200536903 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種低溫硬化性、塗膜硬度、模印記隱蔽 性均優異的消光陰離子電鍍塗料。 【先前技術】 鋁係具有所謂的量輕且加工性容易、以及耐蝕性均優異 的性質，利用鋁之該等性質而可以被使用於大多數的材料， 特別是建材關連材料。 • 該鋁之熱間押出之方法，通常是一種將圓柱形的鋁鑄塊 予以加熱熔融，接著再將此種熔融物投入押出機中，予以按 押於具有預定斷面形狀之孔的模具上，使之依序地通過孔而 得到具有預定形成之型材之方法。 又，鋁材本身之防蝕性、耐摩耗性、耐葯品性通常是不 佳的，因而一般是在將鋁予以陽極氧化處理之後，再藉由消 光之陰離子電鍍塗料而被覆一消光之塗膜。 然而，上述之消光陰離子電鍍塗料經電鍍塗裝於陽極氧 ® 化處理後之鋁型材的情況下，素材之鋁型材的模印記容易明 顯化以致會有商品價値低劣化之問題點。 向來，爲使得像這樣的模印記不易明顯化，已有關於一 種陰離子電鍍塗料之發明；其係將溶解性參數不同的2種丙 烯酸系樹脂、以及和彼等之丙烯酸系樹脂不具相溶性的蜜胺 樹脂予以水分散所形成。〔專利文獻彳〕。另外之發明爲含 有水分散性樹脂和蜜胺樹脂，並藉由樹脂之S P値的差而得 到之消光塗膜。〔專利文獻2〕。 200536903 此等之發明由於需要1 70 °c以上之燒成，因而不但陽極 氧化皮膜容易產生裂縫、精整性及塗膜性能降低，且消耗能 量變多，所以在經濟上也是有問題的。 其他方面，當使用氫氧基及羧基含有樹脂、嵌段化聚異 氰酸酯化合物的塗料之情況下，雖然於1 4 0 °C燒成也可以得 到凝膠分率爲90 %以上之硬化性、及高的塗膜硬度（鉛筆硬 度爲4H以上）之物，然而卻是低光澤（60 °光澤爲1 0以下）、 及模印記隱蔽性也不夠充分〔專利文獻3〕。 φ 另外，一種關於在1分子中具有2個以上之游離異氰酸 酯基的乙烯系共聚物之游離異氰酸酯基的一部分，在1分子 中具有2個以上之氫氧基之丙烯酸樹脂中之該氫氧基的一 部分起反應，接著使全部的殘存之游離異氰酸酯基與嵌段化 劑起反應而成之在1分子中具有倂存的嵌段異氰酸酯基和 氫氧基之樹脂的發明〔專利文獻4〕。就單只將該發明使用 於消光陰離子電鍍塗料而言，是得不到低溫硬化性、塗膜硬 度、模印記隱蔽性均優異的消光塗膜。尙且，消光塗膜之模 • 印記隱蔽性是優異的。 【專利文獻1】特開平1 0-46065號公報 【專利文獻2】特開2001 -1 31 494號公報 【專利文獻3】特開平8-41 380號公報 【專利文獻4】特開平5-2471 75號公報 【發明內容】 【發明所欲解決之課題】 所欲解決之問題點在於：發現一種低溫硬化性、塗膜硬 200536903 度、模印記隱蔽性均優異的消光陰離子電鍍塗料。 【用以解決課題之手段】 本發明人等爲了解決上述之問題點，乃刻意地重複地進 行硏究，結果發現藉由使用一種利用將在1分子中具有2個 以上之游離異氰酸酯基的乙烯系共聚物（a 1 )之該游離異氰 酸酯基的一部分，與具有氫氧基、羧基及烷氧矽烷基之乙烯 系共聚物（a2)之氫氧基的一部分起反應，接著使全部的殘存 之游離異氰酸酯基與嵌段化劑起反應而成之在1分子中具 φ 有倂存的嵌段異氰酸酯基和氫氧基之樹脂（A)與硬化觸媒 (B)所形成之消光陰離子電鍍塗料即可以達成，至此乃完成 本發明。 也就是說，本發明係： 1 . 一種消光陰離子電鍍塗料，其特徵在於：藉由利用將在1 分子中具有2個以上之游離異氰酸酯基的乙烯系共聚物 (a 1)之該游離異氰酸酯基的一部分，與具有氫氧基、羧基 及烷氧矽烷基之乙烯系共聚物（a2)之氫氧基的一部分起 • 反應，接著使全部的殘存之游離異氰酸酯基與嵌段化劑 起反應而成之在1分子中具有倂存的嵌段異氰酸酯基和 氫氧基之樹脂，且乙烯系共聚物（a 1 )和乙烯系共聚物（a2) 之溶解性參數（SP値）的差爲0_4〜1 .0之樹脂（A)予以水 分散化，更且進一步添加硬化觸媒（B)予以分散化所形成 的乳化液而構成，且含有相對於樹脂（A)之總量1 〇〇重量 份計爲〇_1〜10重量份之硬化觸媒（B)。 2.如第1項之消光陰離子電鍍塗料，其中硬化觸媒（B)爲自 200536903 有機錫化合物及胺化合物中所選出之至少1種的化合物。 3. 如第1或2項之消光陰離子電鍍塗料，乙烯系共聚物（a 1 ) 爲由含有異氰酸酯基之乙烯系單體及其他的乙烯系單體 所形成的共聚物。 4. 一種消光塗裝物品，其在經陽極氧化處理的鋁基材上， 塗裝如第1至3項中任一項之消光陰離子電鍍塗料所形 成之塗膜面的60°光澤度係爲10以下。 【發明效果】 • 本發明之消光陰離子電鍍塗料，係可以藉由在14CTC下 進行低溫燒成乾燥20分鐘而得到塗膜硬度（鉛筆硬度爲4H 以上）、及模印記隱蔽性均優異的60 °光澤度爲1 0以下之消 光塗膜。 本發明之組成物由於具有使用以蜜胺樹脂做爲硬化成 分所不能達成之陰離子電鍍塗料之低溫硬化性，所以能夠解 除習用的藉由在170 °C燒成之陽極氧化皮膜的裂縫、及塗膜 性能下降、以及消耗能量變大等之問題點；又且，可以得到 ® 一種使用習用的嵌段化聚異氰酸酯化合物做爲硬化成分之 陰離子電鍍塗料所不能達成之消光塗膜。 【實施方式】 【用以實施發明之最佳形態】 本發明之消光陰離子電鍍塗料係一種含有包括樹脂（A) 和硬化觸媒（B)並進行水分散而成的乳化液之低溫硬化性良 好的消光陰離子電鍍塗料。以下，詳細說明之。 樹脂（A):樹脂（A)係一種在1分子中具有2個以上之游 200536903 離異氰酸酯基的乙烯系共聚物（a 1 )之該游離異氰酸酯基的 一部分，與在側鏈上具有氫氧基、羧基及烷氧矽烷基之乙烯 系共聚物（a2)(以下，簡稱爲水分散乙烯系共聚物（a2)之氫氧 基的一部分起反應，接著使全部的殘存之游離異氰酸酯基與 嵌段化劑起反應而成之在1分子中具有倂存的嵌段異氰酸 酯基和氫氧基之樹脂所構成者。 乙烯系共聚物（a 1 )係以含有異氰酸酯基之乙烯系單體 (以下，簡稱爲「含有NCO基之單體」）當做必要成分，並使 0 用其他的乙烯系單體所形成的共聚物，主要是使在直鏈狀之 共聚物的末端及/或側鏈上具有異氰酸酯基。 含有NCO基之單體係爲一種在1分子中分別具有至少 一個的未嵌段的游離異氰酸酯基、和自由基聚合性雙鍵之化 合物’例如，可以使用自m -或p -異丙烯基-α，α-二甲基苄 基異氰酸酯、2-異氰酸酯乙基甲基丙烯酸酯、含有氫氧基之 乙嫌系單體和二異氰酸酯化合物之1 : 1(莫耳比）加成物等中 所選取的1種或2種以上。 • 在調製含有NCO基之單體上所用的上述含有氫氧基之 乙嫌系單體’係爲一種在1分子中分別具有1個以上之氫氧 基和自由基聚合性雙鍵之化合物，舉例來說，例如其可以是 2-經乙基（甲基）丙烯酸酯、2_羥丙基（甲基）丙烯酸酯、羥丁 基丙嫌酸酯、2,3-二羥丙基丙烯酸酯、2-羥基-3-苯氧乙基丙 稀酸酯、2-羥基-3-乙氧乙基丙烯酸酯等。更且，舉例來說， 例如其可以是丙烯酸或甲基丙烯酸和二醇（碳原子數爲2〜 2〇)等之莫耳加成物等。 *200536903 在調製含有NCO基之單體上所用的上述二異氰酸酯化 合物，係爲在1分子中具有2個異氰酸酯基之物，舉例來說’ 例如其可以是伸甲苯基二異氰酸酯、4,4’-二苯基甲烷二異氰 酸酯、伸二甲苯基二異氰酸酯、六亞甲基二異氰酸酯、離氨 酸二異氰酸酯、4,4’-亞甲基雙（環己基異氰酸酯）、甲基環己 烷-2,4 (2,6)-二異氰酸酯、異弗爾酮二異氰酸酯及三甲基己 烷二異氰酸酯等之脂肪族、芳香族及脂環族系的二異氰酸酯 化合物。 • 上述含有NCO基之單體中較佳之物，從防止後述的乙 烯系共聚物（a2)間之反應中的凝膠化之觀點來看，特佳爲使 用具有第3級異氰酸酯基之m-異丙烯基-α，α -二甲基苄基 異氰酸酯。 又，其他的乙烯系單體，較宜是在1分子中具有自由基 聚合性雙鍵、且不具有可以和異氰酸酯基反應的活性氫之化 合物；具體而言，舉例來說，例如其可以是苯乙烯、α -甲 基苯乙烯、乙烯基甲苯等之芳香族乙烯系單體；甲基（甲基） • 丙烯酸酯、乙基（甲基）丙烯酸酯、丁基（甲基）丙烯酸酯、2-乙基己基（甲基）丙烯酸酯、月桂基（甲基）丙烯酸酯、十三基 (甲基）丙烯酸酯、硬脂酸基（甲基）丙烯酸酯、環己基（甲基） 丙烯酸酯、苄基（甲基）丙烯酸酯等之（甲基）丙烯酸酯類； 必斯可特3F(大阪有機化學社製、商品名、以下表示同 樣的意義），同上3MF、同上8F、同上8MF、全氟環己基（甲 基）丙嫌酸酯、Ν-2·丙基全氟辛院磺酸醢胺乙基（甲基）丙烯酸 酯、氟化乙烯、氟化亞乙烯等之含氟乙烯系單體； -11- 200536903 Ν, Ν’-二乙基胺基乙基（甲基）丙烯酸酯、Ν，Ν’-二乙基胺 基乙基（甲基）丙烯酸酯、Ν，Ν’-二乙基胺基乙基（甲基）丙烯酸 酯、Ν,Ν’-二乙基（甲基）丙烯醯胺等之含氮乙烯系單體；乙烯 基乙基醚、乙烯基丁醚等之乙烯基醚系單體；以及 (甲基）丙烯酸縮水甘油酯、3,4-環乙氧環己基甲基（甲 基）丙烯酸酯、丙烯酸基縮水甘油醚、羥甲基丙烯醯胺之烷 基醚化物、（甲基）丙烯醯胺、（甲基）丙烯酸氯、氯化乙烯、 氯化亞乙烯、（甲基）丙烯腈、r -甲基丙烯酸氧烷基三甲氧矽 # 烷等；可以使用此等之中的1種或混合2種以上。 含有N C Ο基之單體和其他的乙烯系單體間之比例，只 要乙烯系共聚物（a1)之1分子中具有2個以上之游離異氰酸 酯基的範圍的話即可，並沒有特別地限定，然而以含有N C〇 基之單體/其他的乙烯系單體（重量比）爲基準計適宜的範圍 是100/0〜1/99，較宜是在65/35〜30/70之範圍。 又，僅含有NCO基之單體、或者此等以外之其他的乙 烯系單體間之聚合反應，通常較宜是在不具有可以和異氰酸 • 酯基反應之活性氫的惰性有機溶劑中進行。 此種惰性有機溶劑，例如’可以使用己烷、庚烷、辛烷 等之脂肪族烴系、酯系、酮系等之單一、或混合溶劑。具體 而言，例如，可以使用甲氧丙基乙酸酯和t-丁基-過氧異丙 基碳酸酯之混合溶劑。此等之溶劑由於是一種含有水分之 物，因而較宜是視情況需要地預先進行脫水。 此等之聚合反應’通吊是在50〜180 °C之溫度下，使用 自由基聚合起始劑來進行的，乙烯系共聚物（3彳）之分子量可 200536903 以藉由反應濃度、起始劑量等來調整。反應濃度是在聚合物 之20〜80重量％之範圍內進行。 特別是爲了提筒聚合率，較宜是使用過氧化物系或碳酸 酯系起始劑，以1 00 °c以上之反應溫度下進行。更宜是與丙 烯酸酯系單體倂用時，可容易地得到聚合率高之聚合物。聚 起始劑之濃度，雖然可以使用總單體之0 · 0 1〜15重量％之 範圍內者，然而較宜是在0_1〜10重量。/。之範圍內。 此種乙烯系共聚物（a1)之重量平均分子量（註1)宜是 # 500〜50000，特佳是在1500〜30000之範圍。又，合適的 異氰酸酯價是30〜200毫克NC 0/10克。又，乙烯系共聚物 (a1)雖然是在1分子中具有2個以上之游離的異氰酸酯基， 然而較宜是完全沒有可以和該異氰酸酯基反應之活性氫。 (註1)重量平均分子量：以JIS K01 24-83爲基準來進 行，分離管柱係使用TSK GEL 4000 HXL +G 3000 Hu +G 2500 HXL + G 2000 HXL (東洋曹達（股）公司製），於 40°C、1.0 毫升/分鐘之流速下、使用GPC用四氫咲喃做爲溶離液、以 • RI折射計測得色層管柱和聚苯乙烯之檢量線計算而求得。 乙烯系共聚物（a2): 乙烯系共聚物（a2)係適合使用以（1 )含有烷氧矽烷基之 不飽和單體、（2)含有氫氧基之不飽和單體、（3)含有羧基之 不飽和單體當做必要成分，並視情況需要與（4)其他的不飽 和單體共聚合而成之物。此等之單體成分，舉例來說，例如 其可以是以下所述者。 (1 )含有烷氧矽烷基之不飽和單體：舉例來說，例如其 200536903 可以是r -(甲基）丙烯醯基氧丙基三甲氧矽烷、r -(甲基）丙 烯醯基氧丙基甲基二甲氧矽烷、r-(甲基）丙烯醯基氧丙基三 乙氧矽烷、乙烯基三甲氧矽烷等。 (2) 含有氫氧基之不飽和單體：舉例來說，例如其可以 是羥乙基（甲基）丙烯酸酯、羥丙基（甲基）丙烯酸酯、以及此 等以外之普拉庫西爾fivm (戴西爾化學製，商品名，己內醯 胺改性（甲基）丙烯酸羥基酯類）、普拉庫西爾FM2(同左）、普 拉庫西爾FM3(同左）、普拉庫西爾FA1(同左）、普拉庫西爾 # FA2(同左）、普拉庫西爾FA3(同左）等之含有氫氧基之不飽和 單體類等。 (3) 含有羧基之不飽和單體：舉例來說，例如其可以是（甲 基）丙烯酸、馬來酸等。 (4) 其他之不飽和單體：舉例來說，例如其可以是（甲基） 丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基） 丙烯酸丁酯、（甲基）丙烯酸己酯、（甲基）丙烯酸辛酯、（甲基） 丙烯酸月桂酯、（甲基）丙烯酸環己酯等之（甲基）丙烯酸的C1 • 〜C18之烷酯或環烷酯類、苯乙烯等之芳香族乙烯基單體 類、（甲基）丙烯醯胺、N-丁氧甲基（甲基）丙烯醯胺、N-羥甲 基（甲基）丙烯醯胺等之（甲基）丙烯醯胺及其衍生物類、（甲 基）丙烯腈化合物類等。 此等乙烯系共聚物（a2)之重量平均分子量宜是500〜 50000，特佳爲2000〜35000之範圍，特別合適的氫氧基， 基於羥基價計爲20〜200毫克KOH/克之範圍。 就樹脂（A)之製造而言，乙烯系共聚物（a 1 )和乙烯系共聚 200536903 物（a2)間之反應係爲異氰酸酯基和氫氧基間之胺基甲酸酯 化反應’具體而言，可以將乙烯系共聚物（a2)摻混在乙烯系 共聚物（a1)之有機溶液中，通常是在20〜10CTC、較佳爲在 25〜6CTC之溫度下進行胺基甲酸酯化反應。 反應是藉由異氰酸酯基的減少量、亦即異氰酸酯價來進 行控制的。又，在此種反應中，爲了得到低溫硬化性及塗膜 硬度也較宜是使用有機錫化合物等之硬化觸媒。 乙烯系共聚物（a2)之摻混量，只要是每1分子的重量平 φ 均分子量爲500〜50000之乙烯系共聚物（a1 )中可以導入至 少平均〇 · 1個胺基甲酸酯鍵的摻混量即可，然而，較佳爲每 1分子的重量平均分子量爲50 0〜30000之乙烯系共聚物 (a 1 )中可以導入至少平均〇_5〜1 .5個胺基甲酸酯鍵，特別是 以每1分子的乙烯系共聚物（a 1 )中可以導入1個胺基甲酸酯 鍵爲最佳。 其次，藉由使如以上所述之乙烯系共聚物（a2)起反應而 導入胺基甲酸酯鍵，並使得在加成有水分散性乙烯系共聚物 • (a2)之乙烯系共聚物（a1)中所含的殘存之游離的異氰酸酯、 和以下之嵌段劑在通常之20〜1 00 °C的溫度下起反應進行 爰段，即可以得到樹脂（A)。 嵌段劑，舉例來說，例如其可以是酚、甲酚、二甲苯酚、 p-乙酚、〇-異丙酚、P-tert_丁酚、P_tert-辛酚、百里香酚、 p_萘酸、p -硝基酣、p -氯酌等之酿系； 甲醇、乙醇、丙醇、丁醇、乙二醇、甲基溶纖素、乙基 溶纖素、甲基卡必醇、苄基醇、苯基溶纖素、糠基醇、環己 -15- 200536903 醇等之醇系·,丙二酸二甲酯、乙醯乙酸酯等之活性亞甲基系； 丁硫醇、硫酣、tert -十二基硫醇等之硫醇系；乙醯替苯 胺、乙醯替甲氧基苯胺、醋酸醯胺、苯醯胺等之酸醯胺系； 琥珀酸醯胺、馬來酸醯亞胺等之醯亞胺系； 二苯基胺、苯基萘基胺、苯胺、咔唑等之胺系；咪唑、 2-乙基咪唑等之咪唑系；尿素、硫尿素、伸乙基尿素等之尿 素系；N-苯基胺基甲酸苯酯、2-噚唑啉酮等之胺基甲酸鹽 系；伸乙基亞胺等之亞胺系； •甲醛肟、乙醛肟、丙酮肟、甲乙酮肟、甲基異丁酮肟、 環己酮肟等之肟系；亞硫酸蘇打、亞硫酸氫鉀等之亞硫酸鹽 系； ε-己內醯胺、5-戊內醯胺、7 -戊內酯、/3-丙內酯等 之內酯系；3,5-二甲基吡唑、3-甲基吡唑、4-硝基3,5-二甲 基吡唑、以及4-溴-3,5-二甲基吡唑等之吡唑系等。 樹脂（Α)係藉由異氰酸酯基氫氧基間之胺基甲酸酯反 應、透過胺基甲酸酯鍵而將乙烯系共聚物（a 1 )和乙烯系共聚 ®物（a2)鍵結在一起。 如此做法所得到的樹脂（A),其在分子中具有平均至少 一個的嵌段異氰酸酯基和至少一個氫氧基，其重量平均分子 量爲1000〜120000左右，特別是5000〜50000左右，合適 的氫氧基價（毫克KOH/克）係25〜250之範圍。 尤其，爲了得到低光澤（6 0。光澤度爲1 0以下）之消光 塗膜，則乙烯系共聚物（a 1 )和乙烯系共聚物（a2)間之溶解性 參數（SP値（註2))之差値宜是在之範圍，較宜是 200536903 〇_5 〜〇·8 〇 (註2)溶解性參數：SP値係爲Solubility Parameter之 簡稱，表示液體分子之分子間相互作用之尺度。就該S P値 而言，以乙烯系共聚物（a 1 )和水分散性乙烯系共聚物（a2)成 分論’當單體之SP値係爲已知時可以使用下述式（彳）來求得 共聚物單體之S P値，以此之S P値來當做共聚物之S P値使 用。 單體之S P値於油漆技術期刊第4 2卷第1 7 6頁（1 9 7 0 ) # 中已有整理。 SP = SPiXfW1 + SP2xfW2+......SPnXfWn 式（1) (SP1 . SP2、 fwi ' fw2 , _ · · SPn係代表各單體之SP値， fwn係代表各單體相對於單體總量 之重量分率。） 又，當單體之s P値未知時，則可以藉由濁點滴定來測 定，具體而言，可以依照下述式（2)，即K. w. SUH、」.M. Corbett之式（應用高分子科學期刊，帛12卷，第2359 頁’ 1968)做爲基準而計算出來。 式（2) VVh *δ·Η ^ VVp *δη200536903 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a matte anion electroplating coating which is excellent in low temperature hardenability, coating film hardness, and mold impression concealment. [Prior art] Aluminum has so-called light weight, easy workability, and excellent corrosion resistance. It can be used in most materials, especially building materials, because of its properties. • The method of extruding aluminum is usually a method of heating and melting a cylindrical aluminum ingot, and then putting the molten material into an extruder to press it onto a mold having a hole with a predetermined cross-sectional shape. A method of sequentially passing through holes to obtain a profile with a predetermined formation. In addition, the corrosion resistance, abrasion resistance, and chemical resistance of aluminum materials are generally poor. Therefore, after the aluminum is anodized, a matte coating film is generally coated with the matte anion plating coating. However, in the case where the above-mentioned matte anion plating coating is electroplated on the aluminum profile after the anodizing treatment, the stamp of the aluminum profile of the material is easy to be displayed, so that there is a problem that the price of the product is low and deteriorated. In the past, in order to make it difficult to make such imprints obvious, there has been an invention of an anionic electroplating coating; it is a type of acrylic resin that has two different solubility parameters, and honey that is not compatible with their acrylic resins. Amine resin is formed by water dispersion. [Patent Literature 彳]. Another invention is a matte coating film containing a water-dispersible resin and a melamine resin, and obtained by the difference of the resin's SPS. [Patent Document 2]. 200536903 Since these inventions require firing above 1 70 ° C, not only the anodic oxide film is prone to cracks, the finishing and coating performance are reduced, and the energy consumption is increased, so it is also economically problematic. In other respects, when a coating material containing a hydroxyl group and a carboxyl group containing a resin and a blocked polyisocyanate compound is used, it is possible to obtain a hardenability with a gel fraction of 90% or more even if it is fired at 140 ° C, and High coating film hardness (pencil hardness of 4H or more), but low gloss (60 ° gloss of 10 or less), and the concealment of the impression is not sufficient [Patent Document 3]. φ In addition, regarding a part of the free isocyanate group of an ethylene-based copolymer having two or more free isocyanate groups in one molecule, the hydroxyl group in an acrylic resin having two or more hydroxyl groups in one molecule A part of the resin was reacted, and then all the remaining free isocyanate groups were reacted with a blocking agent to form an invention of a resin having a blocked isocyanate group and a hydroxyl group in one molecule [Patent Document 4]. When this invention is used only for a matte anion plating coating, a matte coating film having excellent low-temperature hardenability, coating film hardness, and mold impression concealability cannot be obtained. In addition, the mold of the matte coating film is excellent in the concealment of the imprint. [Patent Document 1] Japanese Patent Application Laid-Open No. 0-46065 [Patent Literature 2] Japanese Patent Application Laid-Open No. 2001-1-1 494 [Patent Literature 3] Japanese Patent Application Laid-Open No. 8-41 380 [Patent Literature 4] Japanese Patent Laid-Open No. 5-2471 [Disclosure of the Invention] [Summary of the Invention] [Problems to be Solved by the Invention] The problem to be solved is to find a matting anionic electroplating coating with excellent low-temperature hardenability, hard coating film 200536903 degrees, and excellent impression concealment. [Means to solve the problem] In order to solve the above-mentioned problems, the inventors deliberately and repeatedly conducted research, and found that by using one kind of ethylene having two or more free isocyanate groups in one molecule, A part of the free isocyanate group of the copolymer (a 1) reacts with a part of the hydroxyl group of the ethylene-based copolymer (a2) having a hydroxyl group, a carboxyl group, and an alkoxysilyl group, and then all the remaining Matte anion electroplating coating formed by the reaction of free isocyanate groups with a blocking agent and having a block isocyanate group and a hydroxyl group in the molecule (A) and a hardening catalyst (B). That is, the present invention has been completed. That is, the present invention is: 1. A matte anion plating coating characterized by using the free isocyanate group of an ethylene-based copolymer (a 1) having two or more free isocyanate groups in one molecule. Partly reacts with a part of the hydroxyl group of the ethylene-based copolymer (a2) having a hydroxyl group, a carboxyl group, and an alkoxysilyl group, and then reacts all the remaining free isocyanate groups with a blocking agent. It is a resin having a block isocyanate group and a hydroxyl group existing in one molecule, and the difference in the solubility parameter (SP 値) of the ethylene-based copolymer (a 1) and the ethylene-based copolymer (a2) is 0_4 The resin (A) of ~ 1.0 is water-dispersed, and an emulsion formed by further adding a hardening catalyst (B) and dispersing it, and contains 1,000 wt.% Of the total amount of the resin (A). Parts are 0-1 to 10 parts by weight of the hardening catalyst (B). 2. The matte anion plating coating according to item 1, wherein the hardening catalyst (B) is at least one compound selected from 200536903 organic tin compounds and amine compounds. 3. The matte anion plating coating according to item 1 or 2, wherein the ethylene-based copolymer (a 1) is a copolymer formed of an isocyanate-containing ethylene-based monomer and other ethylene-based monomers. 4. A matte coating article, the 60 ° gloss of the coating film surface formed by coating the matte anion plating coating of any one of items 1 to 3 on an anodized aluminum substrate is 10 or less. [Effects of the invention] • The matte anion plating coating of the present invention can obtain a coating film hardness (pencil hardness of 4H or more) and 60 ° of excellent impression concealment by low-temperature firing and drying at 14CTC for 20 minutes. Matte coating film with gloss of 10 or less. The composition of the present invention has low-temperature curability of an anionic plating coating which cannot be achieved by using a melamine resin as a hardening component, so it can release cracks and coatings of the conventional anodized film fired at 170 ° C. Problems such as decreased film performance and increased energy consumption; and, a matte coating film that cannot be achieved with an anionic electroplated coating using a conventional block polyisocyanate compound as a hardening component can be obtained. [Embodiment] [The best form for carrying out the invention] The matte anion plating coating of the present invention is an emulsion containing a resin (A) and a curing catalyst (B) and dispersed in water, and has good low-temperature curability. Matting anion plating coating. This will be described in detail below. Resin (A): Resin (A) is a part of the free isocyanate group of an ethylene-based copolymer (a 1) having an isocyanate group and having two or more in one molecule. Group, carboxyl group, and alkoxysilyl group of ethylene-based copolymer (a2) (hereinafter, referred to as a water-dispersible ethylene-based copolymer (a2), a part of the hydroxyl groups reacts, and then all the remaining free isocyanate groups The segmentation agent is formed by reacting a resin having a block isocyanate group and a hydroxyl group existing in one molecule. The ethylene-based copolymer (a 1) is an ethylene-based monomer (hereinafter referred to as an isocyanate group). (Referred to as "NCO group-containing monomer") as a necessary component, and a copolymer of 0 and other vinyl monomers is mainly used at the terminal and / or side chain of a linear copolymer It has an isocyanate group. The NCO group-containing single system is a compound having at least one unblocked free isocyanate group and one radical polymerizable double bond in one molecule. For example, it can be used from m-or p- Isopropenyl- ， Α-dimethylbenzyl isocyanate, 2-isocyanate ethyl methacrylate, 1 to 1 (mole ratio) adducts of ethylene monomers containing hydroxyl groups and diisocyanate compounds, etc. 1 or more of the above. • The above-mentioned hydroxyl group-containing ethyl monomers used in the preparation of NCO group-containing monomers are those having one or more hydroxyl groups and free radicals in one molecule. A compound having a polymerizable double bond, for example, it may be 2-transethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutylpropionate, 2, 3-dihydroxypropyl acrylate, 2-hydroxy-3-phenoxyethyl acrylate, 2-hydroxy-3-ethoxyethyl acrylate, etc. Furthermore, for example, it may be acrylic Or mol adducts of methacrylic acid and diols (2 to 20 carbon atoms), etc. * 200536903 The above-mentioned diisocyanate compound used for preparing NCO group-containing monomers is contained in one molecule. Something having 2 isocyanate groups, for example, 'for example, it may be a tolyl diisocyanate, 4,4'-diphenyl Methane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (2, 6) -Diisocyanate, isophorone diisocyanate, trimethylhexane diisocyanate and other aliphatic, aromatic and cycloaliphatic diisocyanate compounds. • Among the above NCO-containing monomers, From the viewpoint of preventing gelation during the reaction between the ethylene-based copolymers (a2) described later, it is particularly preferable to use m-isopropenyl-α, α-dimethylbenzyl having a third isocyanate group. Isocyanate. Further, other vinyl monomers are preferably compounds having a radically polymerizable double bond in one molecule and not having an active hydrogen capable of reacting with an isocyanate group. Specifically, for example, May be aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, etc .; methyl (meth) • acrylate, ethyl (meth) acrylate, butyl (meth) acrylic Ester, 2-ethylhexyl ( Base) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearate (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) (Meth) acrylic esters such as acrylic esters; Biscott 3F (manufactured by Osaka Organic Chemical Co., Ltd., the same meaning as below), 3MF, 8F, 8MF, perfluorocyclohexyl (methyl ) Fluorinated vinyl monomers such as propionate, N-2 · propyl perfluoroxin sulfonamide ethyl (meth) acrylate, fluorinated ethylene, vinylidene fluoride, etc .; -11- 200536903 Ν, Ν'-diethylaminoethyl (meth) acrylate, Ν, Ν'-diethylaminoethyl (meth) acrylate, Ν, Ν'-diethylaminoethyl Nitrogen-containing vinyl monomers such as (meth) acrylates, N, N'-diethyl (meth) acrylamide; vinyl ether monomers such as vinyl ethyl ether, vinyl butyl ether; And glycidyl (meth) acrylate, 3,4-cycloethoxycyclohexyl methyl (meth) acrylate, acrylic glycidyl ether, hydroxy Alkyl ethers of allyl acrylamide, (meth) acrylamide, chlorine (meth) acrylic acid, ethylene chloride, vinyl chloride, (meth) acrylonitrile, oxyalkyl trimethyl methacrylate Oxysil # alkane, etc .; one kind or a mixture of two or more kinds can be used. The ratio between the NC 0 group-containing monomer and other vinyl monomers is not particularly limited as long as it has a range of two or more free isocyanate groups in one molecule of the vinyl copolymer (a1). However, a suitable range based on the NC0-group-containing monomer / other vinyl-based monomer (weight ratio) is 100/0 to 1/99, and more preferably 65/35 to 30/70. In addition, the polymerization reaction between monomers containing only NCO groups or other vinyl-based monomers is generally preferred in an inert organic solvent having no active hydrogen capable of reacting with isocyanate and ester groups. get on. Such an inert organic solvent can be, for example, a single or mixed solvent of aliphatic hydrocarbon-based, ester-based, ketone-based, or the like, such as hexane, heptane, or octane. Specifically, for example, a mixed solvent of methoxypropyl acetate and t-butyl-peroxyisopropyl carbonate can be used. Since such a solvent is a substance containing water, it is preferable to perform dehydration in advance as necessary. These polymerization reactions are carried out at a temperature of 50 to 180 ° C using a radical polymerization initiator. The molecular weight of the ethylene-based copolymer (3 彳) can be 200536903 by the reaction concentration, starting The dose is adjusted. The reaction concentration is within a range of 20 to 80% by weight of the polymer. In particular, in order to raise the polymerization rate of the cylinder, it is more preferable to use a peroxide-based or carbonate-based initiator at a reaction temperature of 100 ° C or higher. When it is more preferably used with an acrylate monomer, a polymer having a high polymerization rate can be easily obtained. The concentration of the poly-initiator may be in the range of 0. 0 to 1 to 15% by weight of the total monomer, but it is more preferably 0 to 1 to 10% by weight. /. Within range. The weight average molecular weight (Note 1) of such an ethylene-based copolymer (a1) is preferably # 500 to 50,000, and particularly preferably in the range of 1500 to 30,000. A suitable isocyanate value is 30 to 200 mg NC 0/10 g. In addition, although the ethylene-based copolymer (a1) has two or more free isocyanate groups in one molecule, it is preferred that there is no active hydrogen that can react with the isocyanate group at all. (Note 1) Weight average molecular weight: based on JIS K01 24-83. Separation column system uses TSK GEL 4000 HXL + G 3000 Hu + G 2500 HXL + G 2000 HXL (manufactured by Toyo Soda Co., Ltd.), At 40 ° C and 1.0 ml / min flow rate, use GPC with tetrahydrofuran as the eluent, and calculate the calibration curve of the colored column and polystyrene measured with the RI refractometer. Ethylene-based copolymer (a2): The ethylene-based copolymer (a2) is suitable for (1) unsaturated monomers containing alkoxysilyl groups, (2) unsaturated monomers containing hydroxyl groups, and (3) containing The unsaturated monomer of carboxyl group is regarded as an essential component, and it is a product obtained by copolymerizing with (4) other unsaturated monomers as necessary. These monomer components may be, for example, those described below. (1) Unsaturated monomer containing alkoxysilyl group: for example, 200536903 may be r- (meth) acrylfluorenyloxypropyltrimethoxysilane, r- (meth) acrylfluorenyloxypropyl Methylmethyldimethoxysilane, r- (meth) acrylfluorenyloxypropyltriethoxysilane, vinyltrimethoxysilane and the like. (2) Hydroxyl-containing unsaturated monomers: For example, it may be hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and pracicidil other than these Fivm (manufactured by Desir Chemical, trade name, caprolactam-modified (meth) acrylic acid hydroxy esters), pracicill FM2 (same as left), pracicill FM3 (same as left), pula Kusir FA1 (same as left), Prakusir # FA2 (same as left), Prasucill FA3 (same as left) and other unsaturated monomers containing hydroxyl groups. (3) Unsaturated monomer containing a carboxyl group: For example, it may be (meth) acrylic acid, maleic acid, or the like. (4) Other unsaturated monomers: For example, it may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, C1 of (meth) acrylic acid such as hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, etc. • Alkyl esters or naphthenes of ~ C18 Aromatic vinyl monomers such as esters, styrene, (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, etc. (Meth) acrylamide and its derivatives, (meth) acrylonitrile compounds, and the like. The weight average molecular weight of these ethylene-based copolymers (a2) is preferably in the range of 500 to 50,000, particularly preferably in the range of 2,000 to 35,000. Particularly suitable hydroxyl groups are in the range of 20 to 200 mg KOH / g based on hydroxyl valence. In the production of the resin (A), the reaction between the ethylene-based copolymer (a 1) and the ethylene-based copolymer 200536903 (a2) is a urethane reaction between an isocyanate group and a hydroxyl group. In other words, the ethylene-based copolymer (a2) can be blended in the organic solution of the ethylene-based copolymer (a1), and the urethane reaction is usually performed at a temperature of 20 to 10 CTC, preferably 25 to 6 CTC. . The reaction is controlled by the reduction of the isocyanate group, that is, the isocyanate value. Further, in such a reaction, in order to obtain low-temperature curability and coating film hardness, a curing catalyst such as an organic tin compound is preferably used. As long as the blending amount of the ethylene-based copolymer (a2) is at least an average of 0.1 urethane bonds, the ethylene-based copolymer (a1) having an average molecular weight of 500 to 50,000 with a weight average of φ per molecule can be introduced. However, it is preferable that at least an average of 0.5 to 1.5 amino acid can be introduced into the ethylene-based copolymer (a 1) having a weight average molecular weight of 50 to 30,000 per molecule. The ester bond is particularly preferably one urethane bond per one molecule of the ethylene-based copolymer (a 1). Next, a urethane bond is introduced by reacting the ethylene-based copolymer (a2) as described above, and the water-dispersible ethylene-based copolymer (a2) is added to the ethylene-based copolymer. Residual free isocyanate contained in (a1) and the following block agent react at a temperature of usually 20 to 100 ° C to carry out the reaction, and the resin (A) can be obtained. Blocking agents, for example, which may be, for example, phenol, cresol, xylenol, p-ethylphenol, 0-propofol, P-tert-butanol, P_tert-octylphenol, thymol, p_naphthalene Acid, p-nitroamidine, p-chlorine, etc .; methanol, ethanol, propanol, butanol, ethylene glycol, methylcellulysin, ethylcellulysin, methylcarbitol, benzyl Alcohols based on alcohols, phenylcellulosin, furfuryl alcohol, cyclohexyl-15-200536903 alcohols, active methylenes such as dimethyl malonate, acetic acid acetate, etc .; Butanethiol, Thiols such as thionine and tert-dodecyl mercaptan; acetamidine, acetamidine, methoxyaniline, acetamidine, and phenylammonium; acetamide and succinate Acid imines such as acid imine; diamines such as diphenylamine, phenylnaphthylamine, aniline, carbazole; imidazoles such as imidazole, 2-ethylimidazole; urea, thiourea, and ethylene Urea based on urea, etc .; Carbamate based on N-phenylaminophenyl phenate, 2-oxazolinone, etc .; Imine based on ethenimine, etc .; • Formaldehyde oxime, acetaldehyde oxime , Acetone oxime, methyl ethyl ketoxime, methyl isobutanone oxime Oxime systems such as cyclohexanone oxime; sulfite systems such as soda sulfite and potassium bisulfite; ε-caprolactam, 5-valerolactam, 7-valerolactone, / 3-propiolactone Isolactones; 3,5-dimethylpyrazole, 3-methylpyrazole, 4-nitro3,5-dimethylpyrazole, and 4-bromo-3,5-dimethylpyrazole Pyrazoles and the like. Resin (A) is based on the urethane reaction between isocyanate hydroxyl groups and the urethane bond to bond the ethylene-based copolymer (a 1) and the ethylene-based copolymer (a2) to each other. together. The resin (A) obtained in this way has an average of at least one block isocyanate group and at least one hydroxyl group in the molecule, and its weight average molecular weight is about 1,000 to 120,000, especially about 5,000 to 50,000. Suitable hydrogen The oxygen value (mg KOH / g) is in the range of 25 to 250. In particular, in order to obtain a matte coating film having a low gloss (60. Gloss is 10 or less), the solubility parameter (SP 値 (Note 2) between the ethylene-based copolymer (a 1) and the ethylene-based copolymer (a2)) )) The difference should be within the range, more preferably 200536903 〇_5 ~ 〇 · 8 〇 (Note 2) Solubility parameter: SP 値 is the abbreviation of Solubility Parameter, which means the scale of the intermolecular interaction of liquid molecules . With regard to this SP 値, the composition of the ethylene-based copolymer (a 1) and the water-dispersible ethylene-based copolymer (a2) is used. 'When the SP 値 of the monomer is known, the following formula (彳) can be used. The SP 値 of the copolymer monomer is obtained, and the SP 値 is used as the SP 値 of the copolymer. The SP of the monomers has been sorted out in the Journal of Paint Technology Vol. 42, page 176 (1970). SP = SPiXfW1 + SP2xfW2 + ... SPnXfWn Formula (1) (SP1. SP2, fwi 'fw2, _ · · SPn represents SP of each monomer, fwn represents each monomer relative to the total monomer Weight fraction.) Also, when the monomer s P 値 is unknown, it can be measured by cloud point titration. Specifically, it can be according to the following formula (2), that is, K. w. SUH, ". M. Corbett's formula (Journal of Applied Polymer Science, Volume 12, p. 2359, '1968) was used as a reference for calculation. Equation (2) VVh * δ · Η ^ VVp * δη
Vvh+Vvd (式中，VH係表示n-己烷之容積分率，表示去離子水 200536903 之容積分率’ 6 η係表不η-己院之SP値，5 d表示去離子水 之S P値。） 濁點滴定係將做爲試樣的樹脂〇 · 5克（固體物）溶解於1 〇 毫升之丙酮中，慢慢地加入η -己烷，讀出濁點時之滴定量 Η (毫升），同樣地讀出將去離子水加入丙酮溶液中之濁點時 的滴定量D(毫升）使用下式而算出VH、VD、5 η、5 d。另外， 各溶劑之SP値，丙酮：9·75、N-己烷：7·24、去離子水： 23.43 ° • 〔 Vh = H/(10 + H)、Vd = D/(10 + D)、5 h = 9.75x1 0/(1 0 + H) + 7.24 xH/(1〇 + H)、(5 d = 9.75x1 0/(1 0 + D) + 23.43xD/(10 + D)] 又，乙烯系共聚物（a1)、及乙烯系共聚物（a2)之玻璃轉 移溫度（Tg)同時爲1〇°C以上時，對塗膜性之提昇方面而言較 理想。 硬化觸媒（B):本發明之陰離子電鍍塗料是一種低溫硬 化性、塗膜硬度均優異之物，且含有硬化觸媒（B )之必要成 分。當做硬化觸媒（B)之有機錫化合物，例如，可以使用辛 # 酸錫、二丁錫二乙酸鹽、二丁錫二辛酸鹽、二丁錫二月桂酸 鹽、二丁錫二馬來酸鹽、四丁錫、二丁基氧化錫、二丁錫二 苯甲酸鹽氧、二辛錫二苯甲酸鹽氧等； 胺化合物，舉例來說，例如其可以是三甲胺、三乙胺、 二甲基環己胺、N-四甲基己烷-1,6-二胺、N-五甲基二伸乙 三胺、2-甲基-1，4-二氮雜環〔2,2,2〕辛烷等之3級胺。 此等硬化觸媒（B)係可以單獨使用，較宜是藉由2種以 上之混合使用來提昇低溫硬化性、及塗膜硬度。硬化觸媒之 -18- 200536903 總量（換算成固體物）雖然是隨著其種類而異，然而從觸媒能 力和塗料安定方面來看，通常相對於樹脂（A)之總量100重 量份計，硬化觸媒（B)之固體物宜是0.1〜10重量份，較宜 是含有0.5〜8重量份。 製造於本發明之陰離子電鍍塗料使用的乳化液，係可以 藉由在樹脂（A)中加入硬化觸媒（B)，並相對於樹脂（A)之羧基 摻混〇·1〜1 ·5當量、較宜是0_2〜1 .2當量之中和劑（鹼基性 化合物）後，再予以混合分散，接著在此物中加入去離子水， # 使固體物成爲10〜60重量％、較宜是10〜40重量％，接著 滴下中和劑將Ρ Η値調整成7 · 0〜8.0來進行。 上述之中和劑，舉例來說，例如其可以是乙基胺、丙基 胺、丁基胺、苄基胺、一乙醇胺、新戊醇胺、2-胺基丙醇、 3-胺基丙醇等之第1級單胺；二乙胺二乙醇胺、二-η-或二 -iso-丙醇胺、Ν-甲基乙醇胺、Ν-乙基乙醇胺等之第2級單 胺；二甲基乙醇胺、三甲基胺、三乙基胺、三異丙基胺、甲 基二乙醇胺、二甲基胺乙醇等之第3級單胺；二伸乙基三 • 胺、羥基乙胺基乙胺、乙胺基乙胺、甲胺基丙胺等之多胺基 三乙胺等。 本發明之消光陰離子電鍍塗料，可以視情況需要添加顏 料、染料、硬化觸媒、流動調劑，進行Ρ Η値調整，加入去 離子水而得到固體物爲5〜2 0重量％之離子型電鍍塗料。又 且，可以更進一步地摻混紫外線吸收劑、光安定劑而得到高 耐候性之塗膜。 上述之紫外線吸收劑，舉例來說，例如其可以是苯基水 -19- 200536903 楊酸酯、P-辛基苯基水楊酸酯、4-t-丁苯基水楊酸酯等之水 楊酸衍生物；2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲 酮、2,2、二羥基-4-甲氧基二苯甲酮、2-羥基-4-甲氧基-2’-羧基二苯甲酮、2-羥基-4-甲氧基-5-硫二苯甲酮三氫酯、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2-羥基-4-辛基二苯甲酮、 2-羥基-4-八癸氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基- 5-硫二苯甲酮鈉、2,2’，4,4’-四羥基二苯甲酮、4-癸氧基-2-羥 基二苯甲酮、5-氯-2-羥基二苯甲酮、間苯二酚單苯甲酸酯、 • 2,4-二苯甲醯基間苯二酚、4,6-二苯甲醯基間苯二酚、羥基 癸基二苯甲酮、2,2’-二羥基-4(3-甲基丙烯醯氧-2-羥丙氧基） 二苯甲酮等之二苯甲酮系；2-(2’_羥基-5’-甲基苯基）苯并三 唑之苯并三唑系及其他的（草酸苯胺、胺基丙烯酸酯）的化合 物等。 和紫外線吸收劑混合使用之光安定劑，舉例來說，例如 其可以是受阻胺衍生物，具體而言，例如是雙-(2,2’，6,6’_ 四甲基-4-哌啶基）癸二酸酯、4-苯甲醯氧基- 2,2’，6,6’-四甲基 # 哌啶等，而且可以適當地選擇此等中之1種或2種以上來使 用。 就使用本發明之消光陰離子電鍍塗料來形成塗膜而 言，可以使上述所得到的陰離子電鍍塗料做成浴，將該鋁材 料浸漬在此浴中後，使用著色或無著色陽極氧化鋁材當做被 塗物，進行陰離子電鍍塗裝使所形成之乾燥膜厚度成爲約5 〜30微米，不進行水洗（non-rinse)、或進行水洗（rinse)， 接著在室溫定型後，再於60〜150°C、較宜是80〜14CTC下 -20- 200536903 燒成約2 0〜4 0分鐘並藉由乾燥而使形成塗膜。 藉由消光陰離子電鍍塗料之塗裝所得到的被塗物之塗 膜硬度係顯示出4 Η以上之鉛筆硬度（註3 )、4以上之茲孔 (TUKON)硬度（註4)的高塗膜硬度。 (註3)鉛筆硬度，以JIS Κ 5600-5-4爲基準，使鉛筆芯 以約45 °角抵觸試驗塗板面，一邊以約不會折損筆芯左右之 強度按壓試驗塗板面，一邊以均一的速度向前方移動約1 0 毫米。改變試驗處所反復此操作5次，以塗膜不破損情況的 ϋ 最硬之鉛筆硬度記號當做鉛筆硬度。 (註4)茲孔（TUKON)硬度：將塗板在2CTC之恆溫室中放 置4小時後，以美國鏈&纜公司製之TUKON微硬度測試儀 測定而得。 又，消光陰離子電鍍塗料，也可以容易地藉由使用組合 至少2種類的乳化液來調整消光程度。 例如，可以使用含有以相對於乙烯系共聚物（a 1 )和乙烯 系共聚物（a2)之總量1 00重量份計，乙烯系共聚物（a 1 )/乙烯 • 系共聚物（a2) =30〜90重量份/10〜70重量份之摻混比例， 而以水分散所構成的乙烯系共聚物（a 1 )/乙烯系共聚物（a2) =30〜90重量份/10〜70重量份的範圍之乳化液（2)之陰離 子電鍍塗料。 例如，就塗裝線而言，在想要得到變化消光程度之塗裝 物品的情況下，則可以藉由改變乳化液（1 )/乳化液（2)之摻混 比例而適時調整補給到陰離子電鍍塗料。 【實施例】 -21- 200536903 以下，列舉實施例來更進一步詳細地說明本發明。但是 本發明不僅限定於此等實施例而已。又，「份」及「。/(^係、 表示「重量份」和「重量份」 〈製造例1〉 編號1之乙稀系共聚物（a 1 )溶液之製造例 在備有攪拌機、迴流冷卻器及溫度計之反應器中裝入 6 5份之甲氧丙基乙酸酯，加熱並保持於1 3 0 °C，以3小時滴 下25份m-異丙烯基-α，α-二甲基苄基異氰酸酯（m_TMI)、 40份之iso -丁基甲基丙烯酸酯、4份之η -丁基丙烯酸酯、 3 1份之甲氧乙基丙烯酸酯的混合物。 接著以1小時滴下3 5份之甲氧丙基乙酸酯、5.0份之 t-丁基過氧異丙基碳酸酯的混合液，進一步熟成3小時’而 得到固體物爲50%之編號1之乙烯系共聚物（a 1 )溶液。 編號1之乙烯系共聚物（a 1)溶液中之乙烯系共聚物（a1) 之重量平均分子量爲約5000，SP値爲9.0, Tg爲24.1°C ° 〈製造例2〜5〉 和製造例1同樣地按照表1之摻混內容，以溶劑調聲固 體物而得到編號2〜5之乙烯系共聚物（a 1 )溶液。 -22- 200536903 製造例5 編號5 LO CD σ> CO LO C0 1〇 5000 8.4 C0 LO 酣 製造例4 編號4 LO CD 〇 LO C0 LT) S 5000 C0 CO LO CD 製造例3 編號3 LO CD LO CM CvJ 寸 N CO 1〇 C0 m S 5000 8.8 24.4 製造例2 編號2 m CO m CM 33.4 41.6 LO C0 ID S 5000 00 CO 00 00 製造例1 編號1 l〇 CD ΙΟ CM 〇 寸 LO C0 LO 5000 〇 σ! 24.1 乙烯系共聚物(a1)溶液 甲氧丙基乙酸酯 稍 II 簾 ’氍 ΙΕ醜 _稍 E tf iso-丁基甲基丙烯酸酯 η-丁基丙烯酸酯 甲氧乙基丙烯酸酯 2-乙基己基丙烯酸酯 甲基丙烯酸甲酯 甲基丙烯酸乙酯 甲氧丙基乙酸酯 t-丁基過氧異丙基碳酸酯 固體物(％) 重量平均分子量 SP値 Tg(°C) 摻混 特徵Vvh + Vvd (where VH represents the volume fraction of n-hexane, and represents the volume fraction of deionized water 200536903 '6 η represents the SP of η-Yiyuan, 5 d represents the SP of deionized water値.) Cloud point titration is to dissolve 0.5 g (solid) of the resin as a sample in 10 ml of acetone, slowly add η-hexane, and read the titer at the cloud point Η ( Ml) and similarly read out the titer D (ml) when deionized water was added to the cloud point in the acetone solution. VH, VD, 5 η, 5 d were calculated using the following formula. In addition, SP 値 of each solvent, acetone: 9.75, N-hexane: 7.24, deionized water: 23.43 ° • [Vh = H / (10 + H), Vd = D / (10 + D) , 5 h = 9.75x1 0 / (1 0 + H) + 7.24 xH / (1〇 + H), (5 d = 9.75x1 0 / (1 0 + D) + 23.43xD / (10 + D)) and When the glass transition temperature (Tg) of the ethylene-based copolymer (a1) and the ethylene-based copolymer (a2) is 10 ° C or higher at the same time, it is ideal for improving the coating film property. Hardening catalyst (B ): The anionic plating coating of the present invention is a substance which is excellent in low-temperature hardenability and film hardness, and contains the necessary components of the hardening catalyst (B). As the organotin compound of the hardening catalyst (B), for example, it can be used Xin # Acid tin, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin dilaurate, dibutyltin dimaleate, tetrabutyltin, dibutyltin oxide, dibutyltindi Benzoate oxygen, dioctyltin dibenzoate oxygen, etc .; amine compounds, for example, which can be, for example, trimethylamine, triethylamine, dimethylcyclohexylamine, N-tetramethylhexane- 1,6-diamine, N-pentamethyldiethylenetriamine, 2-methyl-1,4 -Tertiary amines such as diazacyclo [2,2,2] octane, etc. These hardening catalysts (B) can be used alone, and it is preferable to improve the low-temperature hardening properties by mixing two or more kinds. And coating film hardness. Hardening catalyst -18- 200536903 The total amount (converted to solid) varies with its type, but in terms of catalyst capacity and coating stability, it is usually higher than that of resin (A). The solid matter of the hardening catalyst (B) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight based on the total amount of 100 parts by weight. The emulsion used in the anionic plating coating produced in the present invention can be borrowed. By adding a hardening catalyst (B) to the resin (A), and blending 0.1 to 1.5 equivalents with respect to the carboxyl group of the resin (A), more preferably 0_2 to 1.2 equivalents of a neutralizing agent (alkali Basic compound), and then mix and disperse, and then add deionized water to this, # make the solids 10 to 60% by weight, more preferably 10 to 40% by weight, and then drop the neutralizing agent to p Η 値The adjustment is performed from 7. 0 to 8.0. The neutralizing agent is, for example, ethylamine, propylamine, Class 1 monoamines such as butylamine, benzylamine, monoethanolamine, neopentanolamine, 2-aminopropanol, 3-aminopropanol, etc .; diethylamine diethanolamine, di-η- or di- iso-propanolamine, N-methylethanolamine, N-ethylethanolamine and other secondary monoamines; dimethylethanolamine, trimethylamine, triethylamine, triisopropylamine, methyldiethanolamine 3rd level monoamines such as dimethylamine, ethanol, etc .; polyaminotriethylamines such as diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, etc. The matte anion plating coating of the present invention can be added with pigments, dyes, hardening catalysts, and flow regulators to adjust P Ρ as needed, and deionized water is added to obtain an ionic plating coating with a solid content of 5 to 20% by weight. . Furthermore, a UV absorber and a light stabilizer can be further blended to obtain a coating film with high weather resistance. The above-mentioned ultraviolet absorbent may be, for example, water such as phenyl water-19-200536903 salicylate, P-octylphenylsalicylate, 4-t-butylphenylsalicylate, etc. Salicylic acid derivatives; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2, dihydroxy-4-methoxybenzophenone, 2-hydroxy 4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-thiobenzophenone trihydroester, 2,2'-dihydroxy-4,4'- Dimethoxybenzophenone, 2-hydroxy-4-octylbenzophenone, 2-hydroxy-4-octadecylbenzophenone, 2,2'-dihydroxy-4,4'- Dimethoxy-sodium 5-thiobenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-decoxy-2-hydroxybenzophenone, 5-chloro-2 -Hydroxybenzophenone, resorcinol monobenzoate, • 2,4-dibenzofluorenylresorcinol, 4,6-dibenzofluorenylresorcinol, hydroxydecyldiol Benzophenones such as benzophenone, 2,2'-dihydroxy-4 (3-methacryloxy-2-hydroxypropoxy) benzophenone; 2- (2'_hydroxy-5 '-Methylphenyl) benzotriazole, benzotriazole and others (aniline oxalate, amine Acrylates). A light stabilizer used in combination with an ultraviolet absorber, for example, it may be a hindered amine derivative, and specifically, for example, bis- (2,2 ', 6,6'_tetramethyl-4-piperazine Pyridyl) sebacate, 4-benzyloxy-2,2 ', 6,6'-tetramethyl # piperidine, etc., and one or more of these can be appropriately selected use. For forming a coating film using the matte anion plating coating of the present invention, the anion plating coating obtained as described above can be made into a bath, and the aluminum material is immersed in the bath, and a colored or uncolored anodized aluminum material is used as the bath. The object to be coated is anion-plated so that the thickness of the dry film formed is about 5 to 30 microns. Non-rinse or rinse is performed, and then set at room temperature. Bake at 150 ° C, preferably 80 ~ 14CTC-20-20200536903 for about 20 ~ 40 minutes, and dry to form a coating film. The coating film hardness of the coating material obtained by the application of the matte anion plating coating is a high coating film showing a pencil hardness of 4 Η or more (Note 3) and a TUKON hardness of 4 or more (Note 4). hardness. (Note 3) The hardness of the pencil is based on JIS KK 5600-5-4. Make the pencil lead touch the test coated surface at an angle of about 45 °. While pressing the test coated surface with a strength that will not damage the lead, the uniformity is uniform. At a speed of about 10 mm. This operation was repeated 5 times while changing the test location. The hardest pencil hardness mark was used as the pencil hardness. (Note 4) TUKON hardness: The coated plate was placed in a 2CTC constant temperature room for 4 hours, and then measured with a TUKON microhardness tester made by American Chain & Cable Co., Ltd. In addition, the matte anion plating coating can be easily adjusted in the degree of matting by using at least two types of emulsions in combination. For example, an ethylene-based copolymer (a 1) / ethylene-based copolymer (a2) containing 100 parts by weight based on the total amount of the ethylene-based copolymer (a 1) and the ethylene-based copolymer (a2) can be used. = 30 to 90 parts by weight / 10 to 70 parts by weight of the blending ratio, and the ethylene-based copolymer (a 1) / ethylene-based copolymer (a2) constituted by water dispersion = 30 to 90 parts by weight / 10 to 70 Anionic plating coating of emulsion (2) in the range of parts by weight. For example, in the case of a coating line, when it is desired to obtain a coating article with a varying degree of matting, the supply of anions can be adjusted in a timely manner by changing the blending ratio of the emulsion (1) / emulsion (2). Electroplating coating. [Examples] -21-200536903 Hereinafter, the present invention will be described in more detail with examples. However, the present invention is not limited to these examples. In addition, "parts" and "./" are used to indicate "parts by weight" and "parts by weight" <Production Example 1> The production example of the ethylene copolymer (a 1) solution of No. 1 is equipped with a stirrer and reflux. The reactor of the cooler and thermometer was charged with 65 parts of methoxypropyl acetate, heated and maintained at 130 ° C, and 25 parts of m-isopropenyl-α, α-dimethyl was dropped over 3 hours. A mixture of benzyl isocyanate (m_TMI), 40 parts of iso-butyl methacrylate, 4 parts of η-butyl acrylate, 31 parts of methoxyethyl acrylate. Then 3 to 5 parts of the mixture were dripped over 1 hour. A mixed solution of methoxypropyl acetate and 5.0 parts of t-butylperoxyisopropyl carbonate was further matured for 3 hours to obtain an ethylene copolymer (a 1) of No. 1 having a solid content of 50%. Solution: The weight average molecular weight of the ethylene-based copolymer (a1) in the solution of the ethylene-based copolymer (a 1) of No. 1 is about 5000, SP 値 is 9.0, and Tg is 24.1 ° C ° <Manufacturing Examples 2 to 5> and Production Example 1 Similarly, according to the blending content of Table 1, the solid matter was tuned with a solvent to obtain the ethylene-based copolymer (a 1) solution numbered 2 to 5. -22- 20053 6903 Manufacturing Example No. 5 LO CD σ > CO LO C0 1〇5000 8.4 C0 LO 酣 Manufacturing Example No. 4 LO CD 〇LO C0 LT) S 5000 C0 CO LO CD Manufacturing Example No. 3 LO CD LO CM CvJ inch N CO 1〇C0 m S 5000 8.8 24.4 Manufacturing Example 2 No. 2 m CO m CM 33.4 41.6 LO C0 ID S 5000 00 CO 00 00 Manufacturing Example 1 No. 1 CD 10 CD CM inch LO C0 LO 5000 〇σ! 24.1 Ethylene Based copolymer (a1) solution methoxypropyl acetate slightly II curtain '氍 ΙΕΕ_ slightly E tf iso-butyl methacrylate η-butyl acrylate methoxyethyl acrylate 2-ethylhexyl acrylate Methyl methacrylate, ethyl methacrylate, methoxypropyl acetate, t-butylperoxyisopropyl carbonate, solids (%), weight average molecular weight, SP 値 Tg (° C), blending characteristics
〈製造例6〉 編號6之乙烯系共聚物（a2)溶液 -23 - 200536903 在反應器中投入2 7 5份之甲氧丙基乙酸酯，並保持於 80 °C，以3小時向其中滴下75份之苯乙烯、155份之甲基 丙烯酸甲酯、9 5份之η - 丁基丙烯酸酯、5 0份之乙基丙烯酸 酯、75份之2-羥乙基丙烯酸酯、35份之丙烯酸、15份之r -甲基丙烯醯氧丙基三甲氧基矽烷、以及1份之疊氮聯二甲 基戊腈的混合物，接著添加3份之疊氮聯二甲基戊腈，保持 於80 °C進行反應3小時，而得到具有烷氧矽烷基之固體物 爲65重量％之編號1之水分散性乙烯系共聚物（a2)溶液。該 ® 編號1之溶液中之水分散性乙烯系共聚物（a2)的SP値爲 9.54，Tg 爲 25〇C。 〈製造例7〉 編號1之樹脂（A)溶液之製造 在備有攪拌機、迴流冷卻器及溫度計之反應器中加入 7〇〇份（固體物爲350份）之固體物爲50%之編號1之乙烯系 共聚物（a 1)溶液、以及1 000份（固體物爲650份）之在製造 例6所得到的編號1之水分散性乙烯系共聚物（a2)溶液，於 φ 室溫（25°C )下攪拌15分鐘，測定異氰酸酯價。混合清漆之 異氰酸酯價爲4 7.6。 接著，邊攪拌邊加熱維持於40 °C，約進行反應3小時 後’在異氰酸酯價變爲45.8的時點加入300份之甲乙酮肟， 於60°C下熟成2小時，而得到固體物爲50.0%、重量平均分 子量爲約1 6000之編號1之樹脂（A)溶液。 〈製造例8〜1 2〉 和製造例7同樣地按照表2之摻混內容，製得編號2 -24- 200536903 之樹脂（A)溶液〜編號6之樹脂（A)溶液。在表2中，括弧內 之表示固體物量。 表2 製造例12 編號6 700 (350) 1000 (650) I- ! 300 | 2000 (1000) 1.14 製造例111 編號5 700 (350) 1000 (650) 300 2000 (1000) 1.24 製造例10 編號4 600 (300) 1077 (700) 323 2000 (1000) 0.54 製造例9 | J 編號3 700 (350) 1000 (650) 300 2000 (1000) 0.74 製造例8 編號2 700 (350) 1000 (650) 300 2000 (1000) 0.74 製造例7 編號1 i I 700 (350) 1000 (650) 300 2000 (1000) 0.54 樹脂㈧溶液(種類） 編號1之乙烯系共聚物(a1)溶液 I 編號2之乙烯系共聚物(a1)溶液 編號3之乙烯系共聚物(a1)溶液 編號4之乙烯系共聚物(a1)溶液 編號5之乙烯系共聚物(a1)溶液 £ S cnj JjV)J 賴 甲乙酮肟 樹脂㈧溶液(摻混量） 1=1 Q-扠⑺ ω Ν K]平、 〈製造例1 3〉 在反應器中投入55份之異丙醇並保持於80 °C，以3小 -25 - 200536903 時向其中滴下15份之苯乙烯、31份之甲基丙烯酸甲酯、15 份之η· 丁基丙烯酸酯、10份之乙基丙烯酸酯、15份之2· 羥乙基丙烯酸酯、7份之丙烯酸、7份之Ν -丁氧甲基丙烯醯 胺、以及1 〇份之疊氮聯二甲基戊腈之混合物，滴下終了後 於此溫度下保持1小時，接著滴下1份之疊氮聯二甲基戊腈 和45份之丁基溶纖素，進一步於80 °C持續進行反應4小 時，而得到固體物爲50重量％、重量平均分子量爲30000、 SP値爲9_60，Tg爲16.5°C之編號7之樹脂溶液。 〈製造例1 4〉 編號1之乳化液之製造 在摻混相對於200份（固體物爲1 〇〇份）之在製造例7所 製作的編號1之樹脂（A)溶液的羧基計爲0.4當量之三乙胺 後，再予以混合分散，並混合〇·5份（固體物）之SCAT-7(註 5)予以分散後，再邊攪拌邊慢慢地滴下去離子水，更進一步 添加三乙胺、以去離子水調使p Η値成7 _ 5而得到固體物爲 1 0 %之編號1之乳化液。 〈製造例1 5〜1 9〉 和製造例1 4同樣地按照表3之摻混內容，製得編號2 〜〜編號6之固體物爲1 〇 %的乳化液。 〈製造例20〉 在1 40份（固體物爲70份）之在製造例1 3所製作的編號 7之樹脂溶液中，混合37_5份（固體物爲30份）之杜拉內特 |\/^-已801\/1(註6)、0.5份（固體物爲0.5份）之30八丁-7(註5)， 邊進行攪拌邊慢慢滴下去離子水，更進一步添加三乙胺、以 -26- 200536903 去離子水調使Ρ Η値成7.5而得到固體物爲1 0 %之編號7之 乳化液。<Manufacturing Example 6> Solution No. 6 of the ethylene-based copolymer (a2) -23-200536903 Put 2 75 parts of methoxypropyl acetate in the reactor, and keep it at 80 ° C, and place it in it for 3 hours. Drop 75 parts of styrene, 155 parts of methyl methacrylate, 95 parts of η-butyl acrylate, 50 parts of ethyl acrylate, 75 parts of 2-hydroxyethyl acrylate, 35 parts of A mixture of acrylic acid, 15 parts of r-methacryloxypropyltrimethoxysilane, and 1 part of azidobisdimethylvaleronitrile, followed by adding 3 parts of azidobisdimethylvaleronitrile and maintaining at The reaction was performed at 80 ° C for 3 hours to obtain a water-dispersible ethylene-based copolymer (a2) solution of No. 1 having a solid content of alkoxysilyl group of 65% by weight. The SP 値 of the water-dispersible ethylene-based copolymer (a2) in the solution of No. 1 was 9.54 and the Tg was 25 ° C. <Manufacturing Example 7> Production of No. 1 resin (A) solution In a reactor equipped with a stirrer, a reflux cooler, and a thermometer, 700 parts (350 parts of solid matter) of 50% of solid matter was placed in No. 1 Solution of the ethylene-based copolymer (a 1) and 1,000 parts (650 parts of solid matter) of the water-dispersible ethylene-based copolymer (a2) solution obtained in Production Example 6 at φ room temperature ( 25 ° C) for 15 minutes, and the isocyanate value was measured. The isocyanate value of the mixed varnish was 4 7.6. Next, heat was maintained at 40 ° C while stirring, and after about 3 hours of reaction, 300 parts of methyl ethyl ketoxime was added at the point when the isocyanate value became 45.8, and matured at 60 ° C for 2 hours to obtain 50.0% solids. A resin (A) solution of No. 1 having a weight average molecular weight of about 16,000. <Manufacturing Examples 8 to 12> In the same manner as in Manufacturing Example 7, the resin (A) solution No. 2-24-200536903 to the resin (A) solution No. 6 were prepared in accordance with the blending contents in Table 2. In Table 2, the solid content is shown in parentheses. Table 2 Manufacturing Example 12 No. 6 700 (350) 1000 (650) I-! 300 | 2000 (1000) 1.14 Manufacturing Example 111 No. 5 700 (350) 1000 (650) 300 2000 (1000) 1.24 Manufacturing Example 10 No. 4 600 (300) 1077 (700) 323 2000 (1000) 0.54 Manufacturing Example 9 | J No. 3 700 (350) 1000 (650) 300 2000 (1000) 0.74 Manufacturing Example 8 No. 2 700 (350) 1000 (650) 300 2000 ( 1000) 0.74 Production Example 7 No. 1 i I 700 (350) 1000 (650) 300 2000 (1000) 0.54 Resin ㈧ solution (type) Ethylene copolymer (a1) solution I No. 2 ethylene copolymer ( a1) Ethylene copolymer with solution number 3 (a1) Ethylene copolymer with solution number 4 (a1) Ethylene copolymer with solution number 5 (a1) Solution £ S cnj JjV) J Lyme ethyl ketoxime resin ㈧ solution (doped with (Mixing amount) 1 = 1 Q-fork ω Ν K] Ping, <Production Example 1 3> Put 55 parts of isopropanol into the reactor and keep it at 80 ° C, 3 hours -25-200536903 at it 15 parts of styrene, 31 parts of methyl methacrylate, 15 parts of η · butyl acrylate, 10 parts of ethyl acrylate, 15 parts of 2 · hydroxyethyl acrylic acid A mixture of 7 parts of acrylic acid, 7 parts of N-butoxymethacrylamide, and 10 parts of azidobisdimethylvaleronitrile. After dripping, the mixture was kept at this temperature for 1 hour, and then 1 part was dropped. The azide bisvaleronitrile and 45 parts of butyl cellolysin were further reacted at 80 ° C for 4 hours to obtain a solid matter of 50% by weight, a weight average molecular weight of 30,000, SP 値 of 9-60, and Tg of No. 7 resin solution at 16.5 ° C. <Manufacturing Example 1 4> The emulsion of No. 1 was prepared by mixing 0.4 parts by weight of the carboxyl group of the resin (A) solution of No. 1 prepared in Production Example 7 with 200 parts (100 parts of solid matter). After triethylamine, it is mixed and dispersed, and 0.5 parts (solid matter) of SCAT-7 (Note 5) is dispersed, and then the ion water is slowly dripped while stirring, and further added triethyl The amine was adjusted to 7-5 with deionized water to obtain an emulsion of No. 1 with a solid content of 10%. <Manufacturing Example 1 5 to 19> In the same manner as in Manufacturing Example 14 according to the blending contents of Table 3, an emulsion having a solid content of Nos. 2 to 6 was 10%. <Manufacturing Example 20> In 1 to 40 parts (70 parts of solid matter) of the resin solution No. 7 prepared in Manufacturing Example 1 3, 37_5 parts (30 parts of solid matter) of Duranite were mixed | \ / ^ -801 \ / 1 (Note 6), 0.5 parts (0.5 parts of solid matter) of 30 octane-7 (Note 5), while stirring, slowly drop down the ion water, and further add triethylamine to -26- 200536903 Deionized water was adjusted to make P Η 値 7.5 to obtain an emulsion of No. 7 with a solid content of 10%.
製造例20 編號7 140(70) 0.5(0.5) 37.5(30) 1 m 画 〇 X— 载 m ιΐΐϊΕ 製造例19 編號6 200(100) 0.5(0.5) 製造例18 編號5 200(100) 0.5(0.5) 製造例17 編號4 200(100) 0.5(0.5) C\T T— 1 製造例16 編號3 200(100) 0.5(0.5) 0.4(0.4) 製造例15 編號2 200(100) 0.5(0.5) 1 製造例14 _i 編號1 200(100) 0.5(0.5) 離7_5 乳化液 編號1之樹脂㈧溶液 編號2之樹脂㈧溶液 編號3之樹脂(A)溶液 編號4之樹脂(A)溶液 編號5之樹脂(A)溶液 編號6之樹脂(A)溶液 編號7之樹脂溶液 SCAT-7(註 5) 杜拉內特MF-80M(註6) U-CAT18X(註 7) 汽內畢328(註8) 汽內畢292(註9) 三乙胺 去離子水 §11 画) -27 - 200536903 (註5)SCAT-7:三共有機合成（股）公司製，商 丁錫雙氫硫基羧酸酯； (註6)杜拉內特MF-B80M :旭化成（股）公司製， 六亞甲基異氰酸酯之異氰酸酯型、甲乙酮肟嵌段t 物爲8 0 % ; (註7)U-CAT18X :三洋化成公司製，商品名， 化觸媒； (註8)汽內畢328 :汽巴蓋記股份有限公司製， 紫外線吸收劑； (註9)汽內畢292 :汽巴蓋記股份有限公司製， 光安定劑； 【實施例1】 於1 000份（固體物爲100份）的編號1之固體 之乳化液中，添加三乙胺使P Η値成爲8 · 5，而得 之陰離子電鍍塗料。 【實施例2〜5】 藉由和實施例1同樣之操作，而得到如表4之 施例2〜5之編號2〜編號5之陰離子電鍍塗料。 【比較例1〜4】 藉由和實施例1同樣之操作，而得到如表5之 較例1〜4之編號6〜編號9之陰離子電鍍塗料。 【比較例5】 使用艾雷庫龍AG-300(關西油漆公司製，商品 品名，二 商品名’ 劑、固體 胺系之硬 商品名， 商品名， 物爲1 0 % 到編號1 內容的實 內容的比 名，丙烯 -28- •200536903 酸樹脂•蜜胺硬化型之陰離子電鍍塗料）。 試驗板之作成 將在實施例及比較例所得到的陰離子電鍍塗料做成 浴，將已實施2次處理（脫脂-蝕刻-中和-陽極氧化處理-封孔） 之被膜厚度爲約10微米的陽極氧化鋁材（銀：大小爲150x 70x0.5毫米）之被塗物浸漬於此浴中，進行電鍍塗裝使乾燥 膜厚度成爲10微米，水洗後再於140 °C燒成20分鐘。 依照下述之試驗條件進行試驗。實施例示於表4，而比 ®較例則示於表5。 表4 實施例1 實施例2 實施例3 實施例4 實施例5 陰離子電鍍塗料 編號1 編號2 編號3 編號4 編號5 摻 混 乳化液 種 編號1 編號2 編號3 編號4 編號1 摻混量 1000 1000 1000 1000 500 種 編號2 摻混量 500 三乙胺 調整成 pH=8.5 <— <— <— <— 塗 膜 性 能 凝膠分率(註10) 95 95 98 93 95 鉛筆硬度(註11) 4H 4H 5H 4H 4H 茲孔硬度(註12) 4 5 6 4 4.5 60°光澤度(註13) 4 8 5 7 6 模印記隱蔽性(註14) 〇 〇 〇 〇 〇 摩擦附著性(註15) ◎ ◎ ◎ ◎ 〇 耐候性(註16) 90 94 91 96 92 -29- 200536903 表5 比較例1 比較例2 比較例3 比較例4 比較例5 陰離子電鍍塗料 編號6 編號7 編號8 編號9 艾雷 庫龍 AG-300 摻 混 乳化液 種 編號5 編號6 編號5 編號7 摻混量 1000 1000 500 1000 種 編號6 摻混量 500 三乙胺 調整成 pH=8.5 <— <— <— 塗 膜 性 能 凝膠分率(註10) 91 93 92 90 84 鉛筆硬度(註11) 2H 2H 2H 2H 2H 茲孔硬度(註12) 3 3 3 2 2 60°光澤度(註13) 23 35 27 38 5 模印記隱蔽性(註14) Δ Δ Δ Δ X 摩擦附著性(註15) 〇 〇 〇 Δ X 耐候性(註16) 87 88 87 91 53 (註10)凝膠分率： 將從塗裝馬口鐵板之馬口鐵板剝離的塗膜裝入300篩 目之不銹鋼製的網狀容器中，使用丙酮/甲醇=1 /1之溶劑、 於迴流溫度下萃取6小時後，依照下式算出凝膠分率。 凝膠分率（％)=(萃取後之塗膜重量）/(萃取前之塗膜重量）x100 (註1 1 )鉛筆硬度： 以J IS K 56 0 0-5-4爲基準，使鉛筆芯以約45°角抵觸試 驗塗板面，一邊以約不會折損筆芯左右之強度按壓試驗塗板 面，一邊以均一的速度向前方移動約1 〇毫米。改變試驗處 所反復此操作5次’以塗膜不破損情況的最硬之鉛筆硬度記 號當做鉛筆硬度。 -30- •200536903 (註12)茲孔（TUKON)硬度： 將塗板在2 0 °C之恆溫室中放置4小時後’以美國鏈&纜 公司製之T U Κ Ο N微硬度測試儀測定而得。數値愈高則表示 塗膜愈硬。 (註1 3)60°光澤度： 塗膜之光澤的程度係依照JIS Κ·5400 7·6(1 990)之60 度鏡面光澤度，分別測定6 0度時之入射角和受光角的反射 率，以鏡面光澤度之基準面的光澤度做爲1 0 0時之百分率來 鲁表示。 (註14)模印記隱蔽性： 以目視評價來評價。 〇：模印記隱蔽性良好。 △:模印記隱蔽性不佳。 X :模印記隱蔽性顯著低劣。 (註1 5)摩擦附著性： φ 在試驗板之中央部長度方向上，切割寬度2 5毫米之平 行線（到達鋁面）。從一方之端面剝離約僅90毫米之薄膜層， 彎曲180度（參照第1圖）。 使用自動繪圖S - D型（島津製作所社製、商品名、附有 溫槽之萬能拉伸試驗機），以50毫米/分鐘之拉伸速度進 行拉伸約30毫米（氛圍氣溫度爲25°C ±5。(：）、並測定薄膜之 剝離強度。 ◎:剝離強度爲39.2 N (4公斤重）以上。 〇：剝離強度爲2 9.4〜3 9.2 N。 -31 - 200536903 △:剝離強度爲20〜29.4N。 X :剝離強度爲小於20Ν。 (註1 6)耐候性： 藉由利用陽光氣候計，評量照射2000小時之光澤保持 率（％)。 【產業利用可能性】 藉由利用本發明之消光陰離子電鍍塗料，可以得到低溫 硬化性、塗膜硬度、模印記隱蔽性均優異的6 0 °光澤度10 ® 以下之消光塗膜、及消光塗裝物品。 【圖式簡單說明】 第1圖爲摩擦附著性試驗之模式圖。 【元件符號說明】 1 塗膜 2 被塗物之鋁 3 副板 4 用以固定試驗板之部分 -32-Manufacturing example 20 No. 7 140 (70) 0.5 (0.5) 37.5 (30) 1 m picture 0X—loading m ι Ε Manufacturing example 19 No. 6 200 (100) 0.5 (0.5) Manufacturing example 18 No. 5 200 (100) 0.5 ( 0.5) Manufacturing example 17 No. 4 200 (100) 0.5 (0.5) C \ TT— 1 Manufacturing example 16 No. 3 200 (100) 0.5 (0.5) 0.4 (0.4) Manufacturing example 15 No. 2 200 (100) 0.5 (0.5) 1 Manufacturing Example 14 _i No. 1 200 (100) 0.5 (0.5) 7_5 Emulsion No. 1 resin ㈧ Solution No. 2 Resin ㈧ Solution No. 3 Resin (A) Solution No. 4 Resin (A) Solution No. 5 of Resin (A) Resin solution No. 6 Resin (A) Resin solution No. 7 SCAT-7 (Note 5) Durant MF-80M (Note 6) U-CAT18X (Note 7) Steam inside 328 (Note 8) ) Steam 292 (Note 9) Triethylamine deionized water § 11 drawing) -27-200536903 (Note 5) SCAT-7: manufactured by Sankyo Organic Synthesis Co., Ltd., butadiene dihydrothio carboxylate; (Note 6) Duranite MF-B80M: manufactured by Asahi Kasei Co., Ltd., the isocyanate type of hexamethylene isocyanate and methyl ethyl ketoxime block t are 80%; (Note 7) U-CAT18X: Sanyo Chemical Company name, trade name, and catalyst; (Note 8) Steamer 328: Ciba Geji Co., Ltd., UV absorber; (Note 9) Steamer 292: Ciba Geji Co., Ltd., [Light stabilizer] [Example 1] Anion electroplating coating was obtained by adding triethylamine to 1,000 parts (100 parts of solid matter) of the solid emulsion of No. 1 to make P Η 値 8 · 5. [Examples 2 to 5] By the same operation as in Example 1, the anion plating coatings No. 2 to No. 5 of Examples 2 to 5 in Table 4 were obtained. [Comparative Examples 1 to 4] By the same operation as in Example 1, the anion plating paints No. 6 to No. 9 of Comparative Examples 1 to 4 in Table 5 were obtained. [Comparative Example 5] Irecuron AG-300 (product name, product name, secondary product name, manufactured by Kansai Paint Co., Ltd., solid amine-based hard product name, product name, material number is 10% to the actual content of number 1 The name of the content is propylene-28- • 200536903 acid resin • melamine hardening type anion plating coating). Preparation of the test plate The anion plating coatings obtained in the examples and comparative examples were made into a bath, and the thickness of the film having been subjected to two treatments (degreasing-etching-neutralization-anodizing treatment-sealing) was about 10 microns. The anodized aluminum material (silver: 150x 70x0.5 mm) was immersed in this bath, electroplated to make the thickness of the dried film 10 micrometers, washed with water and fired at 140 ° C for 20 minutes. The test was performed under the following test conditions. Examples are shown in Table 4 and specific examples are shown in Table 5. Table 4 Example 1 Example 2 Example 3 Example 4 Example 5 Anionic plating coating No. 1 No. 2 No. 3 No. 4 No. 5 Blended emulsion type No. 1 No. 2 No. 3 No. 4 No. 1 No. 1 Blending amount 1000 1000 1000 1000 500 kinds No. 2 Blending amount 500 Triethylamine adjusted to pH = 8.5 < — < — < — < — Coating performance gel fraction (Note 10) 95 95 98 93 95 Pencil hardness (Note 11) 4H 4H 5H 4H 4H Pore hardness (Note 12) 4 5 6 4 4.5 60 ° gloss (Note 13) 4 8 5 7 6 Mold mark concealment (Note 14) 〇〇〇〇〇 Friction adhesion (Note 15) ◎ ◎ ◎ 〇 Weather resistance (Note 16) 90 94 91 96 92 -29- 200536903 Table 5 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Anionic plating paint No. 6 No. 7 No. 8 No. 9 Airekuron AG-300 Blended Emulsion No. 5 No. 6 No. 5 No. 7 Blended amount 1000 1000 500 1000 Kind No. 6 Blended amount 500 Triethylamine adjusted to pH = 8.5 < — < — < — Coating performance Gel fraction (Note 10) 91 93 92 90 84 Pencil hardness (Note 11) 2H 2H 2H 2H 2H Pore hardness (Note 12) 3 3 3 2 2 60 ° Gloss (Note 13) 23 35 27 38 5 Mold mark concealment (Note 14) Δ Δ Δ Δ X Friction adhesion (Note 15) 〇〇〇Δ X Weather resistance (Note 16) 87 88 87 91 53 (Note 10) Gel fraction: Put the coating film peeled from the tinplate coated tinplate into a 300-mesh stainless steel mesh container and use acetone / Methanol = 1/1 solvent, and after extraction at reflux temperature for 6 hours, the gel fraction was calculated according to the following formula. Gel fraction (%) = (Weight of coating film after extraction) / (Weight of coating film before extraction) x100 (Note 1 1) Pencil hardness: Based on J IS K 56 0 0-5-4, make the pencil The core abuts the test coating surface at an angle of about 45 °, and while pressing the test coating surface with a strength that will not damage the pen core, it moves about 10 mm forward at a uniform speed. This operation was repeated 5 times by changing the test location ', and the hardness of the hardest pencil with no damage to the coating film was taken as the pencil hardness. -30- • 200536903 (Note 12) TUKON hardness: After coating the plate in a constant temperature room at 20 ° C for 4 hours, it was measured with a TU κ Ο N microhardness tester made by American Chain & Cable Co., Ltd. To get. The higher the number, the harder the coating film. (Note 1 3) Gloss at 60 °: The degree of gloss of the coating film is a 60-degree specular gloss in accordance with JIS K · 5400 7 · 6 (1 990), and the reflection at the incident angle and the light-receiving angle at 60 degrees is measured respectively The rate is expressed as the percentage when the gloss of the reference surface of the mirror gloss is 100%. (Note 14) Concealment of mold imprint: It was evaluated by visual evaluation. 〇: The concealability of the mold mark is good. △: The concealment of the mold imprint is not good. X: The concealment of the imprint is significantly inferior. (Note 1 5) Friction adhesion: φ Cuts a parallel line with a width of 25 mm (to the aluminum surface) in the length direction of the center of the test plate. A film layer of about 90 mm is peeled from one end surface and bent 180 degrees (refer to Fig. 1). Using an automatic drawing S-D type (made by Shimadzu Corporation, trade name, universal tensile tester with temperature bath), stretch at a speed of 50 mm / min for about 30 mm (atmosphere temperature 25 °) C ± 5. (:), and measure the peel strength of the film. ◎: Peel strength is 39.2 N (4 kg weight) or more. 〇: Peel strength is 2 9.4 to 3 9.2 N. -31-200536903 △: Peel strength is 20 ~ 29.4N. X: Peel strength is less than 20N. (Note 1 6) Weather resistance: The gloss retention rate (%) after 2000 hours of exposure is evaluated by using a solar weather meter. [Industrial use possibility] By using The matte anion electroplating coating material of the present invention can obtain matte coating films and matte coated articles with a gloss of 10 ° or less 60 °, which are excellent in low-temperature hardenability, film hardness, and concealment of mold impression. [Schematic description of the drawings] Figure 1 is a schematic diagram of the friction adhesion test. [Description of component symbols] 1 Coating film 2 Aluminium to be coated 3 Sub-plate 4 The part used to fix the test plate -32-