201000545 六、發明說明： 【發明所屬之技術領域】 本發明係相關於使用於塑膠、薄膜等的塗層劑，其硬 化塗膜之外觀良好，且耐磨損性、耐水性優異之活性能量 線硬化型水性樹脂組成物、含該組成物之活性能量線硬化 型塗料、使用該塗料之硬化塗膜之形成方法及設置塗料的 硬化塗膜而成之物品。 【先前技術】 活性能量線硬化型組成物，因對塗裝基材的熱履歷 少，塗膜硬度和磨損性優異等特點，而使用爲家電製品、 行動電話等塑膠基材用硬塗層劑。此類活性能量線硬化型 組成物，例如具有聚合性不飽和雙鍵之聚合物（例如丙稀 基丙烯酸酯等）或實質上不含聚合性不飽和雙鍵之聚合物 (例如丙烯酸樹脂等）、含有聚合性單體和作爲稀釋劑的有 機溶劑之活性能量線硬化型組成物（非水系活性能量線硬 化型組成物）等。使用此活性能量線硬化型組成物作爲例 如噴霧塗裝用之活性能量線硬化型塗料時，上述有機溶劑 之含量多達以該塗料的重量爲基準之50〜90重量％。因此， 使用含有此樹脂組成物之活性能量線硬化型塗料，於塑膨 等基材表面形成硬化塗膜時，因此塗料中的有機溶劑揮胃 而使作業環境惡化。且此揮發的有機溶劑遂成空氣污染之 原因。 其中，探討以含水的活性能量線硬化型水性組成物# 爲稀釋劑。具體而言，例如揭示一種於平均粒徑爲l〇〜1〇〇nm 之水性樹脂分散體（1)，摻合分子內含有至少1個以上@ -4- 201000545 碳-碳雙鍵之感光性低聚物（2)及分子內含有至少1個以 上的碳-碳雙鍵之感光性單體（3 )而形成之水性感光性塗 層組成物（例如參考專利文獻1 )。具體而言，例如專利文 獻1的實施例1揭示一種在100重量份的丙烯酸系微粒子 乳液[例如東洋油墨製造（股）製NANOCRYLBCX-2914等] 中，含有2.3重量份的水溶性胺甲酸丙烯酸酯及2.3重量份 的三羥甲基丙烷三丙烯酸酯而形成之感光性塗層組成物。 又揭示一種含有具（甲基）丙烯醯基的水溶性樹脂 (A)、多官能（甲基）丙烯酸酯化合物（B)及光聚合引 發劑，且呈乳化狀態之紫外線硬化型水性塗料組成物（例 如參考專利文獻2 )。具體而言，例如中和以甲基丙烯酸甲 酯爲必要成分而製得的含羧基丙烯酸酯樹脂之羧基，將製 得的水分散性丙烯酸酯和胺甲酸丙烯酸酯低聚物分散於水 而成之乳液。 使用用於上述專利文獻1的丙烯酸系微粒乳液，而製 造活性能量線硬化型樹脂組成物時，併用有助於提升耐磨 損性、耐水性的疏水性的聚合性單體與水溶性胺甲酸丙烯 酸酯或自發乳化性胺甲酸丙烯酸酯，補足此丙烯酸系微粒 乳液在水溶性胺甲酸丙烯酸酯或自發乳化性胺甲酸丙烯酸 酯中的分散力和安定性，而使疏水性的聚合性單體分散於 水。因此，無法充分發揮可提升耐磨損性、耐水性的疏水 性聚合性單體之效果，使用專利文獻1的水性感光性塗層 組成物而製得之硬化塗膜係耐磨損性、耐水性不足。 上述專利文獻2揭示的紫外線硬化型水性塗料組成物 中，係使用疏水性的胺甲酸丙烯酸酯低聚物作爲多官能（甲 201000545 基）丙烯酸酯，藉此可提升硬化塗膜的耐磨損性、耐水性。 惟，即使使用於該紫外線硬化型水性塗料組成物的含（甲 基）丙烯醯基水溶性樹脂（A )，亦不具有將疏水性的胺甲 酸丙烯酸酯低聚物分散於水中之充分的分散力，亦不易在 水中使多官能（甲基）丙烯酸酯化合物（B)分散於上述含 (甲基）丙烯醯基水溶性樹脂（A)，且一部分的多官能（甲 基）丙烯酸酯化合物（B)即刻分離。因此，硬化塗膜易發 生龜裂和皺折等缺點。且該紫外線硬化型水性塗料組成物 之儲存安定性亦不佳。 [專利文獻1 ]特開平9 - 3 0 2 2 6 6號公報 [專利文獻2]特開2004-0 1 077 9號公報 【發明内容】 [發明所欲解決之課題] 本發明之課題係提供用於塑膠、薄膜等的塗層劑，其 硬化塗膜之外觀良好，且耐磨損性、耐水性優異之活性能 量線硬化型水性樹脂組成物、含該組成物之活性能量線硬 化型塗料、使用該塗料之硬化塗膜之形成方法及設置塗料 的硬化塗膜之物品。 [解決課題之方法] 本發明者等致力硏究之結果，發現下述的見解。 (1)使用以樹脂形成成分的重量爲基準的2~15重量％之 含碳原子數2〜8的伸烷基，且羧基加成於該伸烷基的末端 之自由基聚合性單體’並使用以樹脂形成成分的重量爲基 準之55~70重量％的甲基丙烯酸甲酯而製得，而且將含有 0.80〜1.29mmol/g已中和的殘基之丙稀酸樹脂（親水性丙烯 201000545 酸樹脂）分散於水中之樹脂分散液，可良好地分散疏水性 的聚合性單體。因此，藉由使用含此類成分的活性能量線 硬化型水性塗料，可製得不易發生龜裂和皺折之硬化塗膜。 (2)使用含8.6〜10.5111111〇1^的聚合性不飽和雙鍵之化合物 作爲疏水性的聚合性單體，藉由使用一種含上述樹脂分散 液與此化合物的重量含量比爲1.5〜6的組成物之活性能量 線硬化型水性塗料，可製得不易發生龜裂和皺折之硬化塗 膜。 (3 )更進一步，使用上述活性能量線硬化型水性塗料而製 得的硬化塗膜，具優異的耐磨損性、耐水性。 (4 )於基材表面塗布上述活性能量線硬化型水性塗料後， 照射活性能量線，使塗布的活性能量線硬化型塗料硬化， 藉此，可容易地形成耐磨損性、耐水性優異之硬化塗膜。 (5 )上述活性能量線硬化型塗料的硬化塗膜係設置於表面 而成之物品，其表面係被覆著無龜裂和皺折之硬化塗膜， 外觀美麗。且爲具有耐磨損性、耐水性之硬化塗膜，故提 昇物品之耐久性。因此，增加物品之價値。又，即使使用 此活性能量線硬化型塗料作爲中間塗層塗料，藉由具耐磨 損性、耐水性之中間塗層而提升物品的耐久性。 本發明係依據上述見解而完成。 亦即，本發明係提供一種活性能量線硬化型水性樹脂 組成物，使用樹脂成分重量的2~15重量!之下述通式（1) 單量體，及樹脂成分重量的5 5〜70重量％之甲基丙烯酸甲 酯而製得，係在將含有0.80〜1.29mmol/g已中和的羧基之丙 烯酸樹脂（A)溶解或分散於水中而成之液中，分散含 8.6~10.5mmol/g的聚合性不飽和雙鍵的化合物（B)之樹脂 201000545 組成物，該丙烯酸樹脂（A)與該化合物（B)之含量比[(B) /(A)]，換算爲重量，係1.5〜6。 R1 ch2=ch—Ccoo——R2——coo—Vh V /n .....(1) (R1係氫原子或甲基，R2係碳原子數2〜8之伸烷基，n係 1〜10之整數。） 本發明係提供一種含有上述活性能量線硬化型水性樹 脂組成物之活性能量線硬化型塗料。 本發明係提供一種硬化塗膜之形成方法，其係於基材 塗布上述活性能量線硬化型塗料後，照射活性能量線，使 塗布的活性能量線硬化型塗料硬化。 本發明更提供一種設置上述活性能量線硬化型塗料的 硬化塗膜而成之物品。 [發明之效果] 本發明的活性能量線硬化型水性樹脂組成物，其硬化 塗膜之外觀良好，且耐磨損性、耐水性優異。藉由使用本 發明的活性能量線硬化型塗料，而製得硬化塗膜的外觀良 好，且耐磨損性、耐水性優異之硬化塗膜。又，本發明的 硬化塗膜係易於製得外觀良好，且耐磨損性、耐水性優異 之硬化塗膜。更進一步，本發明之物品係具有耐磨損性、 耐水性優異之硬化塗膜。 【實施方式】 [實施發明之最佳型態] 使用於本發明的丙烯酸樹脂（A )，係使用以樹脂形成 201000545 成分的重量爲基準之2~15重量％的下述通式（1)表示之 自由基聚合性單體，並使用以樹脂形成成分的重量爲基準 之 55~70重量％的甲基丙烯酸甲酯而製得，而且含有 0.80~1.29mmol/g已中和的羧基。若使用通式（1)表示之 自由基聚合性單體的用量係少於以樹脂形成成分的重量爲 基準的2重量％之丙烯酸樹脂時，則分散安定性不足而發 生沉澱物或分離等問題，而形成儲存安定性不足之活性能 量線硬化型水性樹脂組成物，故不理想。若使用通式（1 ) 表示之自由基聚合性單體的用量係多於以樹脂形成成分的 重量爲基準的15重量％之丙烯酸樹脂時，則形成只能製得 柔軟而耐磨損性不足的硬化塗膜之活性能量線硬化型水性 樹脂組成物，故不理想。使用於本發明的丙烯酸樹脂（A )， 係使用以樹脂形成成分的重量爲基準之3~10重量％的通 式（1)表示之自由基聚合性單體而製得之丙烯酸樹脂，形 成儲存安定性良好之活性能量線硬化型水性樹脂組成物， 故較理想。 若使用甲基丙烯酸甲酯係少於以樹脂形成成分的重量 爲基準的55重量％之丙烯酸樹脂時，則分散安定性不足且 發生沉澱物或分離等問題，而形成儲存安定性不足之活性 能量線硬化型水性樹脂組成物，故不理想。若使用甲基丙 烯酸甲酯係多於以樹脂形成成分的重量爲基準的70重量 %之丙烯酸樹脂時，則丙烯酸樹脂的流動性降低且塗平性 降低’而使塗膜外觀惡化’因製得的丙烯酸樹脂黏度非常 高’而形成不易處理之活性能量線硬化型水性樹脂組成 物’故不理想。使用於本發明的丙烯酸樹脂（A)，係使用 以樹脂形成成分的重量爲基準之55~65重量％的甲基丙烯 201000545 酸甲酯而製得之丙烯酸樹脂，形成儲存安定性良好之活性 能量線硬化型水性樹脂組成物，且製得的硬化塗膜之外觀 與基材黏附性優異，故較理想。 使用於本發明的丙烯酸樹脂（A )，係含有 0.80~1.29mmol/g範圍內的已中和之羧基。若使用已中和羧 基的含量係少於0.80mmol/g之丙烯酸樹脂，則本發明的活 性能量線硬化型樹脂組成物和活性能量線硬化型塗料的硬 化塗膜之外觀發生龜裂和顆粒，故不理想。若使用已中和 羧基的含量係多於1.29mmol/g之丙烯酸樹脂，則本發明的 活性能量線硬化型樹脂組成物和活性能量線硬化型塗料的 硬化塗膜之耐水性降低，故不理想。使用於本發明的丙烯 酸樹脂（A)，係含有0.80〜1.29mmol/g範圍內的已中和的羧 基之丙烯酸樹脂，形成硬化塗膜之外觀良好，且耐磨損性、 耐水性優異之活性能量線硬化型樹脂組成物質和活性能量 線硬化型塗料，故較理想，又尤宜含有0.90~1.20mmol/g|§ 圍內的已中和的羧基之丙烯酸樹脂。 上述已中和的羧基之含量（莫耳量），係與由用於中和 ' 的鹼性化合物的胺價所算出的鹼性化合物之莫耳量（同莫 耳量）相同而求得。用於中和的驗性化合物之胺價係將l.〇g 鹼性化合物試驗物溶解於5 m 1四氫呋喃，使用溴酚藍爲手旨 示藥，於0.5moWl鹽酸溶液中進行中和滴定而求得。 使用於本發明的丙烯酸樹脂（A)，例如可藉由使用以 樹脂形成成分的重量爲基準之2〜15重量％的上述通式（丄） 表7IK之自由基聚合性單體’並使用以樹脂形成成分的重量 爲基準之55~70重量％的甲基丙烯酸甲酯而製得，且合成 含有竣基之丙嫌酸樹脂（a)後’以鹼性化合物來中和丙，燦 -10- 201000545 酸樹脂（a)中之羧基而製得。 使用於本發明的丙烯酸樹脂（A)，係含有 0.80~1.29mmol/g範圍內的如上述般已中和之羧基。爲製得 此類丙烯酸樹脂（A )’可藉由例如使用含有 0.80~1.29mmol/g範圍內的羧基之丙烯酸樹脂作爲丙烯酸樹 脂（a )，以鹼性化合物來中和該丙烯酸樹脂（a )的全部殘 基之方法（中和率100% )、使用含有1.29mmol/g以上的羧 基之丙烯酸樹脂作爲丙烯酸樹脂（a )，以鹼性化合物來中 和該丙烯酸樹脂（a)的一部分羧基之方法等而製得。以鹼 性化合物來中和一部分的該羧基的方法之具體例，例如中 和酸價100mgKOH/g的丙烯酸樹脂（a)中的一部分羧基例 如 60 % ，調製已中和的羧基之含量爲該樹脂中的 1.07mmol/g、中和酸價80mgKOH/g的丙嫌酸樹脂（a)中的 一部分羧基例如8 0% ，調製已中和的羧基之含量爲該樹脂 中的1.14mmol/g等方法。 使用於本發明的丙烯酸樹脂（A)，係使用含有 1.3~2.7mmol/g範圍內的羧基之丙烯酸樹脂，宜爲該樹脂的 已中和羧基爲0.80~ 1.29mmol/g之丙烯酸樹脂，係因可製得 其硬化塗膜之外觀良好，且耐磨損性、耐水性優異之活性 能量線硬化型水性樹脂組成物或活性能量線硬化型塗料。 又，丙烯酸樹脂（a)宜爲酸價75~150mgK〇H/g之丙烯酸樹 脂。 本發明中，含羧基的丙烯酸樹脂（a )等之酸價，係將 l.Og樹脂試驗物溶解於1.5ml甲苯與3.5ml甲醇之混合溶 液’使用酚酞爲指示藥，於0.1 mol/1的氫氧化鉀/乙醇溶液 中進行中和滴定而求得。 -11 - 201000545 含殘基的丙烯酸樹脂（a)係可藉由使用以樹脂形成成 分的重量爲基準之2~15重量％的上述通式（1)表示之自 由基聚合性單體、以樹脂形成成分的重量爲基準之55~70 重量％的甲基丙烯酸甲酯及以含羧基的乙烯性不飽和單體 爲必須成分，依需求更使用混合其他的聚合性單體之混合 物，使該混合物於溶劑中，在聚合引發劑之存在下，進行 自由基聚合反應之溶液聚合法等而合成。該反應係可於常 壓下或高壓下進行，又，分子量之調整係可藉由調整聚合 引發劑之放入量而進行。 上述通式（1)表示之自由基聚合性單體，例如ε-羧 聚己內酯（甲基）丙烯酸酯等。具體而言，例如ε-羧聚己 內酯丙烯酸酯、羧聚己內酯丙烯酸甲酯等。其中宜爲ε -羧聚己內酯丙烯酸酯，係因安定地供應於市場且易於取得 之故。 上述e-羧聚己內酯（甲基）丙烯酸酯，係藉由例如在 酸催化劑之存在下，混合、攪拌（甲基）丙烯酸和ε -己內 酯，使於40〜150°C進行反應而製得。 上述酸催化劑，例如對甲苯磺酸、苯磺酸、氯化鋁、 氯化錫等。酸催化劑之用量’相對於1 〇〇重量份（甲基） 丙烯酸，宜爲1~20重量份之範圍。 上述含羧基乙烯性不飽和單體’例如（甲基）丙烯酸、 巴豆酸、異巴豆酸、2-甲基丙烯氧基琥珀酸乙酯、2-甲基 丙烯氧基六羥苯二酸乙酯、2·甲基丙烯氧基戊二酸乙酯； 馬來酸酐、富馬酸、衣康酸酐等二羧酸及其酸酐；一甲基 馬來酸、一乙基馬來酸、一丁基馬來酸、一辛基馬來酸、 一甲基富馬酸、一乙基富馬酸' 一丁基富馬酸、一辛基富 -12- 201000545 馬酸、一甲基衣康酸、一乙基衣康酸、一丁基衣康酸、一 辛基衣康酸等二羧酸之一烷基酯等。含羧基乙烯性不飽和 單體，宜爲丙烯酸、甲基丙烯酸等（甲基）丙烯酸。含殘 基乙烯性不飽和單體，係可單獨使用一種，亦可倂用二種 以上。含羧基乙烯性不飽和單體中，以低黏度且分散性優 異之丙烯酸樹脂（A)所得之丙烯酸爲佳。丙烯酸、甲基丙嫌 酸等（甲基）丙烯酸之用量，宜爲以樹脂形成成分的重量 爲基準之10~15重量!ίί 。 上述其他的乙烯性不飽和單體，例如丙烯酸甲酯、（甲 基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、異（甲基）丙稀 酸丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲 基）丙烯酸第三丁酯、（甲基）丙烯酸2 -乙基己酯、（甲基） 丙烯酸十二酯、（甲基）丙烯酸十八酯、（甲基）丙烯酸二 十二酯、（甲基）丙烯酸環戊酯、（甲基）丙烯酸環己酯、（甲 基）丙烯酸冰片酯、（甲基）丙烯酸異冰片酯、（甲基）丙 烯酸二環戊酯、（甲基）丙烯酸環烷基酯等（甲基）丙烯酸 烷基酯； (甲基）丙烯酸羥乙酯、（甲基）丙烯酸羥丙酯、（甲基） 丙烯酸羥丁酯等（甲基）丙烯酸羥烷基酯或其單體之ε -己 內酯或r -戊內酯等內酯類加成物等含羥基乙烯性不飽和 單體； 苯乙烯、對-第三丁基苯乙烯、α-甲基苯乙烯、乙烯甲苯 等芳香族乙烯化合物； (甲基）丙烯酸2-甲氧基乙酯、（甲基）丙烯酸4-甲氧基 丁酯等（甲基）丙烯酸ω-烷氧烷酯；Ν,Ν-二甲基（甲基） 丙烯醯胺等含三級醯胺基之乙烯系單體；甲氧基聚乙二醇 (甲基）丙烯酸酯、甲氧基聚丙二醇（甲基）丙烯酸酯等 -13- 201000545 具有聚環氧化物結構之乙烯單體；正經甲基（甲基）丙烯 酿胺、正甲氧甲基（甲基）丙嫌酿胺、正乙氧甲基（甲基） 丙烯醯胺、正丁氧甲基（甲基）丙嫌酿胺、異丁氧甲基（甲 基）丙烯醯胺等烷氧甲基（甲基）丙嫌醯胺； (甲基）丙烯酸正甲胺基乙酯等含有二級胺基之乙烯系單 體；乙烯乙醯乙酸酯、（甲基）丙烯酸2_乙醯乙醯氧乙酯等 含活性亞甲基之乙烯單體；乙烯三甲氧矽烷、3-(甲基） 丙烯醯基氧丙基三甲氧矽烷等含水解性矽烷基之乙烯系單 體； (甲基）丙烯酸三甲基矽烷酯等含矽烷酯基之乙烯系單 體；（甲基）丙烯酸縮水甘油酯、（甲基）丙烯酸甲基縮水 甘油酯、（甲基）丙烯酸3,4-環氧環己酯、縮水甘油乙烯醚、 烯丙基縮水甘油醚等含環氧基之乙烯系單體；2-異氰酸丙 烯酯、2-異氰酸乙酯乙烯醚、2-異氰酸酯甲基丙烯酸乙酯、 間-異戊基-α，〇:-二甲基苄基異氰酸酯等含異氰酸酯基之 乙烯系單體等。可單獨使用一種，亦可倂用二種以上。 使用於本發明的丙烯酸樹脂（Α)，宜爲不含聚合性不 飽和鍵結之丙烯酸樹脂，係因緩和硬化收縮而可製得基材 黏附性優異之硬化塗膜。以上述通式（1)表示的自由基聚 合性單體、甲基丙烯酸甲酯、含羧基乙烯性不飽和單體及 其他聚合性單體爲原料而調製時，爲調製不含聚合性不飽 和鍵之丙烯酸樹脂，例如含羧基乙烯性不飽和單體及其他 聚合性單體係使用含一個乙烯性不飽和單體之單體，藉此 可製得。 使用於本發明的丙烯酸樹脂（Α)宜爲側鏈含有烷基之 丙嫌酸樹脂，係因可製得可形成黏附性優異、外觀良好的 -14- 201000545 硬化塗膜之活性能量線硬化型水性樹脂組成物或活性能量 線硬化型塗料。上述烷基中，尤宜碳原子數2〜8的院基， 係因可製得可形成黏附性優異、外觀良好的硬化塗膜，且 保存安定性優異之活性能量線硬化型樹脂組成物或活性能 量線硬化型塗料。碳原子數2〜8之烷基，例如甲基、乙基、 正丙基、異丙基、正丁基、異丁基、第三丁基、環己基、 2-乙基己基等。 爲製得用爲丙烯酸樹脂（A)之側鏈含有烷基之丙烯酸 樹脂，可藉由例如合成丙烯酸樹脂（a )時，倂用含有烷基 之乙烯性不飽和單體而製得。含有烷基之乙烯性不飽和單 體，係如上述（甲基）丙烯酸烷酯類等。使用於合成丙烯 酸樹脂（a)時之含烷基的乙烯性不飽和單體之用量，宜爲 以樹脂形成成分的重量爲基準之1〜25重量％ ，係因形成儲 存安定性優異的活性能量線硬化型水性樹脂組成物或活性 能量線硬化型塗料，且製得的硬化塗膜與基材之黏附性良 好，外觀亦優異，尤宜3〜20重量％ 。含有烷基之乙烯性不 飽和單體中，（甲基）丙烯酸正丁酯因形成儲存安定性更優 異的活性能量線硬化型水性樹脂組成物或活性能量線硬化 型塗料，故更適用》 使用於本發明的丙烯酸樹脂（A)中，宜爲含羥基的丙 烯酸樹脂，係因可製得儲存安定性優異且製得的硬化塗膜 之耐水性亦良好之活性能量線硬化型水性樹脂組成物或活 性能量線硬化型塗料。含羥基的丙烯酸樹脂中，宜爲羥基 價15~100mgK〇H/g之丙烯酸樹脂，尤宜羥基價爲 25〜65mgKOH/g之丙烯酸樹脂。 丙烯酸樹脂（A)中的含羥基之丙烯酸樹脂，係可藉由 -15- 201000545 使用以樹脂形成成分的重量爲基準之2〜15重量％的上述 通式（1)表示之自由基聚合性單體作爲上述丙烯酸樹脂 (a)、以樹脂形成成分的重量爲基準之55 ~70重量％的甲 基丙烯酸甲酯、含羧基的乙烯性不飽和單體及以含羥基的 乙烯性不飽和單體爲必須成分，依需求更使用混合其他的 聚合性單體之混合物，使該混合物於溶劑中，在聚合引發 劑之存在下’進行自由基聚合反應之溶液聚合法等合成丙 烯酸樹脂後，以鹼性化合物來中和該丙烯酸樹脂中的羧基 而製得。 上述含羥基的乙烯性不飽和單體，例如（甲基）丙烯 酸羥乙酯、（甲基）丙烯酸羥丙酯、（甲基）丙烯酸羥丁酯 等。其中，宜爲（甲基）丙烯酸羥乙酯，係因可製得儲存 安定性優異的活性能量線硬化型水性樹脂組成物和活性能 量線硬化型塗料。 使用於調製作爲丙烯酸樹脂（a)的含羥基丙烯酸樹脂 時之上述含羥基的乙烯性不飽和單體之用量，宜爲以樹脂 形成成分的重量爲基準之3〜20重量％ 。 丙烯酸樹脂（A)等之羥基價，係添加25ml醋酸酐/ 吡啶溶液（體積比1/19)於lO.Og樹脂試驗物中，加熱並 進行1小時反應後，使用酹酞爲指示藥，以0.5 mol/1氫氧 化鉀/乙醇溶液進行中和滴定而求得。 合成上述丙烯酸樹脂（a )時所使用之溶劑，宜爲與水 不分離而混合之水混合性有機溶劑，其中，尤宜在25 °C的 對水溶解度（溶解於100 g水之有機溶劑之公克數）爲3g 以上之有機溶劑。此類水混合性有機溶劑，例如甲醇、乙 醇、丙醇、丁醇等醇系溶劑；丙酮、甲乙酮等酮系溶劑； -16- 201000545 乙二醇一甲醚、乙二醇二甲醚、乙二醇一乙醚、乙二醇二 乙醚、乙二醇一丙醚、乙二醇一異丙醚、一丁醚、二乙二 醇一甲醚、二乙二醇二甲醚、二乙二醇一乙醚、二乙二醇 二乙醚、二乙二醇一異丙醚、二乙二醇一丁醚、三乙二醇 一甲醚、三乙二醇二甲醚、丙二醇一甲醚、丙二醇二甲酸、 丙二醇一丙醚、丙二醇一丁醚、二丙二醇一甲醚、二丙二 醇二甲醚等二醇醚系溶劑等。此類水混合性有機溶劑{系π 單獨使用，亦可倂用二種以上。 f 上述水混合性有機溶劑，可依需求更進一步倂用其他 有機溶劑，例如甲苯、二甲苯等芳香族烴系溶劑；己I完、 庚烷、辛烷、癸烷等脂肪族烴系溶劑；醋酸甲酯、醋酸乙 酯、醋酸異丙酯、醋酸丁酯、醋酸戊酯、甲酸乙酯、丙酸 丁酯等酯系溶劑等，惟因會產生臭氣而降低作業環境，故 不適合使用，即使必須使用時，其用量相對於水性樹脂組 成物之總量，宜爲1 %以下。上述芳香族烴系溶劑中，混 合芳香族烴系溶劑例如索爾貝索（音譯，SolvesscO # 1〇〇、 索爾貝索# 150等市售品。 〇 以上述溶液聚合法等而合成丙烯酸樹脂（a )時，可使 用之自由基聚合引發劑，例如2,2’-偶氮雙（異丁腈）、2,2，-偶氮雙（2-甲基丁腈）、偶氮雙氰戊酸等偶氮化合物；第三 丁基過氧三甲基乙酸酯、第三丁基過氧苯甲酸酯、第三丁 基過氧-2-己酸乙酯、二第三丁基過氧化物、氫過氧化枯 烯、苯甲醯過氧化物、第三丁氫過氧化物等有機過氧化物； 過氧化氫、過硫酸銨、過硫酸鉀、過硫酸鈉等無機過氧化 物，可單獨使用或倂用二種以上。上述自由基聚合引發劑 之用量，相對於構成丙烯酸樹脂的成分之總量，宜爲0.1 ~ 10 -17- 201000545 重量％之範圍內。 進行上述溶液聚合時的反應容器中之不揮發成分之含 量，宜爲30~90重量％ ，尤宜50~80重量％ 。 使用於中和丙烯酸樹脂（a)中的羧基之中和劑（鹼性 化合物），例如一甲胺、二甲胺、三甲胺、一乙胺、二乙胺、 三乙胺、一丙胺、二丙胺、三丙胺等烷胺；一乙醇胺、二 乙醇胺、一異丙醇胺、二異丙醇胺、N-甲基乙醇胺、Ν,Ν-二甲基乙醇胺、Ν，Ν-二乙基乙醇胺、2-胺基-2-甲基丙醇、 2-(二甲胺）-2-甲基丙醇、Ν-甲基二乙醇胺等烷醇胺；乙 二胺、二乙三胺、三乙四胺、四乙五胺等多元胺等有機胺 或氨（水）。鹼性化合物中，因揮發性高，不易殘留於硬化 塗膜，可製得耐水性優異之硬化塗膜，宜爲氨水、三甲胺。 中和劑（鹼性化合物）係可單獨使用，亦可倂用二種以上。 例如藉由將ε -己內酯加成於含羧基的丙烯酸樹脂，可 製得含有由通式（1)所示的化合物之重複單位與直接鍵結 於此的氫原子而形成之結構之丙烯酸樹脂。 使用於本發明的丙烯酸樹脂（a)之數平均分子量 (Μη)，宜爲 5,000~30,000，其中尤宜 8,000〜25,000，係因 可製得儲存安定性優異，且黏度不過度上升之活性能量線 硬化型水性樹脂組成物和活性能量線硬化型塗料。 使用於本發明的丙烯酸樹脂（a)之重量平均分子量 (Mw)，宜爲 1 0,000~ 100,000，其中尤宜 30,000~80,000， 係因可製得儲存安定性優異，且黏度不過度上升之活性能 ' 量線硬化型水性樹脂組成物和活性能量線硬化型塗料。 本發明中，含羧基的丙烯酸樹脂（a)等樹脂的數平均 分子量和重量平均分子量之測定，係使用凝膠滲透層析， -18- 201000545 於下述條件藉由聚苯乙烯換算’去除分子量1000以下的成 分而求得。 測定裝置：東曹股份公司製 HLC-8220 管柱：東曹股份公司製保護管柱HXL-H +東曹股份公司製 TSKgelG5000HXL +東曹股份公司製 TSKgel G4000HXL +東曹股份公司製 TSKgel G3 000HXL +東曹股份公司製 TSKgel G2000HXL 檢測器：RI (微差折射計）201000545 VI. Description of the Invention: [Technical Field] The present invention relates to a coating agent for plastics, films, and the like, which has a good appearance of a hardened coating film and an active energy ray excellent in abrasion resistance and water resistance. A cured water-based resin composition, an active energy ray-curable paint containing the composition, a method for forming a cured coating film using the paint, and an article obtained by providing a cured coating film of a coating material. [Prior Art] The active energy ray-curable composition is used as a hard coating agent for plastic substrates such as home electric appliances and mobile phones because of its low heat history on the coated substrate and excellent hardness and abrasion resistance of the coating film. . Such an active energy ray-curable composition, for example, a polymer having a polymerizable unsaturated double bond (for example, acryl acrylate or the like) or a polymer substantially free of a polymerizable unsaturated double bond (for example, an acrylic resin, etc.) An active energy ray-curable composition (non-aqueous active energy ray-curable composition) containing a polymerizable monomer and an organic solvent as a diluent. When the active energy ray-curable composition is used as an active energy ray-curable coating material for spray coating, for example, the content of the organic solvent is from 50 to 90% by weight based on the weight of the coating material. Therefore, when an active energy ray-curable coating material containing the resin composition is used to form a cured coating film on the surface of a substrate such as plastic, the organic solvent in the coating is swollen to deteriorate the working environment. And the volatile organic solvent is degraded into air pollution. Among them, it is considered to use a water-containing active energy ray-curable aqueous composition # as a diluent. Specifically, for example, an aqueous resin dispersion (1) having an average particle diameter of 10 Å to 1 〇〇 nm is disclosed, and at least one of the blending molecules contains at least one @ -4- 201000545 carbon-carbon double bond photosensitive property. An aqueous photosensitive coating composition formed by the oligomer (2) and the photosensitive monomer (3) having at least one carbon-carbon double bond in the molecule (for example, refer to Patent Document 1). Specifically, for example, Example 1 of Patent Document 1 discloses that 2.3 parts by weight of water-soluble urethane acrylate is contained in 100 parts by weight of an acrylic fine particle emulsion (for example, NANOCRYLBCX-2914 manufactured by Toyo Ink Co., Ltd.). And a photosensitive coating composition formed by 2.3 parts by weight of trimethylolpropane triacrylate. Further, an ultraviolet curable aqueous coating composition containing a water-soluble resin (A) having a (meth)acryl fluorenyl group, a polyfunctional (meth) acrylate compound (B), and a photopolymerization initiator in an emulsified state is disclosed. (For example, refer to Patent Document 2). Specifically, for example, a carboxyl group of a carboxyl group-containing acrylate resin obtained by using methyl methacrylate as an essential component is neutralized, and the obtained water-dispersible acrylate and urethane acrylate oligomer are dispersed in water. The emulsion. When the active energy ray-curable resin composition is produced by using the acrylic fine particle emulsion used in the above Patent Document 1, a hydrophobic polymerizable monomer and a water-soluble uric acid which contribute to improvement of abrasion resistance and water resistance are used in combination. Acrylate or spontaneously emulsifying urethane acrylate, which complements the dispersibility and stability of the acrylic microparticle emulsion in water-soluble urethane acrylate or spontaneous emulsifying urethane acrylate, and disperses hydrophobic polymerizable monomer In the water. Therefore, the effect of the hydrophobic polymerizable monomer which can improve the abrasion resistance and the water resistance can not be sufficiently exhibited, and the cured coating film obtained by using the aqueous photosensitive coating composition of Patent Document 1 is resistant to abrasion. Insufficient water resistance. In the ultraviolet curable aqueous coating composition disclosed in Patent Document 2, a hydrophobic urethane acrylate oligomer is used as the polyfunctional (methyl 201000545 acrylate) acrylate, whereby the abrasion resistance of the cured coating film can be improved. Water resistance. However, even if the (meth)acrylonitrile-based water-soluble resin (A) used in the ultraviolet curable aqueous coating composition does not have sufficient dispersion for dispersing the hydrophobic urethane acrylate oligomer in water It is also difficult to disperse the polyfunctional (meth) acrylate compound (B) in the above-mentioned (meth) acrylonitrile-containing water-soluble resin (A) in water, and a part of the polyfunctional (meth) acrylate compound ( B) Immediate separation. Therefore, the hardened coating film is liable to cause cracks and wrinkles. Moreover, the storage stability of the ultraviolet curable aqueous coating composition is also poor. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2004-0 1 077. A coating agent for plastics, a film, or the like, an active energy ray-curable aqueous resin composition having a good appearance of a cured coating film, excellent abrasion resistance and water resistance, and an active energy ray-curable coating containing the composition A method of forming a cured coating film using the coating material and an article for providing a cured coating film of the coating material. [Means for Solving the Problem] The inventors of the present invention have found the following findings by focusing on the results of the study. (1) A radical polymerizable monomer having 2 to 15% by weight of an alkylene group having 2 to 8 carbon atoms and having a carboxyl group added to the terminal of the alkylene group based on the weight of the resin-forming component It is prepared by using methyl methacrylate in an amount of 55 to 70% by weight based on the weight of the resin-forming component, and an acrylic resin (hydrophilic propylene) containing 0.80 to 1.29 mmol/g of the neutralized residue. 201000545 Acid resin) A resin dispersion dispersed in water to disperse a hydrophobic polymerizable monomer well. Therefore, by using an active energy ray-curable water-based paint containing such a component, a cured coating film which is less likely to be cracked and wrinkled can be obtained. (2) using a compound having a polymerizable unsaturated double bond of 8.6 to 10.5111111〇 as a hydrophobic polymerizable monomer by using a resin-containing dispersion liquid and the compound in a weight ratio of 1.5 to 6 The active energy ray-curable water-based paint of the composition can produce a hardened coating film which is less likely to be cracked and wrinkled. (3) Further, the cured coating film obtained by using the above active energy ray-curable aqueous coating material has excellent abrasion resistance and water resistance. (4) After applying the active energy ray-curable aqueous coating material to the surface of the substrate, the active energy ray is irradiated to cure the applied active energy ray-curable coating material, whereby the abrasion resistance and the water resistance can be easily formed. Hardened film. (5) The cured coating film of the active energy ray-curable coating material is provided on the surface of the article, and the surface thereof is coated with a hard coating film having no cracks and wrinkles, and the appearance is beautiful. Moreover, it is a hardened coating film having abrasion resistance and water resistance, so that the durability of the article is improved. Therefore, increase the price of the item. Further, even if this active energy ray-curable coating material is used as the intermediate coating material, the durability of the article is improved by the intermediate coating having abrasion resistance and water resistance. The present invention has been completed based on the above findings. That is, the present invention provides an active energy ray-curable aqueous resin composition, which has a weight of 2 to 15 parts by weight of the resin component, and a weight of the following formula (1), and a weight of the resin component of 5 5 to 70 The methyl methacrylate is obtained by dissolving or dispersing an acrylic resin (A) containing 0.80 to 1.29 mmol/g of a neutralized carboxyl group in water, and dispersing 8.6 to 10.5 mmol/ The composition of the resin (20) of the polymerizable unsaturated double bond of g, 201000545, the content ratio of the acrylic resin (A) to the compound (B) [(B) / (A)], converted to weight, is 1.5 ~6. R1 ch2=ch—Ccoo——R2——coo—Vh V /n (1) (R1 is a hydrogen atom or a methyl group, R2 is an alkylene group having 2 to 8 carbon atoms, n is 1 An integer of ～10. The present invention provides an active energy ray-curable coating material containing the above active energy ray-curable aqueous resin composition. The present invention provides a method for forming a cured coating film which is applied to a substrate to which the active energy ray-curable coating material is applied, and then irradiated with an active energy ray to cure the applied active energy ray-curable coating material. The present invention further provides an article in which a hard coat film of the above active energy ray-curable paint is provided. [Effects of the Invention] The active energy ray-curable aqueous resin composition of the present invention has a good appearance of a cured coating film and is excellent in abrasion resistance and water resistance. By using the active energy ray-curable coating material of the present invention, a cured coating film having a good appearance of a cured coating film and excellent abrasion resistance and water resistance can be obtained. Further, the cured coating film of the present invention is easy to obtain a cured coating film which is excellent in appearance and excellent in abrasion resistance and water resistance. Further, the article of the present invention is a cured coating film which is excellent in abrasion resistance and water resistance. [Embodiment] [Best Mode for Carrying Out the Invention] The acrylic resin (A) used in the present invention is represented by the following general formula (1) in an amount of 2 to 15% by weight based on the weight of the resin-forming 201000545 component. The radical polymerizable monomer is obtained by using methyl methacrylate in an amount of 55 to 70% by weight based on the weight of the resin component, and contains 0.80 to 1.29 mmol/g of a neutralized carboxyl group. When the amount of the radical polymerizable monomer represented by the formula (1) is less than 2% by weight based on the weight of the resin component, the dispersion stability is insufficient to cause precipitation or separation. Further, an active energy ray-curable aqueous resin composition having insufficient storage stability is formed, which is not preferable. When the radical polymerizable monomer represented by the general formula (1) is used in an amount of more than 15% by weight based on the weight of the resin-forming component, the formation can be made soft and the abrasion resistance is insufficient. The active energy ray-curable aqueous resin composition of the cured coating film is not preferable. The acrylic resin (A) used in the present invention is an acrylic resin obtained by using a radical polymerizable monomer represented by the formula (1) in an amount of 3 to 10% by weight based on the weight of the resin component. It is preferable to have an active energy ray-curable aqueous resin composition having good stability. When a methyl methacrylate type is used in an amount of less than 55% by weight based on the weight of the resin-forming component, the dispersion stability is insufficient and a problem such as precipitation or separation occurs, and an active energy having insufficient storage stability is formed. The wire-curable aqueous resin composition is not preferable. When methyl methacrylate is used in an amount of 70% by weight based on the weight of the resin component, the fluidity of the acrylic resin is lowered and the flatness is lowered to deteriorate the appearance of the coating film. The acrylic resin has a very high viscosity and forms an active energy ray-curable aqueous resin composition which is difficult to handle, which is not preferable. The acrylic resin (A) used in the present invention is an acrylic resin obtained by using 55 to 65% by weight of methacrylic acid 201000545 methyl ester based on the weight of the resin-forming component to form an active energy having good storage stability. The line-hardening type aqueous resin composition is preferable because the obtained cured film has excellent adhesion to the substrate. The acrylic resin (A) used in the present invention contains a neutralized carboxyl group in the range of 0.80 to 1.29 mmol/g. When an acrylic resin having a neutralized carboxyl group content of less than 0.80 mmol/g is used, the appearance of the hardened coating film of the active energy ray-curable resin composition and the active energy ray-curable coating material of the present invention is cracked and granulated. It is not ideal. When an acrylic resin having a content of a neutralized carboxyl group of more than 1.29 mmol/g is used, the water resistance of the active energy ray-curable resin composition of the present invention and the cured coating film of the active energy ray-curable coating material is lowered, which is not preferable. . The acrylic resin (A) used in the present invention is an acrylic resin containing a neutralized carboxyl group in the range of 0.80 to 1.29 mmol/g, and has a good appearance of a cured coating film, and is excellent in abrasion resistance and water resistance. The energy ray-curable resin composition and the active energy ray-curable coating material are preferable, and it is preferable to contain an acrylic resin having a neutralized carboxyl group in the range of 0.90 to 1.20 mmol/g. The content of the neutralized carboxyl group (molar amount) is determined by the same molar amount (the same molar amount) of the basic compound calculated from the amine value of the basic compound used for neutralization. The amine valence of the neutralizing test compound is obtained by dissolving the l. 〇g basic compound test substance in 5 m 1 of tetrahydrofuran, using bromophenol blue as a drug, and performing neutralization titration in 0.5 mol of hydrochloric acid solution. Seek. The acrylic resin (A) used in the present invention can be used, for example, by using 2 to 15% by weight based on the weight of the resin-forming component, and the radical polymerizable monomer of the above formula (IK) It is prepared by using methyl methacrylate in an amount of 55 to 70% by weight based on the weight of the resin-forming component, and synthesizing a thiol-containing acrylic acid resin (a) and then neutralizing C with a basic compound. - 201000545 Manufactured from the carboxyl group in the acid resin (a). The acrylic resin (A) used in the present invention contains a carboxyl group which has been neutralized as described above in the range of 0.80 to 1.29 mmol/g. To obtain such an acrylic resin (A)', the acrylic resin (a) can be neutralized with a basic compound by using, for example, an acrylic resin containing a carboxyl group in the range of 0.80 to 1.29 mmol/g as the acrylic resin (a). Method for all residues (100% neutralization ratio), using an acrylic resin containing 1.29 mmol/g or more of a carboxyl group as an acrylic resin (a), and neutralizing a part of carboxyl groups of the acrylic resin (a) with a basic compound The method is obtained by the method. A specific example of a method of neutralizing a part of the carboxyl group with a basic compound, for example, neutralizing a part of carboxyl groups in the acrylic resin (a) having an acid value of 100 mgKOH/g, for example, 60%, and preparing the neutralized carboxyl group to be the resin. a method of 1.07 mmol/g, neutralizing an acid value of 80 mgKOH/g, a part of carboxyl groups in the acrylic acid resin (a), for example, 80%, and preparing a neutralized carboxyl group to be 1.14 mmol/g in the resin. . The acrylic resin (A) used in the present invention is an acrylic resin containing a carboxyl group in the range of 1.3 to 2.7 mmol/g, and preferably an acrylic resin having a neutralized carboxyl group of 0.80 to 1.29 mmol/g. An active energy ray-curable aqueous resin composition or an active energy ray-curable coating material which is excellent in the appearance of the cured coating film and excellent in abrasion resistance and water resistance can be obtained. Further, the acrylic resin (a) is preferably an acrylic resin having an acid value of 75 to 150 mg K 〇 H / g. In the present invention, the acid value of the carboxyl group-containing acrylic resin (a) or the like is obtained by dissolving 1.0 g of the resin test substance in a mixed solution of 1.5 ml of toluene and 3.5 ml of methanol, using phenolphthalein as an indicator, at 0.1 mol/l. The neutralization titration was carried out in a potassium hydroxide/ethanol solution. -11 - 201000545 Resin-containing acrylic resin (a) is a radically polymerizable monomer represented by the above formula (1), which is 2 to 15% by weight based on the weight of the resin-forming component. Methyl methacrylate and a carboxyl group-containing ethylenically unsaturated monomer having an amount of 55 to 70% by weight based on the weight of the component are essential components, and a mixture of other polymerizable monomers is used as needed to make the mixture. The solution is synthesized in a solvent by a solution polymerization method such as a radical polymerization reaction in the presence of a polymerization initiator. The reaction can be carried out under normal pressure or under high pressure, and the molecular weight can be adjusted by adjusting the amount of the polymerization initiator. The radical polymerizable monomer represented by the above formula (1), for example, ε-carboxypolycaprolactone (meth) acrylate or the like. Specifically, for example, ε-carboxypolycaprolactone acrylate, carboxypolycaprolactone methyl acrylate or the like. Among them, ε-carboxypolycaprolactone acrylate is preferable because it is stably supplied to the market and is easy to obtain. The above-mentioned e-carboxypolycaprolactone (meth) acrylate is reacted at 40 to 150 ° C by, for example, mixing and stirring (meth)acrylic acid and ε-caprolactone in the presence of an acid catalyst. And made. The above acid catalyst is, for example, p-toluenesulfonic acid, benzenesulfonic acid, aluminum chloride, tin chloride or the like. The amount of the acid catalyst is preferably in the range of 1 to 20 parts by weight based on 1 part by weight of the (meth)acrylic acid. The above-mentioned carboxyl group-containing ethylenically unsaturated monomer 'e.g. (meth)acrylic acid, crotonic acid, isocrotonic acid, ethyl 2-methylpropenoxysuccinate, ethyl 2-methylpropoxy hexahydroxyphthalate 2, methyl methoxy glutaric acid ethyl ester; dicarboxylic acid such as maleic anhydride, fumaric acid, itaconic anhydride and its anhydride; monomethyl maleic acid, monoethyl maleic acid, monobutyl Maleic acid, monooctyl maleic acid, monomethyl fumaric acid, monoethyl fumaric acid 'monobutyl fumaric acid, monooctyl rich-12- 201000545 horse acid, monomethyl itaconic acid, An alkyl ester of a dicarboxylic acid such as ethyl itaconic acid, monobutyl itaconic acid or monooctyl itaconic acid. The carboxyl group-containing ethylenically unsaturated monomer is preferably (meth)acrylic acid such as acrylic acid or methacrylic acid. The residue-containing ethylenically unsaturated monomer may be used singly or in combination of two or more. Among the carboxyl group-containing ethylenically unsaturated monomers, acrylic acid obtained by the acrylic resin (A) having a low viscosity and excellent dispersibility is preferred. The amount of (meth)acrylic acid such as acrylic acid or methyl propyl sulfonic acid is preferably 10 to 15 parts by weight based on the weight of the resin-forming component! The above other ethylenically unsaturated monomers, such as methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate Ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate , behenyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, borneol (meth)acrylate, isobornyl (meth)acrylate, (methyl) (alkyl)alkyl (meth)acrylate such as dicyclopentanyl acrylate or cycloalkyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate a hydroxyl group-containing ethylenically unsaturated monomer such as a hydroxyalkyl (meth) acrylate or a monomer such as ε-caprolactone or r-valerolactone lactone; styrene, p- An aromatic vinyl compound such as tributylstyrene, α-methylstyrene or vinyl toluene; (meth)acrylic acid 2-methoxyethyl ester, 4-methoxybutyl (meth)acrylate, etc. (Omega) alkoxylated (meth)acrylate; hydrazine, hydrazine-dimethyl(methyl) acrylamide a vinyl monomer containing a tertiary amide group; methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, etc.-13-201000545 having a polyepoxide structure Ethylene monomer; n-methyl (meth) acrylamide, n-methoxymethyl (methyl) acrylamide, n-ethoxymethyl (meth) acrylamide, n-butoxymethyl (methyl) An alkoxymethyl (meth) propyl amide such as acrylamide or isobutoxymethyl (meth) acrylamide; a methylaminoethyl (meth) acrylate or the like containing a secondary amine group Vinyl monomer; ethylene vinyl acetate-containing, ethylene glycol-containing ethylene monomer such as ethylene glycol methacrylate; ethylene trimethoxy decane, 3-(methyl) propylene hydride a vinyl monomer containing a hydrolyzable alkylene group such as oxypropyltrimethoxyoxane; a vinyl monomer having a decyl ester group such as trimethyldecyl (meth)acrylate; An epoxy group-containing vinyl compound such as glycidyl acrylate, methyl glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, glycidyl vinyl ether or allyl glycidyl ether Monomer; isocyanate containing 2-isoisocyanate, 2-isocyanatoethyl ether, 2-isocyanate ethyl methacrylate, m-isoamyl-α, fluorene-dimethylbenzyl isocyanate A vinyl monomer or the like. One type may be used alone or two or more types may be used. The acrylic resin to be used in the present invention is preferably an acrylic resin which does not contain a polymerizable unsaturated bond, and which is a hardened coating film which is excellent in adhesion of a substrate by moderate hardening shrinkage. When the radical polymerizable monomer, methyl methacrylate, carboxyl group-containing ethylenically unsaturated monomer, and other polymerizable monomer represented by the above formula (1) are used as a raw material, the polymerization is not contained. The acrylic resin of the bond, for example, a carboxyl group-containing ethylenically unsaturated monomer and other polymerizable single system, can be obtained by using a monomer containing one ethylenically unsaturated monomer. The acrylic resin to be used in the present invention is preferably an acrylic acid-containing acid resin having an alkyl group in its side chain, because it can produce an active energy ray-curing type of a hardened coating film which can form an excellent adhesion and a good appearance. An aqueous resin composition or an active energy ray-curable coating. Among the above-mentioned alkyl groups, a hospital base having a carbon number of 2 to 8 is preferable, and an active energy ray-curable resin composition excellent in adhesion and excellent in appearance and excellent in storage stability can be obtained. Active energy ray hardening coating. An alkyl group having 2 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, 2-ethylhexyl or the like. In order to obtain an acrylic resin containing an alkyl group as a side chain of the acrylic resin (A), for example, when the acrylic resin (a) is synthesized, an alkyl group-containing ethylenically unsaturated monomer is used. The ethylenically unsaturated monomer having an alkyl group is, for example, the above-mentioned alkyl (meth)acrylate. The amount of the alkyl group-containing ethylenically unsaturated monomer used in the synthesis of the acrylic resin (a) is preferably from 1 to 25% by weight based on the weight of the resin-forming component, because of the formation of an active energy excellent in storage stability. The line-curable aqueous resin composition or the active energy ray-curable coating material has a good adhesion to the substrate and an excellent appearance, and is particularly preferably 3 to 20% by weight. Among the ethylenically unsaturated monomers containing an alkyl group, n-butyl (meth)acrylate is more suitable for use because it forms an active energy ray-curable aqueous resin composition or an active energy ray-curable coating which is more excellent in storage stability. In the acrylic resin (A) of the present invention, it is preferably a hydroxyl group-containing acrylic resin, which is an active energy ray-curable aqueous resin composition which is excellent in storage stability and has good water resistance of the obtained cured coating film. Or active energy ray-curable coatings. The hydroxyl group-containing acrylic resin is preferably an acrylic resin having a hydroxyl group of 15 to 100 mg K 〇 H / g, and particularly preferably an acrylic resin having a hydroxy value of 25 to 65 mg KOH / g. The hydroxyl group-containing acrylic resin in the acrylic resin (A) is a radical polymerizable monomer represented by the above formula (1), which is 2 to 15% by weight based on the weight of the resin component, by -15 to 201000545. The body is 55 to 70% by weight of methyl methacrylate, a carboxyl group-containing ethylenically unsaturated monomer, and a hydroxyl group-containing ethylenically unsaturated monomer based on the acrylic resin (a) and the weight of the resin component. As an essential component, a mixture of other polymerizable monomers is further mixed as needed, and the mixture is subjected to a solution polymerization method in which a radical polymerization reaction is carried out in a solvent in the presence of a polymerization initiator, and then an alkali is used. A compound is prepared by neutralizing a carboxyl group in the acrylic resin. The hydroxyl group-containing ethylenically unsaturated monomer is, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or hydroxybutyl (meth)acrylate. Among them, hydroxyethyl (meth)acrylate is preferred because it can produce an active energy ray-curable aqueous resin composition and an active energy ray-curable coating which are excellent in storage stability. The amount of the above hydroxyl group-containing ethylenically unsaturated monomer used in the preparation of the hydroxyl group-containing acrylic resin as the acrylic resin (a) is preferably from 3 to 20% by weight based on the weight of the resin component. The hydroxyl value of the acrylic resin (A) or the like is added to 25 ml of an acetic anhydride/pyridine solution (volume ratio of 1/19) in a 1.0 kg resin test, and after heating for 1 hour, the antimony is used as an indicator to The 0.5 mol/1 potassium hydroxide/ethanol solution was obtained by neutralization titration. The solvent used in the synthesis of the above acrylic resin (a) is preferably a water-miscible organic solvent which is mixed without being separated from water, and particularly preferably has a water solubility at 25 ° C (an organic solvent dissolved in 100 g of water). The gram is an organic solvent of 3 g or more. Such a water-miscible organic solvent, for example, an alcohol solvent such as methanol, ethanol, propanol or butanol; a ketone solvent such as acetone or methyl ethyl ketone; -16- 201000545 ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, and B Glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol Monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol A glycol ether solvent such as formic acid, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether or dipropylene glycol dimethyl ether. Such a water-miscible organic solvent {series π may be used singly or in combination of two or more. f The water-miscible organic solvent may further be used in an organic solvent such as an aromatic hydrocarbon solvent such as toluene or xylene; or an aliphatic hydrocarbon solvent such as heptane, heptane, octane or decane; An ester solvent such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate or butyl propionate. However, it is not suitable for use because it causes odor and lowers the working environment. When it is necessary to use it, the amount thereof is preferably 1% or less based on the total amount of the aqueous resin composition. In the aromatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent such as Solbesso (a commercially available product such as SolvesscO #1〇〇, Solbesso #150) is mixed. The acrylic resin is synthesized by the above-described solution polymerization method or the like. (a), a radical polymerization initiator which can be used, for example, 2,2'-azobis(isobutyronitrile), 2,2,-azobis(2-methylbutyronitrile), azobiscyano An azo compound such as valeric acid; tert-butylperoxytrimethylacetate, tert-butylperoxybenzoate, tert-butylperoxy-2-hexanoate, di-tert-butyl Organic peroxides such as peroxide, cumene hydroperoxide, benzamidine peroxide, and third butane hydroperoxide; inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate These may be used singly or in combination of two or more. The amount of the above-mentioned radical polymerization initiator is preferably in the range of 0.1 to 10 -17 to 201000545% by weight based on the total amount of the components constituting the acrylic resin. The content of the non-volatile component in the reaction vessel is preferably 30 to 90% by weight, particularly preferably 50 to 80% by weight. a carboxyl group neutralizing agent (basic compound) used for neutralizing the acrylic resin (a), such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, An alkylamine such as propylamine or tripropylamine; monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, N-methylethanolamine, hydrazine, hydrazine-dimethylethanolamine, hydrazine, hydrazine-diethylethanolamine, Alkanolamines such as 2-amino-2-methylpropanol, 2-(dimethylamine)-2-methylpropanol, hydrazine-methyldiethanolamine; ethylenediamine, diethylenetriamine, triethylenetetramine An organic amine such as a polyamine such as an amine or tetraethylene pentaamine or ammonia (water). The basic compound has high volatility and does not easily remain in the cured coating film, and can obtain a hardened coating film excellent in water resistance, and is preferably ammonia water. Trimethylamine. The neutralizing agent (basic compound) may be used singly or in combination of two or more. For example, by adding ε-caprolactone to a carboxyl group-containing acrylic resin, it is possible to obtain a formula containing 1) an acrylic resin having a structure in which a repeating unit of the compound and a hydrogen atom directly bonded thereto are formed. The acrylic acid used in the present invention The number average molecular weight (Μη) of the resin (a) is preferably 5,000 to 30,000, and particularly preferably 8,000 to 25,000, which is an active energy ray-curable aqueous resin composition which is excellent in storage stability and does not excessively increase in viscosity. And an active energy ray-curable coating material. The weight average molecular weight (Mw) of the acrylic resin (a) used in the present invention is preferably from 10,000 to 100,000, particularly preferably from 30,000 to 80,000, which is excellent in storage stability. And an active energy ray-curable water-based resin composition and an active energy ray-curable coating material which are not excessively increased in viscosity. In the present invention, the number average molecular weight and the weight average molecular weight of a resin such as a carboxyl group-containing acrylic resin (a) are measured, It was determined by gel permeation chromatography, -18-201000545, by removing the component having a molecular weight of 1,000 or less by polystyrene conversion under the following conditions. Measuring device: HCL-8220 manufactured by Tosoh Corporation: Pipeline HXL-H manufactured by Tosoh Corporation + TSKgel G5000HXL manufactured by Tosoh Corporation + TSKgel G4000HXL manufactured by Tosoh Corporation + TSKgel G3 000HXL + manufactured by Tosoh Corporation TSKgel G2000HXL detector manufactured by Tosoh Corporation: RI (differential refractometer)
數値處理：東曹股份公司製 S08010 測定條件：管柱溫度 40°C 溶劑 四氫呋喃 流速 1.0ml/分 標準：聚乙烯 試驗物：以樹脂固形分換算’ 0.4重量!ϋ的四氫呋喃溶 液經過微過濾器過濾之濾液（1 〇〇 V 1 )。 使用於本發明的含羧基的丙烯酸樹脂（a)之玻璃轉移 溫度，宜爲30°C ~ 1〇〇°C，係因製得可形成耐磨損性和基材 黏附性優異的硬化塗膜之活性能量線硬化型水性樹脂組成 物。因此，合成丙烯酸樹脂（a )時，爲使玻璃轉移溫度爲 30°C ~100°C，宜適當地選擇原料成分而組合。尤宜60°C〜90 °C，係因製得耐磨損性和基材黏附性更優異之硬化塗膜。 丙烯酸樹脂（a )等樹脂之玻璃轉移溫度，係依據 JIS-K-7121以微差掃描熱量（DSC)測定而得。 測定裝置：TA儀器製 DSCQ-100 容器：鋁製開口管 -19· 201000545 升溫速度：20°C /分 上述丙烯酸樹脂（a)等樹脂之玻璃轉移溫度，亦可 以下述式來計算。又，下述式之玻璃轉移溫度係絕對溫 度（°K )。Data processing: S08010 manufactured by Tosoh Corporation. Measurement conditions: column temperature 40 ° C Solvent tetrahydrofuran flow rate 1.0 ml / min Standard: Polyethylene test substance: converted to resin solids '0.4 weight! ϋ tetrahydrofuran solution through microfilter Filtered filtrate (1 〇〇V 1 ). The glass transition temperature of the carboxyl group-containing acrylic resin (a) used in the present invention is preferably 30 ° C to 1 ° C, which is a hardened coating film which is excellent in abrasion resistance and substrate adhesion. An active energy ray-curable aqueous resin composition. Therefore, in the case of synthesizing the acrylic resin (a), in order to adjust the glass transition temperature to 30 ° C to 100 ° C, it is preferred to appropriately select the raw material components and combine them. It is particularly suitable for a hardened coating film which is excellent in abrasion resistance and adhesion of a substrate, at 60 ° C to 90 ° C. The glass transition temperature of the resin such as the acrylic resin (a) is measured by differential scanning calorimetry (DSC) in accordance with JIS-K-7121. Measuring device: manufactured by TA Instruments DSCQ-100 Container: open tube made of aluminum -19· 201000545 Heating rate: 20 ° C / min The glass transition temperature of the resin such as the acrylic resin (a) can also be calculated by the following formula. Further, the glass transition temperature of the following formula is an absolute temperature (°K).
Tg1 = Σ Xi · Tgi·1 其中’樹脂係i=l~n爲止的n個單體成分進行共聚。 Xi係第i個單體之重量分率，Tgi係第i個單體的單獨聚合 物之玻璃轉移溫度。單體的單獨聚合物之玻璃轉移溫度， 係可使用 Polymer Handbook ( 4,h Edition) J.Brandrup, E. H. Immergut，E. A. Grulke 著（Wiley Interscience)記載之値。 爲調製丙烯酸樹脂（A)，宜於合成含羧基的丙烯酸樹 月旨（a )後，以鹼性化合物來中和全部或一部分的羧基，惟 亦可藉由使用一種單體，其係預先以鹼性化合物來中和使 用於含羧基的丙烯酸樹脂（a)的合成之含羧基的乙烯性不 飽和單體之全部或一部分，不需經由丙烯酸樹脂（a)，而 直接調製丙烯酸樹脂（A)。 使用於本發明的化合物（B )，係必須含有 8.6〜10.5 mmol/g的聚合性不飽和雙鍵。聚合性不飽和雙鍵 之含量若少於8.6mmol/g，因交聯不足而形成硬化塗膜的耐 摩擦性和耐水性不充分之活性能量線硬化型水性樹脂組成 物和活性能量線硬化型塗料，故不理想。聚合性不飽和雙 鍵之含量若多於10.5mmol/g，則製得的硬化塗膜的於基材 之黏附性低落，亦不理想。爲製得可形成耐磨損性、耐水 性、黏附性優異的硬化塗膜之活性能量線硬化型水性樹脂 組成物和活性能量線硬化型塗料，化合物（B)宜爲含有 9.0〜10.2mmol/g的聚合性不飽和雙鍵之化合物，尤宜含有 -20- 201000545 9.0〜9.8111111〇1/£的聚合性不飽和雙鍵之化合物。 使用於本發明的含有8.6〜10.5mmol/g的聚合性不飽和 雙鍵之化合物（B)，亦可單獨使用，惟宜使用混合含聚合 性不飽和雙鍵的化合物，而聚合性不飽和雙鍵的平均含量 爲8.6〜10.5 mmol/g之混合物。此時所使用的含聚合性不飽 和雙鍵之化合物，可使用含聚合性不飽和雙鍵的含量爲 8.6~10.5mmol/g之化合物’亦可使用含少於8.6mmol/g的聚 合性不飽和雙鍵之化合物，亦可使用含多於10.5mmol/g的 聚合性不飽和雙鍵之化合物。 可單獨使用含8.6~10.5mmol/g的聚合性不飽和雙鍵之 化合物’作爲化合物（B )。此類化合物例如1，6 -己烷二（甲 基）丙嫌酸醋（聚合性不飽和雙鍵之含量：8.8mmol/g)、 二乙二醇二（甲基）丙烯酸酯（聚合性不飽和雙鍵之含量： 9.3mmol/g)、新戊二醇二（甲基）丙烯酸酯（聚合性不飽 和雙鍵之含量：9.4mmol/g)、1,4 -丁二醇二（甲基）丙烯酸 醋（聚合性不飽和雙鍵之含量：10.1mmol/g)、三經甲基丙 烷三（甲基）丙烯酸酯（聚合性不飽和雙鍵之含量： l〇.lmmol/g)、季戊四醇三（甲基）丙烯酸酯（聚合性不飽 和雙鍵之含量：l〇.lmmol/g)、二三羥甲基丙烷四（甲基） 丙烯酸酯（聚合性不飽和雙鍵之含量：8.6mmol/g)、二季 戊四醇五（甲基）丙烯酸酯（聚合性不飽和雙鍵之含量： 9.5mmol/g)、二季戊四醇六（甲基）丙烯酸酯（聚合性不 飽和雙鍵之含量：10.4mmol/g)等。此類化合物，係可使 用爲混合而調製化合物（B)時之原料。 混合而調製化合物（B )時’所使用之含聚合性不飽和 雙鍵之化合物’例如（甲基）丙烯酸異冰片酯（聚合性不 -21 - 201000545 飽和雙鍵之含量：4.8mmol/g)、（甲基）丙烯酸二環戊酯（聚 合性不飽和雙鍵之含量：4.9mm〇i/g)等一（甲基）丙烯酸 酯類； 三丙二醇二（甲基）丙烯酸酯（聚合性不飽和雙鍵之含量： 6.7mmol/g)、雙酚a二縮水甘油醚二（甲基）丙烯酸酯（聚 合性不飽和雙鍵之含量：3.3mmol/g)、新戊二醇二（甲基） 丙稀酸羥三甲基乙酯（聚合性不飽和雙鍵之含量： 6.4mmol/g )、三環癸烷二甲醇（甲基）丙烯酸酯（聚合性 不飽和雙鍵之含量：6.6m mol/g)、環氧乙烷重複單位數爲9 之聚乙二醇二（甲基）丙烯酸酯（聚合性不飽和雙鍵之含 量：3.8 mmol/g)、環氧乙烷重複單位數爲13之聚乙二醇二 (甲基）丙烯酸酯（聚合性不飽和雙鍵之含量： 2.9mm〇l/g )、環氧丙烷重複單位數爲7之聚丙二醇二（甲 基）丙烯酸酯（聚合性不飽和雙鍵之含量：3.8mm〇l/g )、 季戊四醇二（甲基）丙烯酸酯（聚合性不飽和雙鍵之含量： 8.2mmol/g )、二季戊四醇四（甲基）丙烯酸酯（聚合性不 飽和雙鍵之含量：8.5mmol/g)等二（甲基）丙烯酸酯類； 三（2-(甲基）丙烯醯基氧乙基）三聚異氰酸酯（聚合性 不飽和雙鍵之含量：5.6111111〇1^)、每1分子含3個環氧乙烷 鏈之環氧乙烷改良三羥甲基丙烷三（甲基）丙烯酸酯（聚 合性不飽和雙鍵之含量：7.0mmol/g)等三（甲基）丙稀酸 酯類； 季戊四醇四（甲基）丙烯酸酯（聚合性不飽和雙鍵之含量： 1 1.4mmol/g )、己內酯改性二季戊四醇六（甲基）丙烯酸酯 (聚合性不飽和雙鍵之含量：6.5mmol/g)等聚（甲基）丙 烯酸酯類或丙烯醯基嗎啉（聚合性不飽和雙鍵之含量： -22- 201000545 7 . 1 mmol/g )等。 宜使用其中的二季戊四醇五丙烯酸酯、二季戊四醇六 丙烯酸酯，尤宜二季戊四醇五丙烯酸酯和二季戊四醇六丙 烯酸酯之混合物’係因可製得高硬化性且耐摩擦性優異之 塗膜。 化合物（B)例如甲苯二異氰酸酯、異佛爾酮二異氰酸 酯、六亞甲基二異氰酸酯、二環己基甲烷二異氰酸酯、降 茨烷二異氰酸酯等二異氰酸酯化合物、更進一步由此類二 異氰酸酯化合物與多元醇而得之異氰酸酯預聚物、更進一 步由此類二異氰酸酯化合物而得之三聚氰酸酯（nurate)體 和縮二脲體之三異氰酸酯化合物、2-(甲基）丙烯酸羥乙 酯、2-(甲基）丙烯酸羥丙酯、季戊四醇三（甲基）丙烯 酸酯、二季戊四醇五（甲基）丙烯酸酯等與含羥基（甲基） 丙烯酸酯的反應生成物之胺甲酸（甲基）丙烯酸酯等、多 元酸與（甲基）丙烯酸羥烷酯之一、二、三或以上之聚酯、 或雙酚A型環氧丙烯酸酯、酚醛清漆型環氧丙烯酸酯般， 含聚合性不飽和雙鍵之低聚物類或預聚物類等。若聚合性 不飽和雙鍵爲8.6〜10.5mmol/g即可，可使用單一種，亦可 倂用2種以上。於此類含聚合性不飽和雙鍵之化合物，可 倂用聚合性不飽和雙鍵之含量少於8.6 mmol/g之化合物或 含多於10.5mmol/g之化合物或其他含聚合性不飽和雙鍵之 化合物，平均的聚合性不飽和雙鍵係含有8.6〜10.5mmol/g 即可。胺甲酸（甲基）丙嫌酸酯，宜爲例如二異氰酸酯化 合物與季戊四醇三（甲基）丙烯酸酯的反應生成物之胺甲 酸（甲基）丙烯酸酯。 混合二種以上的含聚合性不飽和雙鍵之化合物，作爲 -23- 201000545 使用於本發明的化合物（B)時，例如二季戊四醇六丙烯酸 酯（聚合性不飽和雙鍵之含量：l〇.4mmol/g )與三丙二醇 二丙烯酸酯（聚合性不飽和雙鍵之含量：6.7 mm ol/g )，以 重量比80: 20而混合。藉此，混合物含有9.6mmol/g的聚 合性不飽和雙鍵，可使用爲化合物（B)。 上述化合物（B)，係可個別單獨使用，亦可倂用二種 以上。 使用於本發明的化合物（B)，尤宜爲二季戊四醇五丙 , 烯酸酯、二季戊四醇六丙烯酸酯與胺甲酸（甲基）丙烯酸 酯之混合物，係因可製得可形成耐磨損性優異的硬化塗膜 之活性能量線硬化型水性樹脂組成物和活性能量線硬化型 塗料。此混合物中，宜爲含有含5.5〜9.5 mm ol/g聚合性不飽 和雙鍵的胺甲酸（甲基）丙烯酸酯之混合物。且此混合物 的平均的聚合性不飽和雙鍵之濃度，宜爲9.0〜10.2111111〇1/2。 本發明的活性能量線硬化型水性樹脂組成物所含的上 述丙烯酸樹脂（A )與化合物（B )，係必須在含量比[(B ) /(A)]換算成重量爲1.5〜6之範圍內。若含量比[(B) / l ( A )]小於1 · 5，則硬化塗膜的耐磨損性和耐水性不足，故 不理想。若含量比[(B ) / ( A )]大於6，則儲存安定性不 佳，亦不理想。含量比[(B) / (A)]宜爲1.8~4之範圍內， 其中尤宜2〜3.5之範圍內。 本發明的活性能量線硬化型水性樹脂組成物之製法’ 無特別之限制，例如以下之方法等。 (1)將中和丙烯酸樹脂（a)中的羧基之樹脂（A)與化 合物（B)溶解於水混合性有機溶劑而成溶液後’與水混合’ -24- 201000545 使化合物（B)分散於樹脂（A)溶解或分散於含有水混合 性有機溶劑之水性介質中，和溶有樹脂（A )之樹脂溶液中’ 或樹脂（A)已分散於水中之樹脂分散液中之方法。 (2 )將中和丙烯酸樹脂（a )中的羧基之樹脂（A )與化 合物（B)混合於含有水混合性有機溶劑之水性介質’使化 合物（B)分散於樹脂（A)溶解或分散於水性介質中’和 溶有樹脂（A )之樹脂溶液中，或樹脂（A )已分散之樹脂 分散液中之方法。 (3 )將丙烯酸樹脂（a )和化合物（B )溶解於水混合性 有機溶劑而成溶液後，混合該溶液和鹼性化合物，中和丙 烯酸樹脂（a)中的羧基而得丙烯酸樹脂（A)後，將含有 該丙烯酸樹脂（A)和含聚合性不飽和雙鍵的化合物（B) 之水混合性有機溶劑溶液與水混合，使化合物（B )分散於 樹脂（A )溶解或分散於水性介質中，和溶有丙烯酸樹脂（A ) 之樹脂溶液中，或樹脂（A )分散於水中之樹脂分散液中之 方法。 (4 )將丙烯酸樹脂（a )和化合物（B )溶解於水混合性 有機溶劑而成溶液後，混合該溶液和含有鹼性化合物之 水，以鹼性化合物來中和丙烯酸樹脂（a )中的羧基，使化 合物（B)分散於樹脂（A )溶解或分散於水性介質中，和 溶有丙烯酸樹脂（A)之樹脂溶液中，或樹脂（A)分散於 水中之樹脂分散液中之方法。 上述方法中，宜爲（1)和（3)之方法，係因可簡便 地製得活性能量線硬化型水性樹脂組成物。丙烯酸樹脂（a ) 或丙烯酸樹脂（A)和化合物（B )於水混合性有機溶劑之 -25- 201000545 溶解，不需同時進行’例如可爲丙烯酸樹脂（a)或丙烯酸 樹脂（A )溶解於水混合性有機溶劑後’再與化合物（b ) 混合而使化合物（B)分散之方法。更進一步，使化合物（B) 分散於使中和丙烯酸樹脂（a)中的羧基而成之丙烯酸樹脂 (A)溶解於水中之樹脂溶液，或使丙烯酸樹脂（A)分散 於水中之樹脂分散液中’而形成活性能量線硬化型水性樹 脂組成物後’依需求可去除一部分乃至全部的水混合性有 機溶劑’惟本發明的活性能量線硬化型水性樹脂組成物或 活性能量線硬化型塗料，即使不去除有機溶劑，有機溶劑 之含量亦可低於先前的噴霧塗裝條件之1/10以下。因此， 即不易發生作業環境惡化’因揮發的有機溶劑而引起大氣 污染等問題。 本發明的活性能量線硬化型水性樹脂組成物中，一般 含有光（聚合）引發劑。光（聚合）引發劑，係可使用各 種物質。例如苯乙酮類、二苯甲酮衍生物、米希勒酮、脫 氫苯、苯偶醯衍生物、苯偶姻衍生物、苯偶姻甲醚類、α-、 醯氧酯、噻噸酮類、蒽醌類及其各種衍生物等，例如4 -二 甲胺苯甲酸、4 -二甲胺苯甲酸酯、烷氧苯乙酮、苯偶醯二 甲基縮酮、二苯甲酮、苯甲醯苯甲酸烷酯、二（4_二烷基 胺苯基）酮、苯偶醯、苯偶姻、苯偶姻苯甲酸酯、安息香 烷基醚、2-羥-2-甲基苯丙酮、1-羥環己基苯酮、4-( 2-羥乙 氧）苯基-2-羥-2-丙酮、2-羥-2-甲基-1-苯基-丙烷-1-酮、噻 噸酮、2，4,6-三甲基苯甲醯二苯基膦氧化物、2_甲基-1-[4-(甲基硫）苯基]-2-嗎啉代丙烷-1-酮、2 -苯偶醯-2-二甲胺 -卜（4-嗎啉代苯基）-丁酮-丨_酮等。此等可單獨使用，亦可 -26- 201000545 倂用二種以上。因光（聚合）引發劑通常爲油 劑亦呈安定地分散於水中之狀態。 光（聚合）引發劑之添加量，相對於本發 量線硬化型水性樹脂組成物之固形分，爲0.05-宜爲0.5~10重量％之範圍內。 光（聚合）引發劑之外，亦可倂用各種光 增感劑例如胺類、尿素類、含硫化合物、含磷 氯化合物或腈類或其他含氮化合物等。 本發明的活性能量線硬化型水性樹脂組成 合物（B)分散在丙烯酸樹脂（A)溶解於水之 或該丙烯酸樹脂（A)分散於水之樹脂分散液中 性能量線硬化型水性樹脂組成物，該丙烯酸樹 化合物（B)之含量比[(B) / (A)]，換算成j 即可，可爲一部分的丙烯酸樹脂（A)溶解於7上 可爲一部分的化合物（B )溶解於水之狀態。 本發明的活性能量線硬化型水性樹脂組成 , 在不破壞本發明的硬化之範圍，係可使用乳化 用乳化劑，可提升丙烯酸樹脂（A )與化合物 之分散安定性。 上述乳化劑例如聚氧乙烯烷基醚、聚氧乙 等非離子系乳化劑、烷基硫酸酯鹽、烷基苯磺 乙烯烷基醚硫酸酯鹽等陰離子系乳化劑、四級 子系乳化劑等。使用乳化劑時，爲不使硬化塗 降低，宜儘量少量，尤宜不使用。 製造上述本發明的活性能量線硬化型水性 性，故引發 明的活性能 -2 0重量％ ， 增感劑。光 化合物、含 物，係將化 樹脂溶液中 1，而形成活 脂（A )與該 重量爲1.5~6 〔之狀態，亦 物，依需求 劑。藉由使 (B )在水中 烯烷基苯醚 i酸鹽、聚氧 :銨鹽等陽離 :膜之耐水性 :樹脂組成物 -27- 201000545 時，使丙烯酸樹脂（a)、丙烯酸樹脂（A)、化合物（B)溶 解、分散於水混合性有機溶劑之機械方法，係可採用各種 方法。例如於攪拌翼使用渦輪翼、麥克斯混合翼、Hi-F攪 拌機等，使混合溶解及/或分散之方法，或藉由均質機、索 諾雷特（超音波粉碎機）、分散器、攪拌機等，使混合溶解 及/或分散之方法。 本發明的活性能量線硬化型塗料，係含有本發明的活 性能量線硬化型樹脂組成物。本發明的活性能量線硬化型 塗料，係藉由混合本發明的活性能量線硬化型樹脂組成 物、光引發劑、依需求而使用之塗平劑、消泡劑、液流控 制劑等而製得。 上述塗平劑例如聚醚改性聚二甲基矽氧烷、含丙烯醯 基之聚醚改性聚二甲基矽氧烷等矽系塗平劑、丙烯酸系塗 平劑等。上述消泡劑例如矽系消泡劑、礦質油系消泡劑、 聚合物系消泡劑等。上述液流控制劑例如鹼膨脹型液流控 制劑、鹼膨脹會合型液流控制劑、胺甲酸酯會合型液流控 制劑等。可依需求適當地選擇而使用。 本發明的活性能量線硬化型塗料，係可依需求摻合上 述含聚合性不飽和雙鍵的化合物之乳化物、胺甲酸酯樹脂 或環氧樹脂等之乳化物、自發乳化物或水溶性樹脂等。 本發明的硬化塗膜之形成方法，係於基材上塗布本胃 明的活性能量線硬化型塗料後，照射活性能量線，使塗布 的活性能量線硬化型塗料硬化。塗布係可藉由照相凹版塗 層法、輥塗層法、噴霧塗層法、模口塗層法、點塗層（CC)mma coat)法、螺旋塗層法、浸漬法等塗層法、照相凹版印刷法、 -28- 201000545 網版印刷法等印刷法等而進行。基材例如塑膠、金屬或金 屬蒸鍍面、玻璃、木材、紙等。 上述塑膠例如丙烯酸-丁烯-苯乙烯共聚物（ABS ) '聚 碳酸酯（PC)、聚甲基丙烯酸甲酯（PMMA)、聚對苯二甲酸 乙二醇酯（PET)、聚對苯二甲酸丁二醇酯（PBT)、三乙酸 纖維素（TAC )等或其複合體等。上述金屬例如鋁、不銹 鋼、錫、馬口鐵等。 上述此類基材，可爲預先塗布本發明的活性能量線硬 化型塗料後，照射活性能量線，而具有塗布的活性能量線 硬化型塗料已硬化的硬化塗膜之基材，亦可爲預先塗布本 發明的活性能量線硬化型塗料以外之塗料後，依需求使乾 燥後，而具有已硬化的硬化塗膜之基材。 基材亦可具有各種形狀。例如可爲具厚度之形狀或片 狀、薄膜狀。更進一步，可於基材表面進行凹凸等之設計。 本發明的硬化塗膜之形成方法，例如由以下的步驟而 成之形成方法等。首先，將本發明的活性能量線硬化型塗 • 料塗布於基材。之後進行預乾燥。預乾燥係可藉由例如將 塗布後的基材靜置於50〜100°C的環境下1〜30分鐘而進 行。之後，照射活性能量線。例如基材爲塑膠之場合，預 乾燥係於7 0 °C進行5分鐘左右。 活性能量線，係例如電子線、紫外線、r -射線等。活 性能量線之照射條件，係因應使用的活性能量線硬化型塗 料之組成而定，惟宜進行一般積算光量爲50~5000mj/cm2 之照射，尤宜進行積算光量爲200〜3000mj/cm2之照射。 藉由本發明的硬化塗膜之形成方法來進行住宅地板之 -29- 201000545 修補’例如將本發明的活性能量線硬化型塗料塗布於地 板，以電風扇乾燥後，再使用手提型紫外線照射機來照射 紫外線，使塗膜硬化即可。 本發明的活性能量線硬化型水性樹脂組成物和活性能 量線硬化型塗料中，因應噴霧塗裝等塗布性能，亦可適當 地含有水混合性有機溶劑。本發明的活性能量線硬化型水 性樹脂組成物和活性能量線硬化型塗料中的丙烯酸樹脂 (A)和化合物（B)之總計固形分含率，從黏度適當而易 ’ 於使用爲塗層劑之觀點，宜爲10~70重量％ ，尤宜20〜50 重量％ 。 設置本發明的活性能量線硬化型塗料的硬化塗膜而成 之物品，係具有耐磨損性、耐水性優異之硬化塗膜。該硬 化塗膜係可設置於物品之表面，亦可作爲基礎塗裝（基礎 塗層）或中間塗層塗裝而設置於物品上。即使作爲基礎塗 裝（基礎塗層）或中間塗層塗裝而設置於物品上，亦可補 充表面的硬化塗膜之耐磨損性和耐水性，並延長物品之壽 \ 命。於基材上形成基礎塗層，亦可預防至其次步驟爲止之 基材之損傷。 [實施例] 以下，舉出合成例、實施例及比較例，來具體地說明 本發明。若無預先限定，則各例中的份及％係重量基準。 合成例1 [丙烯酸樹脂（A)之合成] 於具備回流冷卻器、攪拌機及氮導入管的1公升之反 應容器，放入2 80g丙二醇一丙醚，開始攪拌並升溫至120 °C。在氮氣流下，將由434g甲基丙烯酸甲酯、21g甲基丙 -30- 201000545 烯酸丁酯、84g丙烯酸、l〇5g甲基丙烯酸羥乙酯、35.0g亞 羅尼科思（音譯，Aronix) M-5300 (東亞合成股份公司製， ω -羧聚己內醇丙烯酸酯）所形成之單體混合物、和12.6g 第三丁基過氧-2-乙基己酮酯溶解於20g丙二醇一丙醚而成 之引發劑溶液，以4小時並行添加於其中。於同溫度下， 更繼續聚合反應8小時後，結束反應而製得丙烯酸樹脂 (a-Ι)之溶液。該丙烯酸樹脂（a-Ι)的樹脂固形分之酸價 爲102mgK〇H/g，羥基價爲64mgKOH/g，數平均分子量爲 " 15,000,重量平均分子量爲45,000,玻璃轉移溫度爲72 t。 其次，於該溶液中添加2 3.3 g三乙胺、3 6.7 g的2 5 %氨水， 進行中和，以丙二醇一丙醚進行調整，製得丙烯酸樹脂 (A-1)之溶液。該丙烯酸樹脂（A-1)之溶液之不揮發分 爲70% ，已中和的羧基量爲1. lOmmol/g。丙烯酸樹脂（A-1 ) 之特性値和丙烯酸樹脂（a -1 )之物性値，係如表1合倂所 不 ° 合成例2〜9 (同上） 、 依據合成例1之方法，以表1所示的單體混合物及聚 合引發劑之用量’而製得丙烯酸樹脂（A-2 )之溶液及丙烯 酸樹脂（A-9)之溶液。丙烯酸樹脂（A-2)及丙烯酸樹脂 (A-9 )之#性値和丙Μ酸胃月旨（a-l )至丙稀酸_月旨（a.9 ) 之物性値，係如表1及表2合倂所示。 合成例10~14[比較對照用丙烯酸樹脂（a)之合成] 依據合成例1之方法’以表1所示的單體混合物及聚 合引發劑之用量，而製得比較對照用丙烯酸樹脂（A’ -1) 之溶液至比較對照用丙烯酸樹脂（A，-5)之溶液。丙烯酸 -31 - 201000545 樹脂（a’ -1 )及丙烯酸樹脂（a’ -5 )之特性値，係如表3 合倂所示。 合成例15[化合物（B )之合成] 於具備攪拌機的1公升之反應容器中，放入104 g六亞 甲基二異氰酸酯、0.2g甲氧酮、〇.2g二月桂酸二丁酯錫， 開始攪拌並升溫至6 0 °C。於相同溫度，將6 4 5 g亞羅尼科思 Μ 3 05 (東亞合成股份公司製，季戊四醇三丙烯酸酯/季戊四 醇四丙烯酸酯，羥基價110mgKOH/g)分成1〇次，每10分 鐘加入一次。更繼續反應1 0小時，以紅外線光譜來確認 2250CHT1的異氰酸酯基之吸收已消失，結束反應而製得胺 甲酸丙烯酸酯（聚合性不飽和雙鍵之含量：7.8 mmol/g)與 季戊四醇四丙烯酸酯的混合物之化合物（BB-1)。化合物 (BB-1 )的聚合性不飽和雙鍵之濃度爲9.0mmol/g。 合成例16(同上） 於具備攪拌機的1公升之反應容器中，放入128g異佛 爾酮二異氰酸酯、0.2g甲氧酮、〇.2g二月桂酸二丁酯錫， I; 開始攪拌並升溫至601。於相同溫度，將62 lg亞羅尼科思 Μ 3 05分成10次，每10分鐘加入一次。更繼續反應1〇小 時，以紅外線光譜來確認2250(:1111的異氰酸酯基之吸收己 消失，結束反應而製得胺甲酸丙烯酸酯（聚合性不飽和雙 鍵之含量：7.3mmol/g )與季戊四醇四丙烯酸酯的混合物之 化合物（BB-2 )。化合物（BB-2 )的聚合性不飽和雙鍵之濃 度爲 8.6mmol/g。 合成例17[化合物（B)之合成] 於具備攪拌機的1公升之反應容器中，放入250g亞羅 -32- 201000545 尼科思M404 (東亞合成股份公司製，二季戊四醇五丙烯酸 酯/二季戊四醇六丙烯酸酯，羥基價50mgKOH/g)、50g亞羅 尼科思M408 (東亞合成股份公司製的二三羥甲基丙烷四丙 烯酸酯）及200g化合物（BB-1 )，於40°C進行攪拌而製得 化合物（B-1 )。化合物（B-1 )的聚合性不飽和雙鍵之濃度 爲 9_5mmol/g。 合成例18 (同上） 於具備攪拌機的1公升之反應容器中，放入450g亞羅 尼科思M404及50g化合物（BB-1 )，於40°C進行攪拌而製 得化合物（B-2 )。化合物（B-2 )的聚合性不飽和雙鍵之濃 度爲 10.0mmol/g。 合成例19 (同上） 於具備攪拌機的1公升之反應容器中，放入15 Og亞羅 尼科思M404、75g亞羅尼科思M350 (東亞合成股份公司製 的環氧乙烷改良三羥甲基丙烷三丙烯酸酯）及27 5g化合物 (BB-2)，於40°C進行攪拌而製得化合物（B-3)。化合物 ' (B - 3 )的聚合性不飽和雙鍵之濃度爲8.8 mmο 1 /g。 合成例20 (同上） 於具備攪拌機的1公升之反應容器中，放入225g亞羅 尼科思M402 (東亞合成股份公司製，二季戊四醇五丙烯酸 酯/二季戊四醇六丙烯酸酯，羥基價25mgKOH/g)、250g亞 羅尼科思M3 05及25g化合物（BB-1 )，於4CTC進行攪拌而 製得化合物（B-4)。化合物（B-4)的聚合性不飽和雙鍵之 濃度爲 10.4mmol/g。 合成例2 1 [比較對照用化合物（B )之合成] -33- 201000545 於具備攪拌機的1公升之反應容器中，放入75g亞羅 尼科思M4Q4、150g亞羅尼科思M309、275g化合物（BB-2)’ 於40°C進行攪拌而製得化合物（b-i )。化合物（b-Ι )的聚 合性不飽和雙鍵之濃度爲8.4mm〇i/g。 合成例22 (同上） 於具備攪拌機的1公升之反應容器中，放入75g亞羅 尼科思M402及425g亞羅尼科思]v[305，於4(TC進行攪拌 而製得化合物（b - 2 )。化合物（b - 2 )的聚合性不飽和雙鍵 之濃度爲10.6mmol/g。 實施例1 於具備攪拌機的1公升之反應容器中，放入97份合成 例1製得的丙烯酸樹脂（A-1 )之溶液、1 47g合成例8製得 的胺甲酸丙烯酸酯（B-1)，開始攪拌並升溫至70 °C進行攪 拌混合。其次，於40°C邊攪拌邊將340 g離子交換水分成 10次放入，使胺甲酸丙烯酸酯（B-1)分散於丙烯酸樹脂 (A -1 )的溶液中。其次添加1 〇 . 5 g伊魯佳秋亞（音譯， Irgacure) 500 (Ciba Specialty Chemicals 製的光聚合引發 劑）、2.1g矽系塗平劑（BYK製，BYK-333 )並混合，以離 子交換水進行調整，調製不揮發成分35% 、PH7.2之活性 能量線硬化型水性樹脂組成物1。活性能量線硬化型水性 樹脂組成物1中的平均粒徑爲3 30nm。 又，活性能量線硬化型水性樹脂組成物1中的平均粒 徑，係使用MICROTRAC公司製NANOTRAC 150而測定（以 下相同）。 活性能量線硬化型水性樹脂組成物1中的PH，係使用 -34- 201000545 堀場製作所股份公司製PH測定器D-51、電 而測定（以下相同）。 評價製得的活性能量線硬化型水性樹脂 化塗膜的外觀評價、耐磨損性、鉛筆硬度、 性及耐溫水性。硬化塗膜之作成方法和各試 法，係如以下所示。 硬化塗膜（試驗塗裝板）之作成方法。 於PMMA (聚甲基丙烯酸甲酯）板上進 使乾燥後的膜厚度爲10#m，於乾燥機中， 分鐘預乾燥後，使用80W/cm的高壓水銀燈進 之紫外線照射，而製作試驗塗裝板。黏附性 黏附性試驗、耐水性試驗，更進一步，製作 酸-丁烯-苯乙烯共聚物）及PC (聚碳酸酯） 塗裝板，亦進行其相關試驗。 外觀評價：以目視來評價試驗塗裝板之 ◎:平滑且無裂開。 I 〇：平滑，惟稍微有裂開。 △:稍微有凹凸。 X :有明顯的凹凸。 耐磨損性試驗：依據HS-K5 600-5 - 1 0，： 絲棉施加1 K g荷重，並於試驗塗裝板之塗裝i 次後，測定試驗部位之霧度値，藉此而判定 定係使用思佳（音譯，Suga)試驗機股份公司 HAZE COMPUTER。 極型式96 2 1 C 組成物1之硬 於基材之黏附 驗之評價方 行噴霧塗裝， 以70°C進行10 行 1000mJ/cm2 試驗、耐溫水 以A B S (丙烯 爲基材之試驗 外觀。Tg1 = Σ Xi · Tgi·1 wherein n resin components i = 1 to n are copolymerized. The weight fraction of the i-th monomer in the Xi system, and the glass transition temperature of the individual polymer of the i-th monomer of the Tgi. The glass transition temperature of the individual polymer of the monomer can be measured by Polymer Handbook (4, h Edition) J. Brandrup, E. H. Immergut, E. A. Grulke (Wiley Interscience). In order to prepare the acrylic resin (A), it is preferred to synthesize all or a part of the carboxyl group with a basic compound after synthesizing the carboxyl group-containing acrylic acid (a), but it is also possible to use a monomer, which is The alkaline compound is used to neutralize all or a part of the carboxyl group-containing ethylenically unsaturated monomer used for the carboxyl group-containing acrylic resin (a), and the acrylic resin (A) is directly prepared without passing through the acrylic resin (a). . The compound (B) used in the present invention must contain 8.6 to 10.5 mmol/g of a polymerizable unsaturated double bond. When the content of the polymerizable unsaturated double bond is less than 8.6 mmol/g, the active energy ray-curable aqueous resin composition and the active energy ray-curable type which are insufficient in abrasion resistance and water resistance due to insufficient crosslinking are formed. Paint, it is not ideal. When the content of the polymerizable unsaturated double bond is more than 10.5 mmol/g, the adhesion of the obtained cured coating film to the substrate is low, which is not preferable. In order to obtain an active energy ray-curable aqueous resin composition and an active energy ray-curable coating material which can form a cured coating film excellent in abrasion resistance, water resistance and adhesion, the compound (B) preferably contains 9.0 to 10.2 mmol/ A compound of a polymerizable unsaturated double bond of g, particularly preferably a compound having a polymerizable unsaturated double bond of -20 to 201000545 9.0 to 9.8111111〇1/£. The compound (B) containing 8.6 to 10.5 mmol/g of a polymerizable unsaturated double bond used in the present invention may be used singly, and it is preferred to use a compound containing a polymerizable unsaturated double bond, and a polymerizable unsaturated double bond. The average content of the bonds was a mixture of 8.6 to 10.5 mmol/g. The compound containing a polymerizable unsaturated double bond used at this time may be a compound having a content of a polymerizable unsaturated double bond of 8.6 to 10.5 mmol/g, or a polymerizable property containing less than 8.6 mmol/g. As the compound which saturates the double bond, a compound containing more than 10.5 mmol/g of a polymerizable unsaturated double bond can also be used. As the compound (B), a compound ' of 8.6 to 10.5 mmol/g of a polymerizable unsaturated double bond can be used alone. Such a compound is, for example, 1,6-hexane di(methyl)propane vinegar (content of polymerizable unsaturated double bond: 8.8 mmol/g), diethylene glycol di(meth)acrylate (polymerization is not Content of saturated double bond: 9.3 mmol/g), neopentyl glycol di(meth)acrylate (content of polymerizable unsaturated double bond: 9.4 mmol/g), 1,4-butanediol di(methyl) Acrylic vinegar (content of polymerizable unsaturated double bond: 10.1 mmol/g), trimethylmethylpropane tri(meth)acrylate (content of polymerizable unsaturated double bond: l〇.lmmol/g), pentaerythritol Tris(meth)acrylate (content of polymerizable unsaturated double bond: l〇.lmmol/g), ditrimethylolpropane tetra(meth)acrylate (content of polymerizable unsaturated double bond: 8.6 mmol /g), dipentaerythritol penta (meth) acrylate (content of polymerizable unsaturated double bond: 9.5 mmol / g), dipentaerythritol hexa (meth) acrylate (polymerizable unsaturated double bond content: 10.4 mmol /g)etc. Such a compound can be used as a raw material in the case where the compound (B) is prepared by mixing. When compound (B) is mixed, the compound containing a polymerizable unsaturated double bond is used, for example, isobornyl (meth)acrylate (polymerization is not -21 - 201000545 content of saturated double bond: 4.8 mmol/g) , (meth) acrylate such as dicyclopentanyl (meth) acrylate (content of polymerizable unsaturated double bond: 4.9 mm 〇 i / g); tripropylene glycol di (meth) acrylate (polymerization is not Content of saturated double bond: 6.7 mmol/g), bisphenol a diglycidyl ether di(meth)acrylate (content of polymerizable unsaturated double bond: 3.3 mmol/g), neopentyl glycol di(methyl) ) Hydroxytrimethylethyl acrylate (content of polymerizable unsaturated double bond: 6.4 mmol/g), tricyclodecane dimethanol (meth) acrylate (content of polymerizable unsaturated double bond: 6.6 m) Mol/g), polyethylene glycol di(meth)acrylate having an ethylene oxide repeating unit number of 9 (content of polymerizable unsaturated double bond: 3.8 mmol/g), and ethylene oxide repeating unit number 13 polyethylene glycol di(meth)acrylate (content of polymerizable unsaturated double bond: 2.9 mm〇l/g), propylene oxide heavy Polypropylene glycol di(meth)acrylate having a unit number of 7 (content of polymerizable unsaturated double bond: 3.8 mm〇l/g), pentaerythritol di(meth)acrylate (content of polymerizable unsaturated double bond: Di(meth)acrylates such as 8.2 mmol/g), dipentaerythritol tetra(meth)acrylate (content of polymerizable unsaturated double bond: 8.5 mmol/g); tris(2-(methyl)propene oxime Ethoxyethyl)trimeric isocyanate (content of polymerizable unsaturated double bond: 5.6111111〇1^), ethylene oxide modified trimethylolpropane tri(methyl) containing 3 ethylene oxide chains per molecule Tris(methyl) acrylate such as acrylate (content of polymerizable unsaturated double bond: 7.0 mmol/g); pentaerythritol tetra(meth) acrylate (content of polymerizable unsaturated double bond: 1 1.4 Mol/g), poly(meth)acrylate or acryloylmorpholine such as caprolactone-modified dipentaerythritol hexa(meth)acrylate (content of polymerizable unsaturated double bond: 6.5 mmol/g) Content of polymerizable unsaturated double bond: -22- 201000545 7. 1 mmol/g). It is preferable to use a mixture of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and particularly a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, because a coating film excellent in high hardenability and excellent in abrasion resistance can be obtained. The compound (B) is a diisocyanate compound such as toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate or nordane diisocyanate, and further, such a diisocyanate compound and a plurality of diisocyanate compounds An isocyanate prepolymer obtained from an alcohol, a nurate body obtained from such a diisocyanate compound, a triisocyanate compound of a biuret, a hydroxyethyl 2-(meth)acrylate, a urethane (methyl) hydroxypropyl 2-(meth) acrylate, pentaerythritol tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, and a hydroxy group (meth) acrylate-containing reaction product Acrylate, etc., polybasic acid and hydroxyalkyl (meth) acrylate, two, three or more polyesters, or bisphenol A epoxy acrylate, novolac epoxy acrylate, containing no polymerizability An oligomer or a prepolymer of a saturated double bond or the like. When the polymerizable unsaturated double bond is 8.6 to 10.5 mmol/g, one type may be used, or two or more types may be used. For such a compound containing a polymerizable unsaturated double bond, a compound having a polymerizable unsaturated double bond content of less than 8.6 mmol/g or a compound containing more than 10.5 mmol/g or other polymerizable unsaturated double may be used. The compound of the bond may have an average polymerizable unsaturated double bond system of 8.6 to 10.5 mmol/g. The (meth)propionic acid amide is preferably an amine (meth) acrylate such as a reaction product of a diisocyanate compound and pentaerythritol tri(meth) acrylate. When two or more compounds containing a polymerizable unsaturated double bond are mixed and used as the compound (B) of the present invention as -23 to 201000545, for example, dipentaerythritol hexaacrylate (content of polymerizable unsaturated double bond: l〇. 4 mmol/g) and tripropylene glycol diacrylate (content of polymerizable unsaturated double bond: 6.7 mm ol/g) were mixed at a weight ratio of 80:20. Thereby, the mixture contains 9.6 mmol/g of a polymerizable unsaturated double bond, and can be used as the compound (B). The above compound (B) may be used alone or in combination of two or more. The compound (B) used in the present invention is particularly preferably a mixture of dipentaerythritol pentapropyl, enoate, dipentaerythritol hexaacrylate and urethane (meth) acrylate, which can be formed to form abrasion resistance. An active energy ray-curable aqueous resin composition and an active energy ray-curable coating material having an excellent hardened coating film. In the mixture, a mixture of a carboxylic acid (meth) acrylate containing a polymerizable unsaturated double bond of 5.5 to 9.5 mm ol / g is preferred. Further, the concentration of the average polymerizable unsaturated double bond of the mixture is preferably 9.0 to 10.2111111 1/2. The acrylic resin (A) and the compound (B) contained in the active energy ray-curable aqueous resin composition of the present invention are required to have a weight ratio of 1.5 to 6 in terms of a content ratio [(B) / (A)]. Inside. When the content ratio [(B) / l ( A )] is less than 1.5, the abrasion resistance and water resistance of the cured coating film are insufficient, which is not preferable. If the content ratio [(B) / (A)] is more than 6, the storage stability is not good and it is not desirable. The content ratio [(B) / (A)] is preferably in the range of 1.8 to 4, and particularly preferably in the range of 2 to 3.5. The method for producing the active energy ray-curable aqueous resin composition of the present invention is not particularly limited, and examples thereof include the following methods. (1) The resin (A) and the compound (B) which neutralize the carboxyl group in the acrylic resin (a) are dissolved in a water-miscible organic solvent to form a solution of 'mixed with water' -24- 201000545 Disperse the compound (B) A method in which the resin (A) is dissolved or dispersed in an aqueous medium containing a water-miscible organic solvent, and in a resin solution in which the resin (A) is dissolved or the resin (A) is dispersed in water. (2) mixing the resin (A) of the carboxyl group in the acrylic resin (a) with the compound (B) in an aqueous medium containing a water-miscible organic solvent, and dispersing the compound (B) in the resin (A) to dissolve or disperse A method in which an aqueous medium contains a resin solution in which the resin (A) is dissolved, or a resin dispersion in which the resin (A) has been dispersed. (3) After dissolving the acrylic resin (a) and the compound (B) in a water-miscible organic solvent, mixing the solution and the basic compound, and neutralizing the carboxyl group in the acrylic resin (a) to obtain an acrylic resin (A) After that, the water-miscible organic solvent solution containing the acrylic resin (A) and the polymerizable unsaturated double bond-containing compound (B) is mixed with water to disperse the compound (B) in the resin (A) to be dissolved or dispersed. In the aqueous medium, and in the resin solution in which the acrylic resin (A) is dissolved, or the resin (A) is dispersed in the resin dispersion in water. (4) after dissolving the acrylic resin (a) and the compound (B) in a water-miscible organic solvent, mixing the solution and water containing a basic compound, and neutralizing the acrylic resin (a) with a basic compound a carboxyl group, a method in which the compound (B) is dispersed in a resin medium (A) dissolved or dispersed in an aqueous medium, and a resin solution in which the acrylic resin (A) is dissolved, or a resin (A) is dispersed in a resin dispersion in water . Among the above methods, the methods (1) and (3) are preferred because the active energy ray-curable aqueous resin composition can be easily obtained. The acrylic resin (a) or the acrylic resin (A) and the compound (B) are dissolved in the water-miscible organic solvent -25- 201000545, and need not be simultaneously performed, for example, the acrylic resin (a) or the acrylic resin (A) may be dissolved in A method in which a compound (B) is further mixed with a compound (b) after mixing with a water-miscible organic solvent. Further, the resin solution in which the compound (B) is dispersed in the acrylic resin (A) which neutralizes the carboxyl group in the acrylic resin (a) is dissolved in water, or the resin dispersion in which the acrylic resin (A) is dispersed in water In the case of forming an active energy ray-curable aqueous resin composition, a part or all of the water-miscible organic solvent may be removed as required. The active energy ray-curable aqueous resin composition or the active energy ray-curable coating material of the present invention, Even if the organic solvent is not removed, the content of the organic solvent may be less than 1/10 of the previous spray coating conditions. Therefore, problems such as deterioration of the working environment and atmospheric pollution due to the volatile organic solvent are less likely to occur. The active energy ray-curable aqueous resin composition of the present invention generally contains a photopolymerization initiator. For the photopolymerization initiator, various materials can be used. For example, acetophenones, benzophenone derivatives, michelone, dehydrobenzene, benzoin derivatives, benzoin derivatives, benzoin methyl ethers, α-, oxime esters, thioxanthenes Ketones, anthraquinones and various derivatives thereof, such as 4-dimethylamine benzoic acid, 4-dimethylamine benzoate, alkoxyacetophenone, benzoin dimethyl ketal, diphenyl Ketone, alkyl benzhydrazide, bis(4-dialkylamine phenyl) ketone, benzoin, benzoin, benzoin benzoate, benzoin alkyl ether, 2-hydroxy-2- Methylpropiophenone, 1-hydroxycyclohexyl benzophenone, 4-(2-hydroxyethoxy)phenyl-2-hydroxy-2-propanone, 2-hydroxy-2-methyl-1-phenyl-propane-1 -ketone, thioxanthone, 2,4,6-trimethylbenzimidium diphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino Propane-1-one, 2-benzindole-2-dimethylamine-bu (4-morpholinophenyl)-butanone-indole-ketone, and the like. These can be used alone or in combination with -26- 201000545. The photopolymerization initiator is usually in a state in which the oil is also stably dispersed in water. The amount of the light (polymerization) initiator to be added is in the range of 0.05 to 0.5 to 10% by weight based on the solid content of the linear curable aqueous resin composition. In addition to the photopolymerization initiator, various photo-sensitizers such as amines, ureas, sulfur-containing compounds, phosphorus-containing chlorine compounds or nitriles or other nitrogen-containing compounds may be used. The active energy ray-curable aqueous resin composition (B) of the present invention is dispersed in a resin resin (A) dissolved in water or the acrylic resin (A) is dispersed in water, and the resin is dispersed in a neutral energy ray-curable aqueous resin. The ratio of the content of the acrylic tree compound (B) to [(B) / (A)] may be converted into j, and a part of the acrylic resin (A) may be dissolved in 7 to dissolve a part of the compound (B). In the state of water. The active energy ray-curable aqueous resin composition of the present invention can use an emulsifier for emulsification without deteriorating the range of curing of the present invention, and can improve the dispersion stability of the acrylic resin (A) and the compound. The emulsifier is an anionic emulsifier such as a polyoxyethylene alkyl ether or a nonionic emulsifier such as polyoxyethylene, an alkyl sulfate or an alkyl benzene sulfoalkyl ether sulfate, or a quaternary emulsifier. Wait. When the emulsifier is used, in order not to lower the hardening coating, it is preferred to use a small amount as much as possible, and it is particularly preferable not to use it. By producing the above-described active energy ray-curable water-based property of the present invention, it is possible to induce an activity of -20% by weight and a sensitizer. The light compound or the substance is formed into a resin solution (1) to form a living fat (A) and the weight is 1.5 to 6 [, and is also a demanding agent. By making (B) a cation of an alkylene phenyl ether i acid salt, a polyoxygen: ammonium salt, etc. in water: water resistance of the film: resin composition -27-201000545, an acrylic resin (a), an acrylic resin ( A) A mechanical method in which the compound (B) is dissolved and dispersed in a water-miscible organic solvent can be variously used. For example, a method of dissolving and/or dispersing a mixture using a turbine wing, a Maxi mixing wing, a Hi-F mixer, or the like, or a homogenizer, a Sonorette (ultrasonic pulverizer), a disperser, a mixer Etc., a method of dissolving and/or dispersing the mixture. The active energy ray-curable coating material of the present invention contains the active amount wire-curable resin composition of the present invention. The active energy ray-curable coating material of the present invention is prepared by mixing the active energy ray-curable resin composition of the present invention, a photoinitiator, a coating agent used as needed, an antifoaming agent, a liquid flow controlling agent, and the like. Got it. The above-mentioned leveling agent is, for example, a polyether modified polydimethyl siloxane, a fluorene-based polyether-modified polydimethyl siloxane such as an acryl-based coating agent, or an acrylic coating agent. The above antifoaming agent is, for example, a fluorene-based antifoaming agent, a mineral oil-based antifoaming agent, a polymer-based antifoaming agent, or the like. The above-described liquid flow controlling agent is, for example, an alkali-inflated liquid flow control preparation, an alkali expansion-admixed liquid flow control agent, a urethane-compatible liquid flow control preparation, or the like. It can be used as appropriate according to the needs. The active energy ray-curable coating material of the present invention may be an emulsion of a compound containing a polymerizable unsaturated double bond, an emulsion of a urethane resin or an epoxy resin, a spontaneous emulsion or water-soluble, if necessary. Resin, etc. In the method for forming a cured coating film of the present invention, the active energy ray-curable coating material of the present invention is applied onto a substrate, and then the active energy ray is irradiated to cure the applied active energy ray-curable coating material. The coating system can be coated by a gravure coating method, a roll coating method, a spray coating method, a die coating method, a point coating (CC) mma coat method, a spiral coating method, a dipping method, or the like. Photogravure printing method, printing method such as -28-201000545 screen printing method, etc. The substrate is, for example, a plastic, metal or metal vapor deposition surface, glass, wood, paper, or the like. The above plastics such as acrylic acid-butylene-styrene copolymer (ABS) 'polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), poly-p-phenylene Butylene formate (PBT), cellulose triacetate (TAC), or the like, or a complex thereof. The above metals are, for example, aluminum, stainless steel, tin, tinplate, and the like. The above-mentioned substrate may be a substrate on which the active energy ray-curable coating material of the present invention is applied in advance, and then the active energy ray is applied, and the coated active energy ray-curable coating material is cured. After coating the coating material other than the active energy ray-curable coating material of the present invention, the substrate having the cured coating film after curing is dried as required. The substrate can also have a variety of shapes. For example, it may have a shape of a thickness or a sheet shape or a film shape. Further, the design of the unevenness or the like can be performed on the surface of the substrate. The method for forming the cured coating film of the present invention is, for example, a method of forming the film by the following steps. First, the active energy ray-curable coating material of the present invention is applied to a substrate. Then pre-drying is carried out. The pre-drying can be carried out, for example, by allowing the coated substrate to stand in an environment of 50 to 100 ° C for 1 to 30 minutes. Thereafter, the active energy ray is illuminated. For example, when the substrate is a plastic, the pre-drying is carried out at 70 ° C for about 5 minutes. The active energy ray is, for example, an electron beam, an ultraviolet ray, an r-ray or the like. The irradiation conditions of the active energy ray are determined according to the composition of the active energy ray-curable coating to be used, and it is preferable to carry out irradiation with a general integrated light amount of 50 to 5000 mj/cm 2 , and it is particularly preferable to carry out irradiation with an integrated light amount of 200 to 3000 mj/cm 2 . . The -29-201000545 repair of the residential floor is carried out by the method for forming a cured coating film of the present invention. For example, the active energy ray-curable coating of the present invention is applied to a floor, dried by an electric fan, and then a portable ultraviolet ray irradiator is used. Irradiation of ultraviolet rays can harden the coating film. In the active energy ray-curable aqueous resin composition and the active energy ray-curable coating material of the present invention, a water-miscible organic solvent may be appropriately contained in accordance with coating properties such as spray coating. The total solid content fraction of the acrylic resin (A) and the compound (B) in the active energy ray-curable aqueous resin composition and the active energy ray-curable coating material of the present invention is appropriate from the viscosity and is easy to use as a coating agent. The viewpoint is preferably 10 to 70% by weight, particularly preferably 20 to 50% by weight. The article obtained by providing the cured coating film of the active energy ray-curable coating material of the present invention is a cured coating film having excellent abrasion resistance and water resistance. The hard coating film may be disposed on the surface of the article or may be applied to the article as a base coating (base coating) or an intermediate coating. Even if it is applied to the article as a base coat (base coat) or an intermediate coat, it can replenish the abrasion resistance and water resistance of the hardened film on the surface and prolong the life of the article. Forming the base coat on the substrate also prevents damage to the substrate up to the next step. [Examples] Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples. Unless otherwise defined, the parts and % in each example are based on the weight. Synthesis Example 1 [Synthesis of Acrylic Resin (A)] In a 1 liter reaction vessel equipped with a reflux condenser, a stirrer, and a nitrogen introduction tube, 2,80 g of propylene glycol monopropyl ether was placed, stirring was started, and the temperature was raised to 120 °C. Under a nitrogen stream, it will consist of 434 g of methyl methacrylate, 21 g of methyl propyl-30-201000545 butyl acrylate, 84 g of acrylic acid, 10 g of hydroxyethyl methacrylate, and 35.0 g of Aronix. A monomer mixture formed by M-5300 (manufactured by Toagosei Co., Ltd., ω-carboxypolycaprolactone acrylate), and 12.6 g of tert-butylperoxy-2-ethylhexanone ester dissolved in 20 g of propylene glycol-propene An ether-formed initiator solution was added thereto in parallel for 4 hours. After the polymerization was further continued at the same temperature for 8 hours, the reaction was terminated to obtain a solution of an acrylic resin (a-ruthenium). The resin of the acrylic resin (a-ruthenium) had an acid value of 102 mg K 〇 H / g, a hydroxyl value of 64 mg KOH / g, a number average molecular weight of " 15,000, a weight average molecular weight of 45,000, and a glass transition temperature of 72 t. Next, 23.3 g of triethylamine and 3 6.7 g of 25 % aqueous ammonia were added to the solution, neutralized, and adjusted with propylene glycol monopropyl ether to prepare a solution of the acrylic resin (A-1). lOmmol/克。 The solution of the acrylic resin (A-1) having a non-volatile content of 70%, the amount of the neutralized carboxyl group is 1. lOmmol / g. The properties of the acrylic resin (A-1) and the physical properties of the acrylic resin (a-1) are as shown in Table 1 in the synthesis of Examples 2 to 9 (ibid.), according to the method of Synthesis Example 1, and Table 1 A solution of the acrylic resin (A-2) and a solution of the acrylic resin (A-9) were prepared by using the monomer mixture and the polymerization initiator in the amounts shown. The physical properties of the acrylic resin (A-2) and the acrylic resin (A-9) and the physical properties of the acrylic acid (al) to the acrylic acid (a.9) are as shown in Table 1 and Table 2 shows the combination. Synthesis Examples 10 to 14 [Synthesis of Comparative Control Acrylic Resin (a)] According to the method of Synthesis Example 1, the amount of the monomer mixture and the polymerization initiator shown in Table 1 was used to prepare a comparative control acrylic resin (A). A solution of '-1' was compared to a solution of the comparative acrylic resin (A, -5). Acrylic -31 - 201000545 The properties of the resin (a' -1 ) and the acrylic resin (a' -5 ) are shown in Table 3 in combination. Synthesis Example 15 [Synthesis of Compound (B)] In a 1 liter reaction vessel equipped with a stirrer, 104 g of hexamethylene diisocyanate, 0.2 g of methoxyketone, and 0.2 g of dibutyltin dilaurate were placed. Start stirring and warm to 60 °C. At the same temperature, 6 4 5 g of Aronicus Μ 3 05 (manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate / pentaerythritol tetraacrylate, hydroxyl value 110 mg KOH / g) was divided into 1 time, once every 10 minutes. . Further, the reaction was continued for 10 hours, and it was confirmed by infrared spectroscopy that the absorption of the isocyanate group of 2250 CHT1 had disappeared, and the reaction was terminated to obtain a urethane acrylate (content of a polymerizable unsaturated double bond: 7.8 mmol/g) and pentaerythritol tetraacrylate. a mixture of compounds (BB-1). The concentration of the polymerizable unsaturated double bond of the compound (BB-1) was 9.0 mmol/g. Synthesis Example 16 (ibid.) In a 1 liter reaction vessel equipped with a stirrer, 128 g of isophorone diisocyanate, 0.2 g of methoxyketone, 〇.2 g of dibutyltin dilaurate, I was placed, and stirring was started and the temperature was raised. To 601. At the same temperature, 62 lg of Aronicus Μ 3 05 was divided into 10 times and added every 10 minutes. Further, the reaction was continued for 1 hour, and it was confirmed by infrared spectroscopy that the absorption of 2250 (:1111 isocyanate group disappeared), and the reaction was terminated to obtain a urethane acrylate (content of a polymerizable unsaturated double bond: 7.3 mmol/g) and pentaerythritol. Compound (BB-2) of a mixture of tetraacrylates. The concentration of the polymerizable unsaturated double bond of the compound (BB-2) was 8.6 mmol/g. Synthesis Example 17 [Synthesis of Compound (B)] 1 with a stirrer In a liter reaction vessel, 250 g of Yarrow-32-201000545 Nikos M404 (manufactured by Toagosei Co., Ltd., dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate, hydroxyl value 50 mgKOH/g), 50 g of ryonico Si M408 (ditrimethylolpropane tetraacrylate manufactured by Toagosei Co., Ltd.) and 200 g of compound (BB-1) were stirred at 40 ° C to obtain compound (B-1 ). Compound (B-1) The concentration of the polymerizable unsaturated double bond was 9 to 5 mmol/g. Synthesis Example 18 (ibid.) In a 1 liter reaction vessel equipped with a stirrer, 450 g of Aronicus M404 and 50 g of a compound (BB-1) were placed. Compounding at 40 ° C to prepare a compound (B-2) The concentration of the polymerizable unsaturated double bond of the compound (B-2) was 10.0 mmol/g. Synthesis Example 19 (ibid.) In a 1 liter reaction vessel equipped with a stirrer, 15 Og of Yarrow was placed. Nicos M404, 75g Aaron Niss M350 (Ethylene Oxide Modified Trimethylolpropane Triacrylate manufactured by East Asia Synthetic Co., Ltd.) and 27 5g Compound (BB-2) were stirred at 40 ° C. The compound (B-3) was obtained. The concentration of the polymerizable unsaturated double bond of the compound '(B-3) was 8.8 mmο 1 /g. Synthesis Example 20 (ibid.) In a 1 liter reaction vessel equipped with a stirrer, 225g Aaron Niss M402 (manufactured by Toagosei Co., Ltd., dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate, hydroxyl value 25mgKOH/g), 250g Yalonicos M3 05 and 25g compound (BB-1) The compound (B-4) was obtained by stirring at 4 CTC. The concentration of the polymerizable unsaturated double bond of the compound (B-4) was 10.4 mmol/g. Synthesis Example 2 1 [Comparison of Comparative Control Compound (B) ] -33- 201000545 In a 1 liter reaction vessel equipped with a blender, put 75g Aaron Niss M4Q4, 150g Ya Nicos M309 and 275 g of the compound (BB-2) were stirred at 40 ° C to obtain a compound (bi ). The concentration of the polymerizable unsaturated double bond of the compound (b-Ι) was 8.4 mm〇i/g. Synthesis Example 22 (ibid.) In a 1 liter reaction vessel equipped with a stirrer, 75 g of Aronicus M402 and 425 g of aronicus v. 305 were placed, and 4 (TC was stirred to obtain a compound (b). - 2 ). The concentration of the polymerizable unsaturated double bond of the compound (b-2) was 10.6 mmol/g. Example 1 Into a 1 liter reaction vessel equipped with a stirrer, 97 parts of a solution of the acrylic resin (A-1) obtained in Synthesis Example 1 and 1 47 g of a urethane acrylate obtained in Synthesis Example 8 (B-1) were placed. ), stirring was started and the temperature was raised to 70 ° C to carry out stirring and mixing. Next, 340 g of ion-exchanged water was placed in 10 portions while stirring at 40 ° C to disperse the urethane acrylate (B-1) in a solution of the acrylic resin (A -1 ). Next, add 1 〇. 5 g of Irgacure 500 (photopolymerization initiator manufactured by Ciba Specialty Chemicals), 2.1 g of lanthanide coating agent (BYK-333, BYK-333), and mix with ions. The exchange water was adjusted to prepare an active energy ray-curable aqueous resin composition 1 having a nonvolatile content of 35% and a pH of 7.2. The average particle diameter in the active energy ray-curable aqueous resin composition 1 was 3 30 nm. Further, the average particle diameter in the active energy ray-curable aqueous resin composition 1 was measured using NANOTRAC 150 manufactured by MICROTRAC Co., Ltd. (the same applies hereinafter). The pH of the active energy ray-curable water-based resin composition 1 was measured by using a liquid measuring device D-51 manufactured by Horiba, Ltd., and was measured by electricity (the same applies hereinafter). The appearance evaluation, abrasion resistance, pencil hardness, properties, and temperature resistance of the obtained active energy ray-curable aqueous resinized coating film were evaluated. The method for producing the cured coating film and the respective test methods are as follows. A method of forming a cured coating film (test coating plate). After drying on a PMMA (polymethyl methacrylate) plate, the film thickness was 10 #m, and after pre-drying in a drier, a high-pressure mercury lamp of 80 W/cm was used for ultraviolet irradiation to prepare a test coating. Install the board. Adhesive adhesion tests, water resistance tests, and further production of acid-butene-styrene copolymers and PC (polycarbonate) coated panels were also tested. Appearance evaluation: The test coated panels were visually evaluated. ◎: Smooth and crack-free. I 〇: Smooth, but slightly split. △: There is a slight unevenness. X : There are obvious bumps. Abrasion resistance test: According to HS-K5 600-5 - 1 0,: 1 kg load is applied to silk wool, and the haze of the test part is measured after i coating of the test coated plate. It is decided to use the Suga test machine company HAZE COMPUTER. Polar type 96 2 1 C Composition 1 is hard to adhere to the evaluation of the adhesion test of the substrate. 10 rows of 1000 mJ/cm 2 test at 70 ° C, and ABS (propylene-based test appearance) .
於# 0000的鋼 面來回摩擦1 00 。霧度値之測 製 DIGITAL -35- 201000545 〇：3.5以上至低於5.0。 △ : 5.0以上至低於15.0。 X : 1 5.0 以上。 鉛筆硬度試驗：使用JIS-S-6006規定之高級鉛筆，依 據〗IS-K-5400而測試不破壞試驗塗裝板的塗裝面之硬度。 黏附性試驗：依據JIS-K5 600-5-6 ’於試驗塗裝板（使 用PMMA、ABS及PC於基材之試驗塗裝板）之塗裝面，切 入寬度lmm的棋盤格，作成100個塊狀物’使用玻璃紙膠 " 帶來進行剝離試驗，由殘留的棋盤格之個數進行判定。 ◎:全部的試驗塗裝板皆爲100個。 •〇：全部的試驗塗裝板爲80個以上’且一或二個試驗 塗裝板爲100個。 △:全部的試驗塗裝板皆爲80至99個。 X:任一試驗塗裝板皆爲79個以下。 耐溫水黏附性：將試驗塗裝板（使用PMMA、ABS及 PC於基材之試驗塗裝板）浸漬於90°C的溫水中2小時後， * 進行上述黏附性試驗。 ◎:全部的試驗塗裝板皆爲1 00個。 〇：全部的試驗塗裝板爲80個以上，且一或二個試驗 塗裝板爲100個。 △:全部的試驗塗裝板皆爲80至99個。 X :任一試驗塗裝板皆爲79個以下。 耐水性試驗：將試驗塗裝板（使用PMMA、ABS及PC 於基材之試驗塗裝板）浸漬於50°C的溫水中24小時及72 小時後，目視判定塗裝面之白化狀態。 -36- 201000545 ◎:全部的試驗塗裝板於72小時後皆無變化。 〇：全部的試驗塗裝板於24小時後皆無變化，惟至少 一個試驗塗裝板於7 2小時後，發生部分的白化或膨脹。 △:全部的試驗塗裝板於24小時後，發生部分的白化 或膨脹。 X:全部的試驗塗裝板於24小時後，發生全面的白化 或膨脹。 實施例2 ~ 1 4、比較例1〜9 < 依據實施例1之方法，以表2所示之原料組成製得活 性能量線硬化型水性樹脂組成物2〜1 4及比較對照用活性 能量線硬化型水性樹脂組成物1 ’ -9'。進行和實施例！ 相同之各種試驗，其評價結果如表8〜表11所示。 ί -37- 201000545 【表1】 合成例 1 2 3 4 5 丙烯酸觀旨（A) A-1 A-2 A-3 A-4 A-5 •單體混合物（份） MMA 434 434 434 388.5 486.5 BMA 21 36.4 18.9 89.6 EA 14 14 18.9 BA 21 10.5 2EHA 21 AA 84 87.5 66.5 84 84 MAA M-5300 35 16.1 103.6 35 35 HEA 63 HEMA 105 112 63 84 FM-1 •引發劑（份） 12.6 9.8 12.6 14.0 15.4 三乙胺 23.3 19.1 29.0 14.1 42.4 25%氨水 36.7 30.0 19.5 38.1 28.6 通式（1)表示的自由基聚合性單體之用 量（％ ) 5 2.3 14.8 5 5 甲基丙烯酸甲酯之用量α) 62 62 62 55.5 69.5 已中和之羧基量（mmol/g) 1.10 0.90 0.82 1.00 1.20 使用於調製丙烯酸樹脂（Λ)之丙烯酸樹月 旨（a)之物性値 丙烯酸樹脂（a) a-1 a-2 a-3 a-4 a-5 數平均分子量 15000 16000 17000 13000 11000 重量卒均分子量 45000 62000 55000 38000 32000 不揮發成分U) 65 65 65 65 65 固形分酸價 102 101 101 102 102 固形分羥基價 64 69 38 51 43 玻璃轉移溫度ΓΟ 72 76 64 67 60 -38- 201000545 【表2】 合成 例 6 7 8 9 丙烯酸樹脂 A-6 A-7 A-8 A-9 •單體混合物（份） MMA 434 434 462 434 BMA 87.5 31.5 7 EA BA 10.5 2EHA 14 AA 63 115.5 70 84 MAA M-5300 35 35 84 35 HEA HEMA 70 70 28 105 FM-1 14 42 •引發劑（份） 12.6 8.4 12.6 11.2 三乙胺 37.1 0 18.0 23.3 25%氨水 25.0 45.2 28.3 36.7 通式（1)表示的自由基聚合性單體之用量（％ ) 5 5 12 5 甲基丙烯酸甲酯之用量（％ ) 62 62 66 62 已中和之翔基量（mmol/g) 1.05 0.95 0.85 1.10 使用於調製丙烯酸樹脂（A)之丙烯酸樹脂（a)之物性値 丙烯酸樹脂（a) a-6 a-7 a-8 a-9 數平均分子量 13000 18000 16000 15000 重量平均分子量 42000 75000 55000 56000 不揮發成分（％) 65 65 65 65 固形分酸價 79 137 133 102 固形分羥基價 43 48 22 78 玻璃轉移溫度rc) 69 74 72 73 -39- 201000545 【表3】 合成例 10 11 12 13 14 丙烯酸樹脂 A-1 A，-2 A，-3 A-4 A，-5 •單體混合物（份） MMA 434 434 381.5 493.5 434 BMA 32.9 28 66.5 7 55.3 EA 28 BA 28 28 14 2EHA AA 87.5 66.5 84 84 56.7 MAA M-5300 12.6 108.5 35 35 35 HEA HEMA 105 35 105 80.5 105 FM-1 •引發劑（份） 12.6 12.6 14.0 12.6 12.6 三乙胺 23.3 25.4 19.1 21.2 16.6 25%氨水 36.6 40.0 30.0 33.3 26.0 通式（1)表示的自由基聚合性單體之用 量（％ ) 1.8 15.5 5 5 5 甲基丙烯酸甲酯之用量U ) 62 62 54.5 70.5 62 已中和之殘基量（mraol/g) 1.10 1.20 0.90 1.00 0.78 通式（1)表示的自由基聚合性單體之用 量（％ ) 1.8 15.5 5 5 5 使用於調製丙烯酸樹脂（A’）之丙烯酸樹 脂（a，）之物性値 丙烯酸樹脂（a，） a’-l a’-2 a’-3 a，-4 a，-5 數平均分子量 13000 16000 13000 15000 15000 重量平均分子量 41000 56000 39000 45000 51000 不揮發成分（％ ) 65 65 65 65 65 固形分酸價 100 103 102 102 72 固形分羥基價 73 30 73 49 69 玻璃轉移溫度ΓΟ 75 58 68 81 73 表1之註解 MMA :甲基丙烯酸甲酯 BMA :甲基丙烯酸丁酯 EA :丙烯酸乙酯 BA :丙烯酸丁酯 -40- 201000545 BA :丙烯酸丁酯 2EHA :丙烯酸2-乙基己酯 AA :丙烯酸 MAA :甲基丙烯酸 HEA :丙烯酸羥乙酯 HEMA :甲基丙烯酸羥乙酯 M-5300:亞羅尼科思μ·5300 (東亞合成股份公司製， ω-羧聚己內酯丙烯酸酯） FM-1:普拉科西羅（音譯，plaCCEL)FM-1 (戴西爾化 學 股劑 製 丙 之 醚 丙 酯酸 內己 己基 的乙 酯2- - 乙氧 羥過 酸基液 烧丁溶 丙三劑 基第發 甲 g Π 物 成 加 11 ο m 於 解 溶 旨 -41 - 201000545 【表4】 實施例 1 2 3 4 5 6 7 8 9 組成物（份） 1 2 3 4 5 6 7 8 9 A-1溶液 97 A-2溶液 97 A-3溶液 97 A-4溶液 97 A-5溶液 97 A-6溶液 97 A-7溶液 97 A-8溶液 97 A-9溶液 97 B-1 147 147 147 147 147 147 147 147 147 B-2 B-3 B-4 離子交換水 340 340 340 340 340 340 340 340 340 伊魯佳秋亞500 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 矽系塗平劑 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 不揮發成分（％ ) 35 35 36 34 35 35 34 35 36 PH 7.2 6.8 6.8 6.8 7.4 7.2 6.9 6.8 7.2 平均粒徑（nm) 330 330 340 320 350 420 330 350 320 (B) / (A) 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 -42- 201000545 【表5】 實施例 10 11 12 13 14 組成物（份） 10 11 12 13 14 A-1溶液 97 97 97 122.8 48.5 A-2溶液 A-3溶液 A-4溶液 A-5溶液 A-6溶液 A-7溶液 A-8溶液 A-9溶液 B-1 130.2 178.5 B-2 147 B-3 147 B-4 147 離子交換水 340 340 340 330 360 伊魯佳秋亞500 10.5 10.5 10.5 10.5 10.5 矽系塗平劑 2.1 2.1 2.1 2.1 2.1 不揮發成分（％ ) 35 35 35 36 34 PH 7.3 7.3 7.2 7.2 7.3 平均粒徑（nm) 330 320 340 230 470 (B)/(A) 2.3 2.3 2.3 1.6 5.7 -43- 201000545 【表6】 比較例 1 2 3 4 5 比較對象組成物（份） 1’ 2’ 3’ 4’ 5’ A，-1溶液 97 A，-2溶液 97 A’ -3溶液 97 A，-4溶液 97 A’ -5溶液 97 A’ -6溶液 B-1 147 147 147 147 147 B-2 B-3 B-4 離子交換水 340 340 340 340 340 伊魯佳秋亞500 10.5 10.5 10.5 10.5 10.5 矽系塗平劑 2.1 2.1 2.1 2.1 2.1 不揮發成分（％ ) 34 35 35 35 35 PH 7.3 7.5 6.8 6.9 6.6 平均粒徑（nm) 330 360 470 350 550 (B) / (A) 2.3 2.3 2.3 2.3 2.3 【表7】 比較例 6 7 8 9 比較對象組成物（份） 7’ 8， 9’ 10’ A，1溶液 97 97 136 40.4 B-1 122 183.8 b-1 147 b-2 147 離子交換水 340 340 325 360 伊魯佳秋亞500 10.5 10.5 10.5 10.5 矽系塗平劑 2.1 2.1 2.1 2.1 不揮發成分（％ ) 35 35 34 35 PH 7.1 7.1 7.3 6.9 平均粒徑（nm) 350 340 290 460 (B) / (A) 2.3 2.3 1.4 7.0 表4至表7之註解 伊魯佳秋亞 500: Ciba Specialty Chemicals 公司製 -44- 201000545 的光聚合引發劑 矽系塗平劑：BYK製，BYK-333 【表8】 實施例 1 2 3 4 5 6 7 組成物 1 2 3 4 5 6 7 外觀評價 ◎ ◎ ◎ ◎ 〇 ◎ ◎ 耐磨損性試驗 ◎ ◎ 〇 〇 ◎ ◎ ◎ 鉛筆硬度試驗 5H 5H 3H 4H 5H 5H 5H 黏附性試驗 ◎ ◎ ◎ ◎ 〇 ◎ ◎ 耐溫水黏附性試驗 ◎ ◎ ◎ ◎ 〇 ◎ 〇 耐水性試驗 ◎ ◎ ◎ ◎ ◎ ◎ 〇 【表9】 實施例 8 9 10 11 12 13 14 組成物 8 9 10 11 12 13 14 外觀評價 ◎ ◎ ◎ ◎ ◎ 〇 ◎ 耐磨損性試驗 〇 ◎ ◎ 〇 ◎ 〇 ◎ 鉛筆硬度試驗 5H 5H 5H 4H 5H 4H 5H 黏附性試驗 ◎ 〇 〇 ◎ 〇 ◎ 〇 耐溫水黏附性試驗 ◎ 〇 〇 ◎ 〇 〇 〇 耐水性試驗 ◎ 〇 ◎ ◎ 〇 〇 〇 【表10】Rub 1 000 back and forth on the steel surface of # 0000. Measurement of haze DI DIGITAL -35- 201000545 〇: 3.5 or more to less than 5.0. △ : 5.0 or more to less than 15.0. X : 1 5.0 or more. Pencil hardness test: The hardness of the coated surface of the test coated board was tested without damage to the test surface according to JIS-S-6006 using a high-grade pencil specified in JIS-S-6006. Adhesion test: According to JIS-K5 600-5-6 'on the coated surface of the test coated board (test coating board using PMMA, ABS and PC on the substrate), cut into a checkerboard with a width of lmm to make 100 The block 'use cellophane glue' was subjected to a peel test, which was judged by the number of remaining checkerboards. ◎: All test coating plates were 100. • 〇: All test panels are more than 80' and one or two test panels are 100. △: All of the test coated plates were 80 to 99. X: Any of the test coated plates is 79 or less. Heat-resistant water adhesion: After immersing the test coated board (test coating board using PMMA, ABS, and PC on a substrate) in warm water of 90 ° C for 2 hours, * the above adhesion test was performed. ◎: All test coating plates are 100. 〇: All test panels were 80 or more, and one or two test panels were 100. △: All of the test coated plates were 80 to 99. X: Any of the test coated plates are 79 or less. Water resistance test: The test coated board (test coating board using PMMA, ABS, and PC on the substrate) was immersed in warm water of 50 ° C for 24 hours and 72 hours, and the whitened state of the coated surface was visually judged. -36- 201000545 ◎: All test coated panels did not change after 72 hours. 〇: All test panels did not change after 24 hours, but at least one of the test panels was partially whitened or expanded after 72 hours. △: Part of the whitening or swelling occurred after 24 hours of all the test coated sheets. X: All test panels were fully whitened or expanded after 24 hours. Examples 2 to 14 and Comparative Examples 1 to 9 < According to the method of Example 1, the active energy ray-curable aqueous resin compositions 2 to 14 and the comparative control active energy were prepared by the raw material compositions shown in Table 2. Linear hardening type aqueous resin composition 1 '-9'. Carry out and examples! The evaluation results of the same various tests are shown in Table 8 to Table 11. ί -37- 201000545 [Table 1] Synthesis Example 1 2 3 4 5 Acrylic (A) A-1 A-2 A-3 A-4 A-5 • Monomer mixture (parts) MMA 434 434 434 388.5 486.5 BMA 21 36.4 18.9 89.6 EA 14 14 18.9 BA 21 10.5 2EHA 21 AA 84 87.5 66.5 84 84 MAA M-5300 35 16.1 103.6 35 35 HEA 63 HEMA 105 112 63 84 FM-1 • Initiator (parts) 12.6 9.8 12.6 14.0 15.4 Triethylamine 23.3 19.1 29.0 14.1 42.4 25% ammonia water 36.7 30.0 19.5 38.1 28.6 Amount of radical polymerizable monomer represented by the formula (1) (%) 5 2.3 14.8 5 5 Amount of methyl methacrylate α) 62 62 62 55.5 69.5 Amount of neutralized carboxyl group (mmol/g) 1.10 0.90 0.82 1.00 1.20 Acrylic resin used in the preparation of acrylic resin (Λ) (a) Physical properties of acrylic resin (a) a-1 a-2 a -3 a-4 a-5 number average molecular weight 15000 16000 17000 13000 11000 weight average molecular weight 45000 62000 55000 38000 32000 non-volatile content U) 65 65 65 65 65 solid acid value 102 101 101 102 102 solid part hydroxyl price 64 69 38 51 43 Glass transfer temperature ΓΟ 72 76 64 67 60 -38- 201000545 [Table 2] Synthesis Example 6 7 8 9 Acrylic resin A-6 A-7 A-8 A-9 • Monomer mixture (parts) MMA 434 434 462 434 BMA 87.5 31.5 7 EA BA 10.5 2EHA 14 AA 63 115.5 70 84 MAA M-5300 35 35 84 35 HEA HEMA 70 70 28 105 FM-1 14 42 • Initiator (parts) 12.6 8.4 12.6 11.2 Triethylamine 37.1 0 18.0 23.3 25% Ammonia 25.0 45.2 28.3 36.7 General ( 1) Amount of radical polymerizable monomer (%) 5 5 12 5 Amount of methyl methacrylate (%) 62 62 66 62 Neutralized amount of base (mmol/g) 1.05 0.95 0.85 1.10 The acrylic resin (a) is used to prepare the acrylic resin (a). The acrylic resin (a) a-6 a-7 a-8 a-9 number average molecular weight 13000 18000 16000 15000 weight average molecular weight 42000 75000 55000 56000 non-volatile content (%) 65 65 65 65 Solid acid value 79 137 133 102 Solid hydroxyvalence 43 48 22 78 Glass transition temperature rc) 69 74 72 73 -39- 201000545 [Table 3] Synthesis Example 10 11 12 13 14 Acrylic resin A -1 A, -2 A, -3 A-4 A, -5 • Mixture (parts) MMA 434 434 381.5 493.5 434 BMA 32.9 28 66.5 7 55.3 EA 28 BA 28 28 14 2EHA AA 87.5 66.5 84 84 56.7 MAA M-5300 12.6 108.5 35 35 35 HEA HEMA 105 35 105 80.5 105 FM-1 • Initiator (parts) 12.6 12.6 14.0 12.6 12.6 Triethylamine 23.3 25.4 19.1 21.2 16.6 25% ammonia water 36.6 40.0 30.0 33.3 26.0 The amount of the radical polymerizable monomer represented by the formula (1) (%) 1.8 15.5 5 5 5 Amount of methyl acrylate U ) 62 62 54.5 70.5 62 Residual amount of residue (mraol/g) 1.10 1.20 0.90 1.00 0.78 Amount of radical polymerizable monomer represented by the formula (1) (%) 1.8 15.5 5 5 5 Physical properties of acrylic resin (a,) used in the preparation of acrylic resin (A') 値 Acrylic resin (a,) a'-l a'-2 a'-3 a, -4 a, -5 number average Molecular weight 13000 16000 13000 15000 15000 Weight average molecular weight 41000 56000 39000 45000 51000 Non-volatile content (%) 65 65 65 65 65 Solid acid value 100 103 102 102 72 Solid content hydroxyl price 73 30 73 49 69 Glass transfer temperature ΓΟ 75 58 68 81 73 Note to Table 1 MMA: Methyl methacrylate BMA: butyl methacrylate EA: ethyl acrylate BA: butyl acrylate-40- 201000545 BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate AA: Acrylic MAA: Methacrylic acid HEA: Hydroxyethyl acrylate HEMA: Hydroxyethyl methacrylate M-5300: Yalonicos μ·5300 (Manufactured by East Asia Synthetic Co., Ltd., ω-carboxypolycaprolactone acrylate FM-1: Pracosicol (prototype, plaCCEL) FM-1 (Daisier Chemical Co., Ltd. Preparation of Ethyl Ester Ethylhexyl Ester Ethyl Ester 2-Ethyloxyhydroxy Peracid Base Dissolved propane three-agent base hairpin g Π substance addition plus 11 ο m in solution solution -41 - 201000545 [Table 4] Example 1 2 3 4 5 6 7 8 9 Composition (parts) 1 2 3 4 5 6 7 8 9 A-1 solution 97 A-2 solution 97 A-3 solution 97 A-4 solution 97 A-5 solution 97 A-6 solution 97 A-7 solution 97 A-8 solution 97 A-9 solution 97 B- 1 147 147 147 147 147 147 147 147 147 B-2 B-3 B-4 Ion exchange water 340 34 0 340 340 340 340 340 340 340 Irujiaqiuya 500 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 Tanning coating agent 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 Non-volatile content (%) 35 35 36 34 35 35 34 35 36 PH 7.2 6.8 6.8 6.8 7.4 7.2 6.9 6.8 7.2 Average particle size (nm) 330 330 340 320 350 420 330 350 320 (B) / (A) 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 -42- 201000545 [Table 5 Example 10 11 12 13 14 Composition (parts) 10 11 12 13 14 A-1 solution 97 97 97 122.8 48.5 A-2 solution A-3 solution A-4 solution A-5 solution A-6 solution A-7 Solution A-8 solution A-9 solution B-1 130.2 178.5 B-2 147 B-3 147 B-4 147 Ion exchange water 340 340 340 330 360 Irujiaqiu 500 10.5 10.5 10.5 10.5 10.5 Lanthanide coating agent 2.1 2.1 2.1 2.1 2.1 Non-volatile content (%) 35 35 35 36 34 PH 7.3 7.3 7.2 7.2 7.3 Average particle size (nm) 330 320 340 230 470 (B) / (A) 2.3 2.3 2.3 1.6 5.7 -43- 201000545 [ Table 6] Comparative Example 1 2 3 4 5 Comparative object composition (parts) 1' 2' 3 4' 5' A, -1 solution 97 A, -2 solution 97 A' -3 solution 97 A, -4 solution 97 A' -5 solution 97 A' -6 solution B-1 147 147 147 147 147 B-2 B-3 B-4 Ion exchange water 340 340 340 340 340 Irujiaqiuya 500 10.5 10.5 10.5 10.5 10.5 Lanthanide coating agent 2.1 2.1 2.1 2.1 2.1 Non-volatile content (%) 34 35 35 35 35 PH 7.3 7.5 6.8 6.9 6.6 Average particle size (nm) 330 360 470 350 550 (B) / (A) 2.3 2.3 2.3 2.3 2.3 [Table 7] Comparative Example 6 7 8 9 Comparison object composition (parts) 7' 8, 9' 10' A,1 solution 97 97 136 40.4 B-1 122 183.8 b-1 147 b-2 147 Ion exchange water 340 340 325 360 Irujiaqiu 500 10.5 10.5 10.5 10.5 Lanthanide coating agent 2.1 2.1 2.1 2.1 Non-volatile components (%) 35 35 34 35 PH 7.1 7.1 7.3 6.9 Average particle size (nm) 350 340 290 460 (B) / (A) 2.3 2.3 1.4 7.0 Notes to Tables 4 to 7 Iru Jiaqiu 500: Ciba Specialty Chemicals Company-44-201000545 Photopolymerization initiator lanthanide coating agent: BYK system, BYK-333 [Table 8] Example 1 2 3 4 5 6 7 Composition 1 2 3 4 5 6 7 Appearance evaluation ◎ ◎ ◎ ◎ 〇 ◎ ◎ Abrasion resistance test ◎ ◎ 〇〇 ◎ ◎ ◎ Pencil hardness test 5H 5H 3H 4H 5H 5H 5H Adhesion test ◎ ◎ ◎ ◎ 〇 ◎ ◎ Temperature-resistant water adhesion test ◎ ◎ ◎ ◎ 〇 ◎ 〇 Water resistance test ◎ ◎ ◎ ◎ ◎ ◎ 〇 [Table 9] Example 8 9 10 11 12 13 14 Composition 8 9 10 11 12 13 14 Appearance evaluation ◎ ◎ ◎ ◎ ◎ 〇 ◎ abrasion resistance test 〇 ◎ ◎ 〇 ◎ 〇 ◎ pencil hardness test 5H 5H 5H 4H 5H 4H 5H adhesion test ◎ 〇〇 ◎ 〇 ◎ 〇 heat-resistant water adhesion test ◎ 〇〇◎ 〇〇〇 Water resistance test ◎ 〇 ◎ ◎ 〇〇〇 [Table 10]
比較例 1 2 3 4 5 組成物 Γ 2， 3， 4’ 5， 外觀評價 ◎ ◎ ◎ ◎ X 耐磨損性試驗 ◎ Δ 〇 ◎ 〇 鉛筆硬度試驗 5H 2H 4H 5H 4H 黏附性試驗 ◎ ◎ ◎ Δ Δ 耐溫水黏附性試驗 ◎ ◎ ◎ Δ X 耐水性試驗 ◎ ◎ ◎ Δ X -45- 201000545 【表11】 比較例 6 7 8 9 組成物 6’ 7’ 8’ 9， 外觀評價 ◎ ◎ 〇 ◎ 耐磨損性試驗 X ◎ X ◎ 鉛筆硬度試驗 3H 5H 3H 5H 黏附性試驗 〇 Δ ◎ Δ 耐溫水黏附性試驗 〇 Δ Δ Δ 耐水性試驗 〇 Δ Δ Δ 【圖式簡單說明】 〇 /»w 【主要元件符號說明】 〇 j\w -46 -Comparative Example 1 2 3 4 5 Composition Γ 2, 3, 4' 5, Appearance Evaluation ◎ ◎ ◎ ◎ X abrasion resistance test ◎ Δ 〇 ◎ 〇 pencil hardness test 5H 2H 4H 5H 4H adhesion test ◎ ◎ ◎ Δ Δ Heat-resistant water adhesion test ◎ ◎ ◎ Δ X Water resistance test ◎ ◎ ◎ Δ X -45- 201000545 [Table 11] Comparative Example 6 7 8 9 Composition 6' 7' 8' 9, Appearance evaluation ◎ ◎ 〇 ◎ Abrasion resistance test X ◎ X ◎ Pencil hardness test 3H 5H 3H 5H Adhesion test 〇 Δ Δ Δ Heat-resistant water adhesion test 〇 Δ Δ Water resistance test 〇 Δ Δ Δ [Simple diagram] 〇/»w [Main component symbol description] 〇j\w -46 -