如市面已販售減少V ◦ C成分並以大豆油取代之印刷 油墨。因這些油墨的乾燥性較以前的油墨差，故將印刷後 的物質重疊後印刷面間或印刷油墨面和紙會黏著，容易發 生所謂的「保護性不佳」的現象。 ㈢【發明內容】 本發明的目的係提供一種不含有害性高的鈷、對環境和 健康的不良影響小之氧化聚合乾燥型印刷油墨用乾燥齊K & 含該乾燥劑之印刷油墨。 本發明的其他目的係提供以大豆油作爲展色料$ _ # 並減少V 0 C含量的環境考量型印刷油墨中，可防止保iS性 200403316 不良之氧化聚合乾燥型印刷油墨用乾燥劑及含該乾燥劑之 印刷油墨。 本發明者們爲要提供一種對環境無不良影響，且具備印 刷時不影響作業性的乾燥性之印刷油墨，重複硏究開發的 結果而完成本發明。 亦即，本發明的氧化聚合乾燥型油墨用乾燥劑含有脂肪 酸的鈽鹽及脂肪酸的錳鹽。 單獨使用脂肪酸的鈽鹽幾乎不具有乾燥劑之效果，若與 脂肪酸的錳鹽倂用，即使不使用對環境和健康有不良影饗 的鈷亦具有印刷油墨所需適當的乾燥性。 又，本發明的乾燥劑的其他形態係含有鈽佔金屬成分的 5 0質量％以上的脂肪酸的金屬鹽及脂肪酸的錳鹽之乾燥 劑。此乾燥劑使印刷油墨具有適當的乾燥性。 其他的型態例如含有脂肪酸的鐵鹽及脂肪酸的錳鹽之 乾燥劑。 單獨使用脂肪酸的鐵鹽具有的乾燥劑之效果小，若與脂 肪酸的錳鹽倂用，即使不使用對環境和健康有不良影響的 鈷亦具有印刷油墨所需適當的乾燥性。 鐵較鈽更便宜，可降低原料費。添加鐵鹽的油墨有褐色 的著色傾向，無法使用於明亮色或薄色的油墨。惟和錳鹽 倂用可降低鐵鹽的添加量，可預防油墨的著色並擴大應用 範圍。 將上述的乾燥劑添加在油墨中’藉此可提供不含鈷之油 EJ3 墨。 在B增加大豆油含量的印刷油墨中添加含有脂肪酸的 200403316 鐵鹽及脂肪酸的錳鹽之乾燥劑後，可改善此油墨的乾燥 . 性，不易發生上述保護性不佳的問題。 【發明的效果】 依據本發明可製得不含對環境和健康有不良影響的 ‘ 鈷，減少錳含量的氧化聚合乾燥型油墨用乾燥劑。本發明 中倂用脂肪酸的鈽鹽和脂肪酸的錳鹽之乾燥劑除了對環境 的不良影響少，且具有與含脂肪酸的鈷鹽和脂肪酸的錳鹽 之乾燥劑相同的乾燥促進性。 又，本發明中倂用脂肪酸的鐵鹽和脂肪酸的錳鹽之乾燥 · 劑可減少有油墨著色問題之鐵鹽的添加量。脂肪酸的鐵鹽 較脂肪酸的鈽鹽便宜，可削減乾燥劑之成本。 VOC的含量減少，在以大豆油等作爲展色料主成分之印 刷油墨中，藉著使用本發明的乾燥劑可改善保護性不佳的 現象。 ㈣【實施方式】 (1 )本發明的乾燥劑的第一形態係含有脂肪酸的鈽鹽及脂 肪酸的錳鹽之乾燥劑。 Φ 脂肪酸的鈽鹽和脂肪酸的錳鹽，例如可使用辛酸的金屬 鹽、環烷酸的金屬鹽、新葵酸的金屬鹽等脂肪酸的金屬鹽。 (2 )本發明的乾燥劑的第二形態係含有鈽鹽佔金屬成分5 0 的質量％以上的脂肪酸的金屬鹽及脂肪酸的錳鹽之乾燥 劑。鈽雖昂貴，惟只要含量大於5 0 %即可充分達到本發明 的效果，藉著倂用脂肪酸的錳鹽可發揮鈽的效果，較使用 只含有脂肪酸的錳鹽之乾燥劑時具有優異的乾燥性。 (3 )本發明的乾燥劑的第三形態係含有脂肪酸的鐵鹽和脂 -10 - 200403316 酸 烷 環 f 酸 辛 如 例 鹽 鐡 的 酸 肪 脂。 ο 鹽 劑鐵 燥的 乾酸 之肪 鹽脂 锰等 的酸 酸葵 肪新 本心明的印刷油墨用乾燥劑之製法，係可藉著將脂肪酸 的金屬鹽溶解在油脂類、脂肪酸酯類、印刷油墨用高沸點 石油類溶劑等單獨或這些的混合溶劑中。溶解脂肪酸的金 屬鹽之彳谷劑以大丑油等植物油和大豆油脂肪酸酯等植物性 月旨肪酸酯較理想。藉此，可減少油墨中的VOC成分之含量。 本發明的印刷油墨用乾燥劑之金屬含量爲3〜1 2質量％ 較理想，更理想爲4〜6質量％ 。 可藉著在氧化聚合乾燥型印刷油墨中添加本發明的印 刷油墨用乾燥劑使印刷油墨具有充分的乾燥性。在印刷油 墨的製造工程中將本發明的印刷油墨用乾燥劑添加於印刷 油墨中，經由攪拌機的攪拌工程或輥磨機等的捏合工程均 勻地分散在印刷油墨中。 本發明的印刷油墨用乾燥劑中，將含有脂肪酸的鐵鹽及 脂肪酸的錳鹽之乾燥劑添加在藉著單獨或混合使用大豆油 等植物油類和大豆油脂肪酸等植物油脂肪酸酯類使油墨中 的V 0 C成分含量減少爲小於1 %之印刷油墨時，可使印刷 油墨具有充分的乾燥性。 上述 VOC成分的含量小於1 %的印刷油墨，例如含有 2 0〜60質量％大豆油及/或大豆油脂肪酸酯之印刷油墨。可 使用的大豆油脂肪酸酯例如大豆油脂肪酸甲酯、大豆油脂 肪酸乙酯、大豆油脂肪酸正丁酯、大豆油脂肪酸第三丁酯、 大豆油脂肪酸2 -乙基己酯等公知的脂肪酸酯。 上述VOC成分的含量小於1 %的印刷油墨之其他例，例 200403316 如含有20〜60質量!大豆油及/或妥爾油脂肪酸酯，且大S # 油的含量大於2 0質量％之印刷油墨。可使用的妥爾油脂肪 酸酯例如妥爾油脂肪酸甲酯、妥爾油脂肪酸乙酯、妥爾油 脂肪酸丁酯、妥爾油脂肪酸2 -甲基己酯、妥爾油脂肪酸異 戊四醇酯等公知的脂肪酸酯。 又，在印刷油墨中使用上述（1 )中記載的乾燥劑時， 添加含脂肪酸的鈽鹽之乾燥劑（金屬含有率3 %〜1 2% )使 油墨中含有0.00 3〜0.36質量％的鈽，添加含脂肪酸的錳鹽 之乾燥劑（金屬含有率 3 %〜12 % )使印刷油墨中含有 Φ 0.003〜0.12質量％的錳之情況較理想。 又，在印刷油墨中使用上述（2 )中記載的鈽成分佔金 屬成分的5 0質量％以上之脂肪酸的金屬鹽乾燥劑時，添加 含鈽成分佔金屬成分的5 0質量％以上的脂肪酸的金屬鹽 之乾燥劑（金屬含有率3 %〜12 % )使印刷油墨中含有 0.00 3〜0.36質量％的鈽，添加含脂肪酸的錳鹽之乾燥劑（金 屬含有率3 %〜1 2 % )使印刷油墨中含有〇 . 〇 〇 3〜〇 . 1 2質量％200403316 Mei and Fei Ming explained, (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and the drawings are briefly explained) ㈠ [Technical field to which the invention belongs] The present invention is related to the oxidative polymerization dry type Desiccant for printing ink and printing ink containing the same.先前 [Prior art] A desiccant is added to promote drying after printing of oxidative polymerization drying inks such as lithographic offset printing inks. Usually such desiccants are used alone or in combination with manganese salts of fatty acids and cobalt salts of fatty acids. Cobalt is a heavy metal. From the data of toxicity evaluation in Table 1, it can be known that cobalt is not a harmless metal. The components of lithographic offset printing inks contain components that cause a burden on the environment. Therefore, in order to develop a lithographic offset printing ink that is environmentally-friendly and contains as few harmful components as possible, it is desirable not to use a cobalt component. However, the use of calcium salts and iron salts of fatty acids, which have lower environmental impacts and less adverse health effects, when used alone, has almost no effect as a desiccant. Because it is not easy to find other alternatives, desiccants containing manganese or cobalt are used. Table 1 shows the data comparing the toxicity of cobalt and manganese. It is known from the table that cobalt is more toxic. 200403316 Table 1 Comparison of Toxicity of Cobalt and Manganese (Source: REGISTRY OF TOXIC EFFECTS OF CHEMICAL SUBSTANCES) LD50 (rat mouth) Cobalt metal 6.17g / kg Manganese metal 9.0g / kg Cobalt naphthenate (general desiccant) 3.9 g / kg Naphthenic acid reference (general desiccant) 6.0g / kg Due to the increasing awareness of environmental issues in recent years, the amount of inks using vegetable oils as raw materials has increased. A petroleum-based solvent commonly used since ancient times is a solvent for printing inks, which is a representative volatile organic compound (also known as VOC). This organic compound is replaced with a vegetable oil to reduce its use. In addition, according to the definition of wΗ〇 (World Health Organization), V 0 C in the present invention refers to an organic compound having a boiling point range of about 50 to 25 ° C. For example, benzene, toluene, xylene and the like. For example, printing inks that have reduced V ◦ C and replaced with soybean oil have been sold on the market. Because these inks are less dry than previous inks, the printed matter may adhere to the printed surface or the printed ink surface and paper after the printed materials are superimposed, which is likely to cause the phenomenon of "poor protection". [Summary of the Invention] The object of the present invention is to provide a drying ink K & d, a drying ink for oxidative polymerization dry printing inks that does not contain highly harmful cobalt and has a small adverse effect on the environment and health. Another object of the present invention is to provide an environmentally-friendly printing ink using soybean oil as a coloring material $ _ # and reducing the content of V 0 C, which can prevent the oxidative polymerization drying printing ink which has poor 200S316 properties. The printing ink of the desiccant. The present inventors have repeatedly studied the results of development in order to provide a printing ink that has no adverse effects on the environment and has drying properties that do not affect workability during printing. That is, the desiccant for the oxidative polymerization drying ink of the present invention contains a phosphonium salt of a fatty acid and a manganese salt of a fatty acid. The phosphonium salt of a fatty acid alone has almost no effect as a desiccant. If it is used with a manganese salt of a fatty acid, even if cobalt, which has adverse effects on the environment and health, is not used, it has the appropriate drying properties required for printing inks. In another form of the desiccant of the present invention, it is a desiccant containing a metal salt of a fatty acid containing 50% by mass or more of a metal component and a manganese salt of a fatty acid. This desiccant gives the printing ink proper drying properties. Other types include desiccants containing iron salts of fatty acids and manganese salts of fatty acids. The use of iron salts of fatty acids alone has a small effect as a desiccant. If used with manganese salts of fatty acids, even if cobalt, which does not have an adverse effect on the environment and health, is used, it has the appropriate drying properties required for printing inks. Iron is cheaper than hafnium and reduces raw material costs. Iron salt-added inks have a brown coloring tendency and cannot be used for bright or thin inks. However, the use of manganese salts can reduce the amount of iron salts added, prevent the coloration of inks, and expand the scope of application. Adding the above-mentioned desiccant to the ink 'can provide cobalt-free oil EJ3 ink. Adding a 200403316 iron salt containing fatty acid and a manganese salt of fatty acid to a printing ink with an increased soybean oil content in B can improve the drying properties of the ink and prevent the aforementioned problems of poor protection. [Effects of the Invention] According to the present invention, it is possible to prepare an oxidative polymerization drying type ink drying agent which does not contain ‘cobalt, which has an adverse effect on the environment and health, and reduces the content of manganese. The desiccant of the phosphonium salt of a fatty acid used in the present invention and the manganese salt of a fatty acid has less adverse effects on the environment and has the same drying promoting properties as that of a desiccant containing a cobalt salt of a fatty acid and a manganese salt of a fatty acid. In addition, in the present invention, an iron salt of a fatty acid and a manganese salt of a fatty acid are used as a drying agent to reduce the amount of iron salts added to the ink coloring problem. Iron salts of fatty acids are cheaper than phosphonium salts of fatty acids, which can reduce the cost of desiccants. The content of VOC is reduced. In a printing ink containing soybean oil or the like as a main component of a coloring material, the use of the desiccant of the present invention can improve the phenomenon of poor protection. [Embodiment] (1) The first aspect of the desiccant of the present invention is a desiccant containing a phosphonium salt of a fatty acid and a manganese salt of a fatty acid. As the phosphonium salt of a fatty acid and a manganese salt of a fatty acid, for example, a metal salt of a fatty acid such as a metal salt of caprylic acid, a metal salt of naphthenic acid, or a metal salt of neonic acid can be used. (2) A second aspect of the desiccant of the present invention is a desiccant containing a metal salt of a fatty acid and a manganese salt of a fatty acid in which the phosphonium salt accounts for 50% by mass or more of the metal component. Although osmium is expensive, the effect of the present invention can be fully achieved as long as the content is more than 50%. The effect of osmium can be exerted by using a manganese salt of a fatty acid, which has better drying than using a desiccant containing only a manganese salt of a fatty acid. Sex. (3) The third form of the desiccant of the present invention contains an iron salt of a fatty acid and a fat -10-200403316 acid alkane ring f acid octanoate, such as an example of an acid fat of salt 鐡. ο Salting agent Dry iron fatty acid salt Fatty acid salt such as manganese acid and manganese acid, etc. The new method of making drying agent for printing ink is to dissolve the metal salt of fatty acid in oils, fatty acid esters, High-boiling-point petroleum-based solvents for printing inks may be used alone or in a mixture of these solvents. Cereals for dissolving fatty acid metal salts are preferably vegetable oils such as ugly oil and vegetable fatty acids such as soybean oil fatty acid esters. This can reduce the content of VOC components in the ink. The metal content of the desiccant for printing ink of the present invention is preferably 3 to 12% by mass, and more preferably 4 to 6% by mass. By adding the drying agent for printing inks of the present invention to oxidative polymerization drying type printing inks, the printing inks can have sufficient drying properties. In the printing ink manufacturing process, the desiccant for printing inks of the present invention is added to the printing ink, and uniformly dispersed in the printing ink via a stirring process of a mixer or a kneading process such as a roll mill. In the desiccant for printing inks of the present invention, a desiccant containing iron salts of fatty acids and manganese salts of fatty acids is added to the ink by using vegetable oils such as soybean oil and vegetable oil fatty acid esters such as soybean oil fatty acids alone or in combination. When the V 0 C component content is reduced to less than 1%, the printing ink can have sufficient drying properties. The printing ink whose content of the VOC component is less than 1%, for example, a printing ink containing 20 to 60% by mass of soybean oil and / or soybean oil fatty acid ester. Usable soybean oil fatty acid esters include known fatty acids such as soybean oil fatty acid methyl ester, soybean oil fatty acid ethyl ester, soybean oil fatty acid n-butyl ester, soybean oil fatty acid third butyl ester, soybean oil fatty acid 2-ethylhexyl ester, and the like. ester. Other examples of printing inks with a content of less than 1% of the above VOC components, such as 200403316 If it contains 20 to 60 masses! Soy oil and / or tall oil fatty acid esters, and the content of large S # oil is greater than 20% by mass Ink. Tall oil fatty acid esters that can be used such as tall oil fatty acid methyl ester, tall oil fatty acid ethyl ester, tall oil fatty acid butyl ester, tall oil fatty acid 2-methylhexyl ester, tall oil fatty acid isoprene tetraol Well-known fatty acid esters, such as esters. When a desiccant as described in (1) is used in a printing ink, a desiccant (a metal content of 3% to 12%) containing a phosphonium salt containing a fatty acid is added so that the ink contains 0.00 3 to 0.36 mass% of rhenium. It is desirable to add a desiccant containing a fatty acid-containing manganese salt (a metal content of 3% to 12%) to make the printing ink contain Φ 0.003 to 0.12% by mass of manganese. When a metal salt desiccant having a rhenium component as described in (2) above which contains a fatty acid of 50% by mass or more of the metal component is used in the printing ink, a phosphonium component containing 50% by mass or more of the fatty acid as the metal component is added. Metal salt desiccant (metal content 3% ~ 12%) to make printing ink contain 0.00 3 ~ 0.36 mass% of rhenium, add fatty acid-containing manganese salt desiccant (metal content 3% ~ 12%) to Printing ink contains 〇〇〇〇3〜〇. 1 2 mass%
的錳之情況較理想。 G 又’在印刷油墨中使用上述（3 )中記載的脂肪酸的金 屬鹽之乾燥劑時，添加含脂肪酸的鐵鹽之乾燥劑（金屬含 有率3 %〜1 2 % )使油墨中含有〇 . 〇 〇 3〜〇 . 3 6質量。的鐵，添 加含脂肪酸的錳鹽之乾燥劑（金屬含有率3 %〜丨2 % )使印 刷油墨中含有0.003〜0· 12質量％的錳之情況較理想。 又’巾面已販售以大豆油取代V 〇 C成分減少V 0 C含量 之印刷油墨，惟這類的印刷油墨之乾燥性較以前的印刷油 墨之乾燥性更差，印刷後重複堆積後會發生印刷面間或印 -12- 200403316 刷面和紙面附著在一起所謂的「保護性不佳」的問題，藉 > 著使用本發明的含有脂肪酸的鐵鹽及脂肪酸的錳鹽之乾燥 劑，可去除或降低上述「保護性不佳」的現象。 本發明的印刷油墨中除了含有上述乾燥劑及顏料等色 材、展色料（淸漆）之外，亦可含有蠟質等各種印刷油墨 用添加劑。 此展色料（淸漆）之製法係松香變性苯酚樹脂、松香酯、 石油樹脂、醇酸樹脂、石油樹脂變性松香•苯酚樹脂、石 油樹脂變性松香酯、石油樹脂變性醇酸樹脂、醇酸樹脂變 · 性松香•苯酚樹脂、醇酸樹脂變性松香酯、丙烯變性松香 •苯酚樹脂、丙烯變性松香酯、胺甲酸變性松香·苯酚樹 脂、胺甲酸變性松香酯、胺甲酸變性醇酸樹脂、環氧變性 松香•苯酚樹脂、環氧變性松香酯、環氧變性醇酸樹脂等 用於印刷油墨的公知樹脂類，及亞麻仁油、大豆油、桐油、 棕侶油、蓖麻子油等植物油類、大豆油脂肪酸甲酯、大豆 油脂肪酸丁酯、大豆油脂肪酸異丁酯、大豆油脂肪酸2 _乙 基己酯、亞麻仁油脂肪酸丁酯、亞麻仁油脂肪酸異丁酯、 G 妥爾油脂肪酸丁酯、妥爾油脂肪酸2 -乙基己酯、妥爾油脂 肪酸辛酯、妥爾油脂肪酸異戊四醇酯、棕梠油脂肪酸甲酯、 棕梠油脂肪酸丁酯、棕梠油脂肪酸異丁酯、棕梠油脂肪酸 2 -乙基己酯、蓖麻子油脂肪酸甲酯、蓖麻子油脂肪酸丁酯、 蓖麻子油脂肪酸異丁酯、蓖麻子油脂肪酸2_乙基己酯等脂 肪酸酯類，公知的可使用於印刷油墨之高沸點石油類溶 劑，螯合劑係一般稱爲鋁螯合劑者，例如正丁氧化鋁、異 丁氧化鋁、第二丁氧化鋁的衍生物、正丁氧基、異丁氧基、 -13- 200403316 第一丁氧基等各個基中任一個基被乙基乙酸酯或甲基乙醯 > 乙酸醋取代之化合物等的螯合劑，螯合劑之外的交聯劑例 如含環氧基之單體或樹脂、含異氰酸酯基之單體或樹脂 等’亦可使用交聯上述公知的樹脂之交聯劑、BHT等抗氧 化齊!I等’將這些物質加熱溶解即可製造展色料（淸漆）。 又’可使用的蠟質例如聚乙烯鱲、PTFE蠟、颯哲奴蠟 (S A S〇L· w a X)等公知的臟類。 1 ’含有本發明的乾燥劑之印刷油墨爲氧化聚合乾燥 型’故即使在保存時和空氣接觸後亦會乾燥形成皮膜。此 € 現象稱爲結皮現象，爲要不易發生結皮現象可添加兒茶 酸。添加兒茶酸時其添加時期無特別的限制，通常在調整 印刷油墨後添加較理想。添加的方法係於印刷油墨中充分 攪拌使均勻地分散即可，亦可使用輥磨機等進行捏合。印 刷油墨中乾燥劑的添加量爲〇. 〇 1〜1. 〇質量較理想。 又，硼酸的金屬鹽亦可和本發明的印刷油墨用乾燥劑倂 用。The situation of manganese is ideal. G and 'When using a desiccant of a metal salt of a fatty acid as described in the above (3) in a printing ink, a desiccant (a metal content of 3% to 12%) of a fatty acid-containing iron salt is added so that the ink is contained in the ink. 〇〇3〜〇. 3 6 mass. It is desirable to add a desiccant containing a fatty acid manganese salt (metal content 3% to 2%) to make the printing ink contain 0.003 to 0.12% by mass of manganese. Also, towel inks have been sold with soy oil instead of V OC components and printing inks with reduced V 0 C content. However, the drying properties of this type of printing ink are worse than those of previous printing inks. The problem of the so-called "poor protection" between the printed surface or the printed surface is printed on December 12, 200403316. By using the desiccant containing iron salts of fatty acids and manganese salts of fatty acids of the present invention, Can remove or reduce the "poor protection" phenomenon mentioned above. The printing ink of the present invention may contain various additives for printing inks, such as wax, in addition to the above-mentioned desiccant, pigments and other color materials, and color developing materials (paints). The production method of this pigment (lacquer) is rosin modified phenol resin, rosin ester, petroleum resin, alkyd resin, petroleum resin modified rosin • phenol resin, petroleum resin modified rosin ester, petroleum resin modified alkyd resin, alkyd resin. Modified rosin • phenol resin, alkyd resin modified rosin ester, propylene modified rosin • phenol resin, propylene modified rosin ester, carbamic acid modified rosin · phenol resin, carbamic acid modified rosin ester, carbamic acid modified alkyd resin, epoxy resin Modified rosin • phenol resin, epoxy modified rosin ester, epoxy modified alkyd resin and other well-known resins used in printing inks; and linseed oil, soybean oil, tung oil, palm oil, castor oil and other vegetable oils, etc. Soybean oil fatty acid methyl ester, soybean oil fatty acid butyl ester, soybean oil fatty acid isobutyl ester, soybean oil fatty acid 2-ethylhexyl ester, linseed oil fatty acid butyl ester, linseed oil fatty acid isobutyl ester, G tall oil fatty acid butyl ester , Tall oil fatty acid 2-ethylhexyl ester, Tall oil fatty acid octyl ester, Tall oil fatty acid isoprene tetraol ester, Palm oil fatty acid methyl ester, Emu oil fatty acid butyl ester, palm emu oil fatty acid isobutyl ester, palm emu oil fatty acid 2-ethylhexyl ester, castor oil fatty acid methyl ester, castor oil fatty acid butyl ester, castor oil fatty acid isobutyl ester, castor oil fatty acid 2 _Ethylhexyl esters and other fatty acid esters, well-known high-boiling petroleum solvents that can be used in printing inks. Chelating agents are generally called aluminum chelating agents, such as n-butyl aluminum oxide, isobutyl aluminum oxide, and second butadiene oxide. Derivatives of aluminum, n-butoxy, isobutoxy, -13-200403316 compounds in which any one of the groups, such as the first butoxy group, is replaced by ethyl acetate or methyl ethyl acetate, etc. Chelating agents, cross-linking agents other than chelating agents such as monomers or resins containing epoxy groups, monomers or resins containing isocyanate groups, etc. Oxidation! I, etc. 'These materials can be heated to dissolve to produce pigments (paints). Examples of usable waxes include well-known dirt such as polyethylene fluorene, PTFE wax, and senolite wax (SA SOL · w a X). 1'The printing ink containing the desiccant of the present invention is an oxidative polymerization drying type ', so that it will dry to form a film even after being stored in contact with air. This € phenomenon is called crusting. To prevent crusting, catechin can be added. When adding catechin, there is no particular limitation on the period of addition, and it is usually desirable to add it after adjusting the printing ink. The method of addition may be sufficient stirring in the printing ink to uniformly disperse it, and kneading may also be performed using a roll mill or the like. The added amount of desiccant in the printing ink is 〇 1〜1. 〇 The quality is ideal. Moreover, the metal salt of boric acid can also be used with the drying agent for printing inks of this invention.
(實例） G 其次，以實例說明本發明，惟本發明不受限於這些實 例。實例中的份及％若無特別說明均以質量爲基準。 實例1係相關於含有脂肪酸的鈽鹽及脂肪酸的錳鹽之印 刷油墨用乾燥劑。 實例2係相關於含有脂肪酸的鐵鹽及脂肪酸的錳鹽之印 刷油墨用乾燥劑。 在實例1、2及比較例1、2中，添加乾燥劑之印刷油墨 的基本係根據下列的組成而調製。 -14- 200403316 6〇質量份。 35質量份。 5質量份。 "&由松香變性苯酚樹 高沸點石油類溶劑等 a) 大日本_德工業_^___八 b) 大日本油靴學工她飼謂旨»咖153 c) 0 mm 上述的a)基本油墨係將顏料分散 脂、亞麻仁油及/或大豆油等油脂類、 組成的淸漆中而形成。 〜、b )的淸漆係以松香變性苯1分樹脂及亞麻仁油·大豆油 等油脂、高沸點石油類溶劑等爲主要成分。(Example) G Next, the present invention will be described with examples, but the present invention is not limited to these examples. Parts and% in the examples are based on mass unless otherwise specified. Example 1 relates to a desiccant for printing inks which contains a sulfonium salt of a fatty acid and a manganese salt of a fatty acid. Example 2 relates to a desiccant for printing inks, which contains iron salts of fatty acids and manganese salts of fatty acids. In Examples 1, 2 and Comparative Examples 1 and 2, the printing inks to which the desiccant was added were basically prepared according to the following compositions. -14- 200403316 60 mass parts. 35 parts by mass. 5 parts by mass. " & Rosin denatured phenol tree high boiling point petroleum solvents, etc. a) Dainippon_German Industry _ ^ ___ Eight b) Dainippon Oil Bootman ’s purpose »Ca153c) 0 mm a) above The ink is formed by varnishes composed of pigment-dispersed fat, linseed oil, and / or soybean oil, and the like. ~, B) The lacquer is mainly composed of rosin-denatured benzene 1-point resin, linseed oil and soybean oil, and other high-boiling petroleum solvents.
Μ寸））的物貝混合後’添加規定量的各自使用之乾 燥劑並以輕磨機使呈均句分散狀態、，並使已完成的印刷油 墨進行乾燥試驗。 根據JIS Κ5 70 1 -1「平版油墨試驗方法（第一冊）」的「依 據4. 4. 3 C型乾燥g式驗機之方法」中記載之方法進行乾燥 試驗。 實例1 將下列所示的1 )、2)二種類的乾燥劑依表2所示的規定 墓混合’並添加於上述的印刷油墨中，進行此乾燥劑的乾 燥試驗。 1 )環烷酸錳.....含金屬率爲5 %的錳類乾燥劑（表 示爲Μ η -5 )。 2)含鈽的金屬和辛酸形成的鹽，含金屬率爲6 %的鈽類乾 燥劑（表示爲C e -6 )。 其中環烷酸錳乾燥劑的用量爲〇. 1、〇. 3、0.5 % 3種，辛 酸和含鈽的金屬形成的鹽的乾燥劑之用量爲〇、〇 · 5、1.0、 1 · 5 % 4 種。 4 4200403316 比較例1係在印刷油墨中單獨添加環烷酸錳乾燥劑。 乾燥試驗之結果如表2所示。 表2 (實例1的乾燥試驗結果） 實例 實例1-2 實例1-3 比較例1 C e -6 0.5% 1.0% 1.5% 0.0% Mn-5 0.1% 700分 620分 500分 880分 Μ η-5 0.3% 350分 310分 280分 470分 Mn-5 0.5% 270分 240分 210分 350分 紙張油墨的乾燥時間係依用途而異，通常在2 5 °C的狀態 下約爲500〜800分較適當。 從表2得知，比較例1將Μη- 5減少至0.1 %後乾燥時間 則超過800分鐘，實例中藉著添加 〇·1% Μη-5及0.5% Ce-6，可縮短乾燥時間爲小於8 0 0分鐘。又，可依需求藉 著改變Μη-5或Ce-6的用量更可控制縮短乾燥時間。 實例2 1 )環烷酸錳，含金屬率爲5 %的錳類乾燥劑（表示爲 Μ η - 5 ) 〇 2 )環烷酸鐵’含金屬率爲5 %的鐵類乾燥劑（表示爲Fe-5 ) ° 將上述1 )及2)的乾燥劑依規定的量混合在上述的印刷 油墨中，進行其乾燥試驗。 其中環烷酸錳乾燥劑的用量爲〇 . 1、〇 . 3、0 · 5 % 3種，環 烷酸鐵乾燥劑之用量爲〇、〇 . 5、1 . 0、1 . 5 % 4種。 比較例2係在印刷油墨中單獨添加環烷酸錳乾燥劑。 車乙無S式驗之結果如表3所示。 -16- 200403316 表3 (實例2的乾燥試驗結果） 實例2-1 實例2-2 實例2-3 比較例2 Fe-5 0.5% 1.0% 1.5% 0.0% Mn-5 0.1% 640分 520分 480分 880分 Mn-5 0.3% 350分 270分 260分 470分 Mn-5 0.5% 260分 240分 200分 350分M inch)) After the shellfish is mixed, a predetermined amount of the desiccant used is added, and the homogeneous sentence is dispersed with a light mill, and the completed printing ink is subjected to a drying test. The drying test was performed in accordance with the method described in "Method for 4.4.3 Type C Dry G-type Inspection Machine" in JIS KK5 70 1 -1 "Lithographic Ink Test Method (Vol. 1)". Example 1 Two types of desiccants 1) and 2) shown below were mixed according to the specifications shown in Table 2 and added to the above-mentioned printing ink, and a drying test of the desiccant was performed. 1) Manganese naphthenate ..... a manganese-based desiccant with a metal content of 5% (indicated as M η -5). 2) A salt formed by a rhenium-containing metal and caprylic acid, and a rhenium-based desiccant having a metal content of 6% (expressed as Ce-6). Among them, the amount of manganese naphthenate desiccant is 0.1, 0.3, 0.5%, and the amount of desiccant of salt formed by caprylic acid and rhenium-containing metal is 0, 0.5, 1.0, 1.5%. 4 types. 4 4200403316 Comparative Example 1 A manganese naphthenate desiccant was separately added to the printing ink. The results of the drying test are shown in Table 2. Table 2 (Drying test results of Example 1) Example Example 1-2 Example 1-3 Comparative Example 1 C e -6 0.5% 1.0% 1.5% 0.0% Mn-5 0.1% 700 points 620 points 500 points 880 points M η- 5 0.3% 350 minutes 310 minutes 280 minutes 470 minutes Mn-5 0.5% 270 minutes 240 minutes 210 minutes 350 minutes The drying time of paper and ink varies depending on the application, usually about 500 to 800 minutes at a temperature of 25 ° C More appropriate. As can be seen from Table 2, Comparative Example 1 reduced the drying time to more than 800 minutes after reducing Mη-5 to 0.1%. In the example, by adding 0.1% Mη-5 and 0.5% Ce-6, the drying time can be shortened to less than 80 minutes. In addition, the drying time can be controlled by changing the amount of Mn-5 or Ce-6 as required. Example 2 1) Manganese naphthenate, a manganese-based desiccant with a metal content of 5% (indicated as M η-5) 〇2) Iron naphthenate 'iron-based desiccant with a metal content of 5% (indicated as Fe-5) ° The desiccants of 1) and 2) were mixed with the above-mentioned printing ink in a predetermined amount, and the drying test was performed. Among them, the amount of manganese naphthenate desiccant is 0.1, 0.3, 0.5%, and the amount of iron naphthenate desiccant is 0, 0.5, 1.0, 1.5%. . In Comparative Example 2, a manganese naphthenate desiccant was separately added to a printing ink. The results of Che B without S-type test are shown in Table 3. -16- 200403316 Table 3 (Drying test results of Example 2) Example 2-1 Example 2-2 Example 2-3 Comparative Example 2 Fe-5 0.5% 1.0% 1.5% 0.0% Mn-5 0.1% 640 points 520 points 480 880 points Mn-5 0.3% 350 points 270 points 260 points 470 points Mn-5 0.5% 260 points 240 points 200 points 350 points
從表3得知，比較例2將Μ η- 5減少至0 . 1 %後乾燥時間 則超過8 0 0分鐘，實例2-1〜2-3藉著添力Π 0.1% Μ η-5及0.5 % Fe-5，可縮短乾燥時間爲小於8 0 0分鐘。又，可依需求 藉著改變Μη-5或Fe-5的用量更可控制縮短乾燥時間。 表4中，比較例3〜1 2係參考單獨使用各種脂肪酸的金 屬鹽時的乾燥時間。 -17- 200403316 表4 比較例3 比較例4 比較例5 比較例6 比較例7 比較例8 比較例9 比較例10 比較例1〗 比較例η Mn-5 0.5% 1.0% Co-12 0.5% 1.0% Co-Na 0.5% 1.0% Ce-6 0.5% 1.0% Fe-5 0.5% 1.0% 乾燥時間 (分） 350 270 170 90 360 200 1680< 1680< 1680< 1680<As can be seen from Table 3, Comparative Example 2 reduced Μ η-5 to 0.1%, and then the drying time exceeded 800 minutes. Examples 2-1 to 2-3 added Tim Π 0.1% Μ η-5 and 0.5% Fe-5, which can shorten the drying time to less than 800 minutes. In addition, the drying time can be further controlled by changing the amount of Mn-5 or Fe-5 as required. In Table 4, Comparative Examples 3 to 12 refer to the drying time when metal salts of various fatty acids are used alone. -17- 200403316 Table 4 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 1 Comparative Example η Mn-5 0.5% 1.0% Co-12 0.5% 1.0 % Co-Na 0.5% 1.0% Ce-6 0.5% 1.0% Fe-5 0.5% 1.0% Drying time (minutes) 350 270 170 90 360 200 1680 < 1680 < 1680 < 1680 <
表4中，Co-Na表示爲鈷金屬鹽的一種，含金屬率爲6 %之環烷酸鈷乾燥劑。又，Co-12表示爲含金屬率爲12% 之辛酸鈷乾燥劑。 實例3 實例3的印刷油墨，係在含大豆油及/或大豆油脂肪 酸的印刷油墨中添加含脂肪酸的鐵鹽及脂肪酸的錳鹽之乾 燥齊1J。 在實例3及比較例1 3中，添加乾燥劑之印刷油墨的基 本係根據下列的組成而調製。 a)大日本油墨化學工業股份公司製藍基質油墨B 60質量份。 b )大日本油墨化學工業股份公司製樹脂淸漆B 35質量份。 c)曰淸製油股份公司製大豆油沙拉油 5質量份。 上述的a )基本油墨係將顏料分散在由松香變性苯酚樹 脂、大豆油等油脂類、大豆油脂肪酸酯等脂肪酸酯組成的 淸漆中而形成。 200403316 b )的淸漆係以松香變性苯酚樹脂及大豆油等油脂、 大豆油脂肪酸酯等脂肪酸酯等爲主要成分。 比較例1 3的油墨，係在上述的印刷油墨中添加含脂肪 酸的錳鹽及脂肪酸的鈷鹽之乾燥劑。 油墨的組成及防黏粘性試驗結果如表5所示。 表5 油墨組成及防黏粘性試驗結果 實例3 比較例13 藍基質B 60 60 淸漆B 33.4 34.8 大豆油 5 5 鐵乾燥劑 1.5 0 錳乾燥劑 0.1 0.1 銘乾燥劑 0 0.1 合計__ 100.0 100.0 防黏粘性試驗結果 4.5 3In Table 4, Co-Na is a kind of cobalt metal salt, and cobalt naphthenate desiccant with a metal content of 6%. In addition, Co-12 is expressed as a cobalt octoate desiccant having a metal content of 12%. Example 3 The printing ink of Example 3 was dried by adding 1J to a printing ink containing soybean oil and / or fatty acid of soybean oil by adding iron salts containing fatty acids and manganese salts of fatty acids. In Example 3 and Comparative Examples 1 to 3, the printing ink to which the desiccant was added was basically prepared according to the following composition. a) 60 parts by mass of Blue Matrix Ink B manufactured by Dainippon Ink Chemical Industry Co., Ltd. b) 35 parts by mass of resin paint B made by Dainippon Ink Chemical Industry Co., Ltd. c) 5 parts by mass of soybean oil salad oil made by Tongzhi Oil Co., Ltd. The above a) basic ink is formed by dispersing a pigment in a varnish composed of oils and fats such as rosin-denatured phenol resin, soybean oil, and fatty acid esters such as fatty acid esters of soybean oil. 200403316 b) The lacquer is mainly composed of rosin-denatured phenol resin and fats such as soybean oil, fatty acid esters such as fatty acid esters of soybean oil, and the like. The ink of Comparative Example 13 was a desiccant containing a manganese salt of a fatty acid and a cobalt salt of a fatty acid added to the above-mentioned printing ink. The composition of the ink and the results of the anti-sticking test are shown in Table 5. Table 5 Ink composition and anti-stick test results Example 3 Comparative Example 13 Blue matrix B 60 60 Lacquer B 33.4 34.8 Soybean oil 5 5 Iron desiccant 1.5 0 Manganese desiccant 0.1 0.1 Ming desiccant 0 0.1 Total __ 100.0 100.0 Prevention Viscosity test result 4.5 3
防黏粘性試驗係將印刷油墨印刷在紙面後將印刷面重 疊，在施加壓力的狀態下，於高溫、多濕的條件下放置一 晚，翌日，剝開印刷面間，採用目視的方式以5階段評估 其剝落狀況（5 (優）> 3 > 1 (劣））。本實例係於溫度5 〇 °C、濕度8 0 %的條件下進行。 評估的判斷基準係印刷面無黏合現象時爲良好，即使有 黏合現象其印刷面的剝落情況少時亦屬良好。 實例4 實例4的印刷油墨，係在含大豆油及/或妥爾油脂肪酸 的印刷油墨中添加含脂肪酸的鐵鹽及脂肪酸的鑑鹽之乾燥 劑。 200403316 在貫例4及比較例！ 4中，添加乾燥劑之印刷油墨的基 本係根據下列的組成而調製。 60質量份。 35質量份。 5質量份。 a) 大日本油墨化學工業股份公司製藍基質油墨ς b) 大日本油墨化學工業股份公司製樹脂淸漆C Ο日淸製油股份公司製大豆油沙拉油 上述的a )基本油墨係將顏料分散在由松香變性苯酚 樹恥、大丑油等油脂類、妥爾油脂肪酸酯等脂肪酸酯組成 的淸漆中而形成。The anti-adhesion test is to print the printing ink on the paper surface and overlap the printing surfaces. Under pressure, place it under high temperature and humidity conditions for one night. On the next day, peel off the printing surface. The stage evaluates its peeling condition (5 (excellent)> 3> 1 (inferior)). This example was performed under the conditions of a temperature of 50 ° C and a humidity of 80%. The evaluation criterion is good when the printed surface is free of sticking, and even if there is little peeling of the printed surface, it is good. Example 4 The printing ink of Example 4 is a desiccant in which a printing ink containing soybean oil and / or tall oil fatty acid is added with an iron salt containing fatty acid and a salt of fatty acid. 200403316 In case 4 and comparative example! In 4, the printing ink to which a desiccant is added is prepared based on the following composition. 60 parts by mass. 35 parts by mass. 5 parts by mass. a) Blue matrix ink made by Dainippon Ink Chemical Industry Co., Ltd. b) Resin varnish C by Dainippon Ink Chemical Industry Co., Ltd. Soy oil salad oil manufactured by Nippon Oil Co., Ltd. a) The above basic ink is a pigment dispersed in It is formed from varnishes composed of rosin-modified phenolic shavings, oils such as ugly oil, and fatty acid esters such as tall oil fatty acid esters.
b )的淸漆係以松香變性苯酚樹脂及大豆油等油脂、 妥爾油脂肪酸酯等脂肪酸酯等爲主要成分。 比較例4的印刷油墨，係在上述的印刷油墨中添加含脂 肪酸的鑑鹽及脂肪酸的鈷鹽之乾燥劑。 印刷油墨的組成及防黏粘性試驗結果如表6所示。 表6 油墨組成及防黏粘性試驗結果 實例3 比較例13 藍底漆C 60 60 淸漆C 33.4 34.8 大豆油 5 5 鐵乾燥劑 1.5 0 錳乾燥劑 0.1 0.1 鈷乾燥劑 —ggssass — ' - ' 丨 ·π 丨丨二 ___ 0 0.1 合計 .1 _ - — !^="= ·=Γ' ---- ; 100.0 100.0 防黏粘性試驗結果 4.5 3 ㈤【圖式簡單說明】 無 -20-The base paint of b) contains rosin-denatured phenol resin, soybean oil and other fats and oils, such as tall oil fatty acid esters, as main components. The printing ink of Comparative Example 4 was a desiccant in which the above-mentioned printing ink was added with a salt of a fatty acid and a cobalt salt of a fatty acid. The composition of the printing ink and the results of the anti-sticking test are shown in Table 6. Table 6 Ink composition and anti-stick test results Example 3 Comparative Example 13 Blue primer C 60 60 Paint C 33.4 34.8 Soybean oil 5 5 Iron desiccant 1.5 0 Manganese desiccant 0.1 0.1 Cobalt desiccant —ggssass — '-' 丨· Π 丨 丨 Second ___ 0 0.1 Total. 1 _-—! ^ = &Quot; = · = Γ '----; 100.0 100.0 Anti-adhesion test result 4.5 3 ㈤ [Simplified description of the figure] None -20-