1285661 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於一種耐衝擊性的甲基丙烯酸樹脂模塑物 件，彼之製法及形成該物件之樹脂組成物。 【先前技術】 甲基丙烯酸樹脂澆鑄模塑物件，其可含彈性粒子且可 得自澆鑄聚合，可用於室內隔間板、道路隔音板等，曰本 專利申請公開案（JP-A-) 8- 1 5 1 498揭示一種用於製造耐衝 擊性甲基丙烯酸樹脂澆鑄模塑物件之方法，其係在聚合元 件內將含甲基丙烯酸甲酯作爲主要成份之單體之組成物、 甲基丙烯酸甲酯單元作爲主要單元組成之甲基丙烯酸樹脂 、彈性粒子及聚合引發劑聚合，Ρ_Α-8· 1 5 1 498也揭示有機 過氧化物、偶氮化合物等可作爲聚合引發劑使用。 傳統上，耐衝擊性甲基丙烯酸樹脂澆鑄模塑物件需要 有足夠的耐衝擊性、在物件中殘留很少的單體且有足夠的 透明度。 但是，經由傳統製造方法所得的耐衝擊性甲基丙烯酸 樹脂澆鑄模塑物件含相當大量殘留的單體且其透明度不足 【發明內容】 本發明之一個目的是提供一種用於製造含很少殘留的 單體且具有足夠高的透明度之耐衝擊性甲基丙烯酸樹脂澆 (2) 1285661 鑄模塑物件，根據本發明者之硏究結果，經發現含很少殘 留的單體且具有足夠的耐衝擊性及進一步改良的透明度之 耐衝擊性甲基丙烯酸樹脂澆鑄模塑物件可以使用含多種具 有不同10-小時半衰期溫度的單官能基有機過氧化物作爲 聚合引發劑之樹脂組成物製造。 本發明提供一種樹脂組成物，其含： 至少一種含甲基丙烯酸甲酯單體之單體， 含甲基丙烯酸甲酯單元之甲基丙烯酸樹脂， 彈性粒子， 10-小時半衰期溫度是60 °c或更低之第一種單官能基 有機過氧化物， 1〇_小時半衰期溫度是高於60 t且是80°c或更低之 第二種單官能基有機過氧化物，及 10-小時半衰期溫度是高於8(TC之第三種單官能基有 機過氧化物。 本發明也提供一種使用上述樹脂組成物及甲基丙烯酸 樹脂模塑物件製造方法所得之甲基丙烯酸樹脂模塑物件。 【實施方式】 在本發明中的一種樹脂組成物含： 至少一種含甲基丙烯酸甲酯單體之單體， 含甲基丙烯酸甲酯單元之甲基丙烯酸樹脂， 彈性粒子， 10-小時半衰期溫度是60°c或更低之第一種單官能基 -5- (3) 1285661 有機過氧化物， 10-小時半滾期溫度是高於60 °C且是80°C或更低之 第二種單官能基有機過氧化物，及 10-小時半衰期溫度是高於80 °C之第三種單官能基有 機過氧化物。 在本發明中使用的單體含甲基丙烯酸甲酯單體，此單 體較宜含甲基丙烯酸甲酯單體作爲主要成份，且更宜含至 少50重量％之甲基丙烯酸甲酯單體。 此單體可以是甲基丙烯酸甲酯單體本身或是甲基丙烯 酸甲酯單體與可和甲基丙烯酸甲酯單體共聚合的單體之混 合物，可和甲基丙烯酸甲酯單體共聚合的單體之實例包括 例如丙烯酸酯例如丙烯酸甲酯、丙烯酸乙酯及丙烯酸2-乙基己酯；甲基丙烯酸酯例如甲基丙烯酸乙酯、甲基丙烯 酸正丁酯、甲基丙烯酸異丁酯及甲基丙烯酸2-乙基己酯 ;甲基丙烯酸；馬來酸酐；苯乙烯；環己基馬來醯亞胺； 丙烯腈等，注意該甲基丙烯酸酯不包括甲基丙烯酸甲酯， 這些可共聚合的單體可以單獨使用或可結合二或多種單體 使用，在使用含可共聚合的單體之混合物之情形下，甲基 丙烯酸甲酯如同上述較宜含50重量％或更高的量之此混 合物。 甲基丙烯酸甲酯及可和甲基丙烯酸甲酯單體共聚合的 單體可以是寡聚物之形式例如二聚物、三聚物等° 在本發明中使用的甲基丙烯酸樹脂是含甲基丙烯酸甲 酯單元之甲基丙烯酸樹脂，較宜是含甲基丙烯酸甲醋單元 -6 - (4) 1285661 爲主要單元之甲基丙烯酸樹脂，且更宜是含甲基丙烯酸甲 酯單元的量是50重量％或更高之甲基丙烯酸樹脂。 該甲基丙烯酸樹脂可以是甲基丙烯酸甲酯之均聚合物 或是甲基丙烯酸甲酯與可和甲基丙烯酸甲酯共聚合的單體 之共聚合物，在共聚合物中可和甲基丙烯酸甲酯共聚合的 單體之實例包括上述舉例的單體其可包含在含甲基丙烯酸 甲酯單體且可和甲基丙烯酸甲酯共聚合之單體，在使用共 聚合物作爲甲基丙烯酸樹脂之情形下，在共聚合物中甲基 丙烯酸甲酯單元之含量較宜是50重量％或更高，甲基丙 烯酸樹脂之黏度平均分子量較宜是約1 0,000或更高且約 300,000或更低。 在本發明中使用的彈性粒子可以是單層結構的彈性體 之彈性粒子，或者是，該彈性粒子可以是有多層結構之彈 性粒子例如彈性體作爲核心且在核心周圍形成甲基丙烯酸 樹脂層之兩層結構彈性粒子；甲基丙烯酸樹脂作爲核心、 在核心周圍形成的彈性體之中間層及在中間層外圍形成的 甲基丙烯酸樹脂外層之三層結構彈性粒子。 此彈性粒子之粒子直徑是0.1微米或更大且1微米或 更小，且較宜是0.2微米或更大且0.8微米或更小，當粒 子直徑是小於〇· 1微米時，耐衝擊性容易被破壞，當其超 過1微米時，透明性容易被破壞，較宜使用多層結構之彈 性粒子，尤其是三層結構之彈性粒子，因爲所得的耐衝擊 性甲基丙烯酸樹脂澆鑄模塑物件具有更極佳的透明性。 此種彈性粒子可得自商業化供應作爲耐衝擊性甲基丙 -7- (5) 1285661 嫌酸樹脂，例如”Sumipex HT01X”（Sumitomo Chemical Co·，Ltd.販賣）、”〇r〇glas DR”（Sumitomo-Haas Co·販賣） 等，此種可得自商業化供應的彈性粒子是分散在甲基丙烯 酸樹脂中的狀態。 在本發明中的樹脂組成物之甲基丙烯酸樹脂/彈性粒 子含量比例（其係甲基丙烯酸樹脂對彈性粒子之含量比例） 範圍較宜是從3/7重量至7/3重量，甲基丙烯酸樹脂及彈 性粒子之總量較宜是1 0重量組份或更多且40重量組份或 更低，以單體、甲基丙烯酸樹脂及彈性粒子總量之1 00重 量組份爲基準，當甲基丙烯酸樹脂及彈性粒子之總量低於 1 〇重量組份時，所得的模塑物件之耐衝擊性容易不足， 且當總量高於40重量組份時，樹脂組成物有非常高的黏 性，其造成塡入聚合元件之困難。 在本發明中的樹脂組成物含10-小時半衰期溫度是60 °C或更低之第一種單官能基有機過氧化物、1 0-小時半衰 期溫度是高於60 °C且是80 °C或更低之第二種單官能基 有機過氧化物、及10-小時半衰期溫度是高於80°C之第三 種單官能基有機過氧化物作爲聚合引發劑。 在本發明中的各有機過氧化物是一種有機化合物，在 其分子中含下式代表的鍵： 有機過氧化物經由鍵的分解而產生基，在本發明中的 -8 - (6) 1285661 10-小時半衰期溫度（1[)是當有機過氧化物單獨加熱時，半 數的有機過氧化物在1 0小時內分解之溫度，對於待測量 的有機過氧化物之一級分解反應，此溫度可得自 Arrhenius公式，此公式是得自分解產物隨著時間通過之 量變化，其中有機過氧化物是溶解在惰性溶劑例如苯且隨 後將所得的溶液在定溫下加熱而產生分解產物。 在本發明中的單官能基有機過氧化物在其分子中含上 述鍵（-0-0-)，當使用在其分子中含二或多個此鍵之多官 能基有機過氧化物例如過氧三甲基己二酸二第三丁酯時， 殘留在所得模塑物件中的單體含量容易增加。 第一種單官能基有機過氧化物之實例包括例如過氧新 癸酸第三己酯（T (10-小時半衰期溫度）= 45°C)、過氧二碳 酸二甲氧基丁酯（T = 46°C )、過氧新癸酸第三丁酯（T = 46°C ) 、過氧特戊酸第三己酯（T = 53°C)、過氧特戊酸第三丁酯 (T = 55°C)、3,5,5-三甲基己醯基過氧化物（T = 59°C)等，因 爲處理容易，較宜使用10 -小時半衰期溫度是40 °C或更高 之第一種單官能基有機過氧化物，且更宜10-小時半衰期 溫度是5 0 °C或更高。 第二種單官能基有機過氧化物之實例包括例如辛醯基 過氧化物（T = 62°C )、月桂醯基過氧化物（T = 62°C )、硬脂醯 基過氧化物（T = 62°C)、過氧-2-乙基己酸1，1，3,3·四甲基丁 酯（T = 66t)、琥珀醯化過氧化物（T = 66t)、過氧-2-乙基己 酸1-環己基-1-甲基乙酯（T = 68°C)、過氧-2-乙基己酸第三 己酯（T = 70°C)、過氧-2-乙基己酸第三丁酯（T = 72°C)、過氧 (7) 1285661 異丁酸第三丁酯（T = 78°C)等。 第三種單官能基有機過氧化物之實例包括例如過氧異 丙基單碳酸第三己酯（T = 95 °C)、過氧馬來酸第三丁酯 (T = 96°C)、過氧-3,5,5-三甲基己酸第三丁酯（T = 97°C)、過 氧月桂酸第三丁酯（T = 98°C)、過氧異丙基碳酸第三丁酯 (T = 99°C)、過氧-2-乙基己基單碳酸第三丁酯（T = 99t：)、過 氧苯甲酸第三己酯（T = 99aC )、過氧醋酸第三丁酯（T=1〇2CC )、過氧苯甲酸第三丁酯（T=104 t )、二枯基過氧化物 (T=119°C)、第三丁基枯基過氧化物（T=120°C)，因爲在聚 合時的最高溫度可以相當低，較宜使用1 〇_小時半衰期溫 度是110 °C或更低之第三種單官能基有機過氧化物。 因爲可以得到透明度更佳的耐衝擊性甲基丙烯酸樹脂 澆鑄模塑物件，第一種單官能基有機過氧化物之1 0-小時 半衰期溫度（TJ與第二種單官能基有機過氧化物之ίο-小 時半衰期溫度（T2)之差異（ΛΤ12)較宜是10°C或更高，且更 宜是13 °C或更高，且可以是30 °C或更低，而且，因爲可 以得到透明度更佳的耐衝擊性甲基丙烯酸樹脂澆鑄模塑物 件，第二種單官能基有機過氧化物之1 0-小時半衰期溫度 (T2)與第三種單官能基有機過氧化物之ίο·小時半衰期溫 度（Τ3)之差異（ΔΤ23)較宜是10°C或更高，且更宜是18t 或更高，且更宜是35 t或更低。 本發明樹脂組成物之第一種單官能基有機過氧化物/ 第二種單官能基有機過氧化物含量比例（其係第一種單官 能基有機過氧化物對第二種單官能基有機過氧化物之含量 -10- (8) 1285661 比例）範圍是從3/7重量至7/3重量，且較宜是從4/6重量 至6/4重量，而且，本發明樹脂組成物之第一及第二種單 官能基有機過氧化物總量對第三種單官能基有機過氧化物 之含量比例範圍是從3/7重量至7/3重量，且較宜是從 4/6重量至6/4重量，總量中的第一、第二及第三種單官 能基有機過氧化物含量是從〇.〇5重量組份至0.5重量組 份，以包括甲基丙烯酸甲酯單體之單體之1〇〇重量組份爲 基準。 第一種單官能基有機過氧化物、第二種單官能基有機 過氧化物及第三種單官能基有機過氧化物可以使用分別用 溶劑稀釋之狀態，此惰性溶劑可根據單官能基有機過氧化 物之種類而適當地選擇，且惰性溶劑之實例包括飽和的脂 族烴溶劑例如石油腦及礦油精、烴溶劑例如苯及甲苯、丙 酮、枯烯、二苯基乙烷、醋酸乙酯等。 除了單體、甲基丙烯酸樹脂、彈性粒子、第一種單官 能基有機過氧化物、第二種單官能基有機過氧化物及第三 種單官能基有機過氧化物以外，本發明樹脂組成物還可含 添加劑例如抗氧化劑、UV吸收劑、脫模劑、染料等，決 定於所要的耐衝擊性甲基丙烯酸樹脂澆鑄模塑物件之應用 〇 經由聚合上述的樹脂組成物，在本發明中可以製造具 有足夠耐衝擊性、含很少殘留的單體及極佳的透明度之甲 基丙烯酸樹脂模塑物件。 聚合方法沒有特別的限制，且可舉例如本體聚合、澆 -11 - 1285661 (9) 鑄聚合等，以下敘述在聚合元件中進行聚合之澆鑄聚合， 其不能構成本發明範圍之限制。 當在聚合元件進行聚合時，使用的聚合元件沒有特別 的限制，且可使用普遍用在澆鑄聚合方法之任何聚合元件 ，例如在要獲得板狀甲基丙烯酸樹脂澆鑄模塑物件之情形 中，可以使用彼此平行排列的兩個基板組成之批次型元件 或彼此平行的兩條連續帶組成之連續元件。 當使用批次型元件時，可以利用玻璃基板或金屬基板 作爲其基板，此兩個基板可以排列成彼此分離且作爲元件 的兩個牆，以及軟性密封材料其可作爲元件剩餘的四個牆 ，樹脂組成物在元件中聚合，也就是在兩個基板及軟性密 封材料環繞的區域內聚合，基板i間的距離可以適當地選 擇，決定於所要的板狀模塑物件之厚度，且可以是約5毫 米或更厚且3 0毫米或更薄，經由改變軟性密封材料之厚 度，可以調整基板之間的距離，另外，其可經由擠壓兩個 基板並壓縮軟性密封材料而調整。 樹脂組成物在聚合元件中進行的聚合，可以經由將組 成物倒入聚合元件並加熱所得的元件，例如，經由保持溫 度（例如溫度是30°C或更高）至少5°C低於第一種單官能基 有機過氧化物之10-小時半衰期溫度（TJ經10小時或更長 ，且隨後將溫度增加至溫度至少5 °C高於第三種單官能基 有機過氧化物之10-小時半衰期溫度（T3)但低於例如約140 t，聚合溫度可以逐步或連續增加，較宜逐步增加溫度， 當溫度是逐步增加時，進行聚合較宜經由保持溫度至少5 -12- (10) 1285661 °C低於第一種單官能基有機過氧化物之1 0-小時半衰期溫 度（TO經10小時或更長，然後保持溫度在從低於約5°C之 溫度至高於約1 0 °C之溫度之第一種單官能基有機過氧化 物之10-小時半衰期溫度（TJ經1小時或更長，然後保持 溫度在從低於約1 0 °C之溫度至高於約1 (TC之溫度之第二 種單官能基有機過氧化物之10-小時半衰期溫度（T2)經1 小時或更長，且最後增加溫度至至少5 °c高於第三種單官 能基有機過氧化物之10-小時半衰期溫度（τ3)，增加溫度 時，可以使用熱水、熱空氣或蒸汽。 在本發明中，樹脂組成物的第一種單官能基有機過氧 化物、第二種單官能基有機過氧化物及第三種單官能基有 機過氧化物是經由加熱分解而產生基，其使得樹脂組成物 聚合而形成模塑物件。 在聚合元件中進行聚合後，經由分開聚合元件可以取 出耐衝擊性的甲基丙烯酸樹脂澆鑄模塑物件，在此方式下 所得的耐衝擊性的甲基丙烯酸樹脂澆鑄模塑物件具有足夠 耐衝擊性及極佳的透明度，因此，該模塑物件可用於例如 提供室內隔間板之板材、道路之隔音板、防彈板等。 根據本發明，可以製造含很少殘留的單體、具有足夠 耐衝擊性及極佳的透明度之耐衝擊性甲基丙烯酸樹脂澆鑄 模塑物件。 經由如此敘述本發明後，其明顯地可在多種方式下改 變，這些改變視爲在本發明之精神及範圍內，且從事此藝 者了解的全部這些修改都視爲在下列申請專利之範圍內。 -13- (11) 1285661 在2002年8月5日提出的日本專利申請案2002-227032之整份敘述，包括說明、申請專利範圍、附圖及 摘要，整份倂於本文供參考。 實例 本發明經由下列實例更詳細地說明，其不能構成本發 明範圍之限制。 經由下列方法測量各實例中所得的模塑物件含的殘留 單體量： 從各模塑物件切下樣本（〇. 1克）並溶解在20毫升二氯 甲烷，在所得的溶液中加入15微升甲基異丁基酮（作爲內 標），經由氣相層析法定量測量溶液中含的單體成份。 將模塑物件在恆溫器內保持2 3 °C之溫度經1小時， 根據JIS K7 136測量模塑物件之濁度値。 使用樣本1型根據JIS K71 1 1測量模塑物件之Charpy 衝擊強度。 實例1 製備樹脂組成物： 將甲基丙烯酸甲酯（77.5重量組份）、95重量％甲基丙 烯酸甲酯單元與5重量％丙烯酸甲酯單元共聚物之甲基丙 烯酸樹脂（13.5重量組份；黏度平均分子量約1 1 0,000)及 三層結構之彈性粒子（9重量組份；粒子大小是〇 · 3微米） 混合並在6 0 °C攪拌2小時，冷卻後，在所得的混合物中 -14- (12) 1285661 加入過氧特戊酸第三丁酯（0.014重量組份；（T (10-小時半 衰期溫度）是55 °C )溶解在飽和脂肪烴溶劑之溶液（濃度是 70重量％; 0.02重量組份）、過氧-2-乙基己酸第三丁酯 (〇 . 〇 2重量組份，純度是9 7重量％或更高；約0.0 2重量組 份之純成份；T是72°C)、過氧異丙基碳酸第三丁酯（〇.〇3 重量組份；T是99 °C )溶解在烴溶劑之溶液（濃度是75重 量％; 0.04重量組份）、UV吸收劑（0.01重量組份；商標 名稱”Sumisorb 200”；由 Sumitomo Chemical Co.，Ltd.販 賣）及脫模劑（0.05重量組份；商標名稱”Sanseparer”；由 Sanyo Chemical Industries，Ltd.販賣），再攪拌 1 小時後， 將所得的混合物在87kPa (絕對壓力）下脫氣30分鐘，得 到樹脂組成物。 聚合： 將上述所得的樹脂組成物注射至兩片玻璃板（3 0公分 X 3 0公分，厚度是1 0毫米）及軟性聚氯乙烯組成的密封材 料組成之聚合元件內，將聚合元件內的樹脂組成物加熱並 在46°C之溫度保持16小時，在0.25°C/分鐘之溫度增加 速率下再加熱至溫度是5 1 °C，在5 1°C之溫度保持4小時 ，在0.45°C/分鐘之溫度增加速率下再加熱至溫度是60°C ，在60°C之溫度保持3小時，然後在0.5 °C/分鐘之溫度 增加速率下再加熱至溫度是70°C，在70°C之溫度保持3 小時，然後在〇.5°C/分鐘之溫度增加速率下再加熱至溫度 是85°C，在85°C之溫度保持3小時，最後在〇.5°C /分鐘 -15- (13) 1285661 之溫度增加速率下再加熱至溫度是12(TC，並在120°C之 溫度保持2小時，在從120°C至125 °C之溫度範圍保持3 小時，使用熱空氣循環型加熱爐進行加熱，加熱後，使所 得的組成物冷卻，然後將聚合元件打開而得到樹脂組成物 聚合結果之耐衝擊性甲基丙烯酸樹脂澆鑄模塑物件（板狀 ，大小是30公分X 30公分X 10毫米（厚度））。 評定： 從所得的模塑物件切下樣本，使用此樣本測量模塑物 件殘留的單體含量、濁度値及Charpy衝擊強度，結果殘 留的單體含量是〇·9重量％，濁度値是0.7%且Charpy衝 擊強度是36千焦耳/平方米，評定結果列在表i。 實例2 除了在甲基丙烯酸甲酯、甲基丙烯酸樹脂及三層結構 彈性粒子混合後在60°C之溫度攪拌1 3小時外，相同於實 例1之方法得到板狀耐衝擊性甲基丙烯酸樹脂澆鑄模塑物 件，所得模塑物件之評定結果列在表1。 實例比較1 除了單獨使用0.08重量組份之2,2-偶氮雙異丁腈（一 種偶氮化合物；T是65 °C)代替過氧特戊酸第三丁酯溶液 、過氧-2-乙基己酸第三丁酯溶液及過氧異丙基碳酸第三 丁酯溶液以外，相同於實例1之方法得到板狀耐衝擊性甲 -16- (14) 1285661 基丙烯酸樹脂澆鑄模塑物件，所得模塑物件之評定結果列 在表1。 實例比較2 除了單獨使用0 · 0 8重量組份（約〇 . 〇 8重量組份之純成 份）之過氧-2-乙基己酸第三丁酯（純度是97重量％或更高） 代替過氧特戊酸第三丁酯溶液、過氧-2_乙基己酸第三丁 酯溶液及過氧異丙基碳酸第三丁酯溶液以外，相同於實例 1之方法得到板狀耐衝擊性甲基丙烯酸樹脂澆鑄模塑物件 ，所得模塑物件之評定結果列在表1。 實例比較3 除了使用〇·〇2重量組份之2,2’_偶氮雙（2,4_二甲基戊 腈）（一種偶氮化合物；T是51t )代替過氧特戊酸第三丁 酯溶液以外，相同於實例1之方法得到板狀耐衝擊性甲基 丙烯酸樹脂澆鑄模塑物件，所得模塑物件之評定結果列在 表1。 實例比較4 除了單獨使用0.23重量組份（約0.1 15重量組份之純 成份）之過氧三甲基己二酸二第三丁酯（一種多官能基有機 過氧化物）溶解在異鏈烷烴之溶液（濃度是50重量％)代替 過氧特戊酸第三丁酯溶液、過氧-2-乙基己酸第三丁酯溶 液及過氧異丙基碳酸第三丁酯溶液以外，相同於實例1之 -17- (15) 1285661 方法得到板狀耐衝擊性甲基丙烯酸樹脂澆鑄模塑物件，所 得模塑物件之評定結果列在表1。1285661 (1) Field of the Invention The present invention relates to an impact-resistant methacrylic resin molded article, a process for producing the same, and a resin composition for forming the article. [Prior Art] A methacrylic resin cast molded article which can contain elastic particles and can be obtained by casting polymerization, can be used for indoor partition boards, road soundproof boards, etc., and the present patent application publication (JP-A-) 8 - 1 5 1 498 discloses a method for producing an impact-resistant methacrylic resin cast molded article, which is a composition of a monomer containing methyl methacrylate as a main component in a polymeric member, methacrylic acid The methyl ester unit is polymerized as a main unit composition of a methacrylic resin, an elastic particle, and a polymerization initiator, and Ρ_Α-8·1 5 1 498 also discloses that an organic peroxide, an azo compound, or the like can be used as a polymerization initiator. Conventionally, impact-resistant methacrylic resin cast molded articles require sufficient impact resistance, little monomer remaining in the article, and sufficient transparency. However, the impact-resistant methacrylic resin cast molded article obtained by the conventional manufacturing method contains a considerable amount of residual monomers and has insufficient transparency. [Invention] It is an object of the present invention to provide a product for producing a residue containing little residue. Monomer and impact-resistant methacrylic resin with sufficient transparency to cast (2) 1285661 cast molded article, according to the results of the present inventors, found to contain little residual monomer and sufficient impact resistance And a further improved transparency of the impact-resistant methacrylic resin cast molded article can be produced using a resin composition containing a plurality of monofunctional organic peroxides having different 10-hour half-life temperatures as a polymerization initiator. The present invention provides a resin composition comprising: at least one monomer containing methyl methacrylate monomer, a methacrylic resin containing methyl methacrylate unit, elastic particles, a 10-hour half-life temperature of 60 ° C Or lower first monofunctional organic peroxide, 1 〇 hr half-life temperature is higher than 60 t and is 80 ° C or lower of the second monofunctional organic peroxide, and 10-hour The half-life temperature is a third monofunctional organic peroxide higher than 8 (TC). The present invention also provides a methacrylic resin molded article obtained by using the above resin composition and a methacrylic resin molded article production method. [Embodiment] A resin composition in the present invention contains: at least one monomer containing methyl methacrylate monomer, methacrylic resin containing methyl methacrylate unit, elastic particles, 10-hour half-life temperature It is the first monofunctional 5-(3) 1285661 organic peroxide at 60 ° C or lower, and the 10-hour half-rolling temperature is higher than 60 ° C and is the second of 80 ° C or lower. Monofunctional organic peroxygen The compound, and the 10-hour half-life temperature is a third monofunctional organic peroxide higher than 80 ° C. The monomer used in the present invention contains a methyl methacrylate monomer, and the monomer preferably contains a methyl group. The methyl acrylate monomer as a main component, and more preferably contains at least 50% by weight of a methyl methacrylate monomer. The monomer may be a methyl methacrylate monomer itself or a methyl methacrylate monomer and Examples of a monomer copolymerizable with a methyl methacrylate monomer, and a monomer copolymerizable with a methyl methacrylate monomer include, for example, acrylates such as methyl acrylate, ethyl acrylate, and 2-ethyl acrylate. Ethyl hexyl ester; methacrylate such as ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and 2-ethylhexyl methacrylate; methacrylic acid; maleic anhydride; styrene; Cyclohexylmaleimide; acrylonitrile, etc., note that the methacrylate does not include methyl methacrylate, these copolymerizable monomers may be used alone or in combination with two or more monomers, Co-aggregated list In the case of a mixture, methyl methacrylate is preferably present in an amount of 50% by weight or more as described above. Methyl methacrylate and a monomer copolymerizable with methyl methacrylate monomer may be The form of the oligomer such as a dimer, a trimer, etc. The methacrylic resin used in the present invention is a methacrylic resin containing a methyl methacrylate unit, preferably a methacrylate containing methacrylate unit - 6 - (4) 1285661 is a main unit of methacrylic resin, and more preferably a methacrylic resin containing 50% by weight or more of a methyl methacrylate unit. The methacrylic resin may be methyl a homopolymer of methyl acrylate or a copolymer of methyl methacrylate and a monomer copolymerizable with methyl methacrylate, a monomer copolymerizable with methyl methacrylate in the copolymer. Examples include the above-exemplified monomers which may be contained in a monomer containing a methyl methacrylate monomer and copolymerizable with methyl methacrylate, in the case of using a copolymer as a methacrylic resin, in copolymerization Object Content of methyl methacrylate is more appropriate units of 50 wt% or more, methacrylic acid resin viscosity average molecular weight is more appropriate about 1 to about 0,000 or more and 300,000 or less. The elastic particles used in the present invention may be elastic particles of a single layer structure of an elastomer, or the elastic particles may be elastic particles having a multilayer structure such as an elastomer as a core and a methacrylic resin layer formed around the core. Two-layered elastic particles; a methacrylic resin as a core, an intermediate layer of an elastomer formed around the core, and a three-layered elastic particle of an outer layer of a methacrylic resin formed on the periphery of the intermediate layer. The particle diameter of the elastic particles is 0.1 μm or more and 1 μm or less, and is preferably 0.2 μm or more and 0.8 μm or less, and the impact resistance is easy when the particle diameter is less than 〇·1 μm. When it is more than 1 micrometer, the transparency is easily broken, and it is preferable to use the elastic particles of the multilayer structure, especially the elastic particles of the three-layer structure, because the obtained impact-resistant methacrylic resin cast molded article has more Excellent transparency. Such elastic particles are commercially available as impact-resistant methyl propyl-7-(5) 1285661 septic resin, such as "Sumipex HT01X" (sold by Sumitomo Chemical Co., Ltd.), "〇r〇glas DR" (Sumitomo-Haas Co., etc.), such an elastic particle which can be obtained from a commercial supply is dispersed in a methacrylic resin. The ratio of the methacrylic resin/elastic particle content of the resin composition in the present invention, which is a ratio of the content of the methacrylic resin to the elastic particles, is preferably from 3/7 to 7/3 by weight, methacrylic acid. The total amount of the resin and the elastic particles is preferably 10 parts by weight or more and 40 parts by weight or less, based on 100 parts of the total amount of the monomer, the methacrylic resin and the elastic particles. When the total amount of the methacrylic resin and the elastic particles is less than 1 〇 by weight, the impact resistance of the obtained molded article is liable to be insufficient, and when the total amount is more than 40 parts by weight, the resin composition is very high. Viscosity, which makes it difficult to break into polymeric components. The resin composition in the present invention contains a first monofunctional organic peroxide having a 10-hour half-life temperature of 60 ° C or lower, and a 10-hour half-life temperature of more than 60 ° C and 80 ° C. Or a lower second monofunctional organic peroxide, and a third monofunctional organic peroxide having a 10-hour half-life temperature higher than 80 ° C as a polymerization initiator. Each of the organic peroxides in the present invention is an organic compound having a bond represented by the following formula in its molecule: an organic peroxide generates a group via decomposition of a bond, in the present invention -8 - (6) 1285661 The 10-hour half-life temperature (1[) is the temperature at which half of the organic peroxide decomposes in 10 hours when the organic peroxide is heated alone. For the one-stage decomposition reaction of the organic peroxide to be measured, this temperature can be From the Arrhenius formula, this formula is derived from the amount of decomposition product that passes over time, wherein the organic peroxide is dissolved in an inert solvent such as benzene and the resulting solution is then heated at a fixed temperature to produce a decomposition product. The monofunctional organic peroxide in the present invention contains the above-mentioned bond (-0-0-) in its molecule, when a polyfunctional organic peroxide having two or more such bonds in its molecule is used, for example, In the case of ditributol trioxymethylene adipate, the content of the monomer remaining in the obtained molded article is apt to increase. Examples of the first monofunctional organic peroxide include, for example, perhexyl neodecanoate (T (10-hour half-life temperature) = 45 ° C), dimethoxybutyl peroxydicarbonate (T = 46 ° C ), peroxy neodecanoic acid tert-butyl ester (T = 46 ° C), peroxypivalic acid third hexyl ester (T = 53 ° C), peroxypivalic acid tert-butyl ester ( T = 55 ° C), 3,5,5-trimethylhexyl peroxide (T = 59 ° C), etc., because of the ease of handling, it is better to use a 10-hour half-life temperature of 40 ° C or higher. The first monofunctional organic peroxide, and more preferably a 10-hour half-life temperature of 50 ° C or higher. Examples of the second monofunctional organic peroxide include, for example, octyl peroxide (T = 62 ° C), lauryl peroxide (T = 62 ° C), stearic sulfhydryl peroxide (T = 62°C), 1,1,3,3·tetramethylbutyl peroxy-2-ethylhexanoate (T = 66t), amber oxidized peroxide (T = 66t), peroxy-2- 1-cyclohexyl-1-methylethyl ethylhexanoate (T = 68 ° C), perhexyl peroxy-2-ethylhexanoate (T = 70 ° C), peroxy-2-B Tert-butyl hexanoate (T = 72 ° C), peroxy (7) 1285661 tert-butyl isobutyrate (T = 78 ° C) and the like. Examples of the third monofunctional organic peroxide include, for example, third hexyl peroxyisopropyl monocarbonate (T = 95 ° C), and third butyl peroxymaleate (T = 96 ° C), Tert-butyl peroxy-3,5,5-trimethylhexanoate (T = 97 ° C), third butyl laurate (T = 98 ° C), third peroxyisopropyl carbonate Butyl ester (T = 99 ° C), perbutyl 2-ethylhexyl monocarbonate (T = 99t:), third hexyl peroxybenzoate (T = 99aC), peracetic acid third Butyl ester (T=1〇2CC), tert-butyl peroxybenzoate (T=104 t), dicumyl peroxide (T=119°C), tert-butyl cumyl peroxide (T = 120 ° C), since the maximum temperature at the time of polymerization can be relatively low, it is preferred to use a third monofunctional organic peroxide having a half-life temperature of 110 ° C or lower. Since a more transparent impact-resistant methacrylic resin cast molded article can be obtained, the 10-time half-life temperature of the first monofunctional organic peroxide (TJ and the second monofunctional organic peroxide) The difference in ίο-hour half-life temperature (T2) (ΛΤ12) is preferably 10 ° C or higher, and more preferably 13 ° C or higher, and may be 30 ° C or lower, and because transparency is obtained Better impact resistant methacrylic resin cast molded article, 10 - hour half-life temperature (T2) of the second monofunctional organic peroxide and ίο· hour of the third monofunctional organic peroxide The difference in half-life temperature (Τ3) (ΔΤ23) is preferably 10 ° C or higher, and more preferably 18 t or higher, and more preferably 35 t or lower. The first monofunctional of the resin composition of the present invention Base organic peroxide / second monofunctional organic peroxide content ratio (which is the content of the first monofunctional organic peroxide to the second monofunctional organic peroxide - 10 (8) 1285661 ratio) ranges from 3/7 weight to 7/3 weight, and is preferably from 4/6 by weight to 6/4 by weight, and the ratio of the total amount of the first and second monofunctional organic peroxides of the resin composition of the present invention to the third monofunctional organic peroxide ranges from 3/7 by weight to 7/3 by weight, and more preferably from 4/6 by weight to 6/4 by weight, the total amount of the first, second and third monofunctional organic peroxides in the total amount is from 〇. 〇 5 parts by weight to 0.5 parts by weight, based on 1 〇〇 by weight of the monomer comprising methyl methacrylate monomer. The first monofunctional organic peroxide, the second monofunctional group The organic peroxide and the third monofunctional organic peroxide may be used in a state of being diluted with a solvent, and the inert solvent may be appropriately selected depending on the kind of the monofunctional organic peroxide, and examples of the inert solvent include saturation. Aliphatic hydrocarbon solvents such as petroleum brain and mineral spirits, hydrocarbon solvents such as benzene and toluene, acetone, cumene, diphenylethane, ethyl acetate, etc. In addition to monomers, methacrylic resins, elastic particles, first Monofunctional organic peroxide, second monofunctional group In addition to the organic peroxide and the third monofunctional organic peroxide, the resin composition of the present invention may further contain additives such as an antioxidant, a UV absorber, a mold release agent, a dye, etc., depending on the desired impact-resistant methyl group. Application of Acrylic Resin Cast Molded Article 〇 By polymerizing the above-described resin composition, a methacrylic resin molded article having sufficient impact resistance, containing little residual monomer, and excellent transparency can be produced in the present invention. The polymerization method is not particularly limited, and examples thereof include bulk polymerization, pouring -11 - 1285661 (9) casting polymerization, etc., and casting polymerization in which polymerization is carried out in a polymerization element, which does not constitute a limitation of the scope of the present invention. When the element is polymerized, the polymer element to be used is not particularly limited, and any of the polymer elements generally used in the casting polymerization method can be used, for example, in the case where a plate-like methacrylic resin cast molded article is to be obtained, it can be used in parallel with each other. A batch-type element composed of two substrates arranged in series or a continuous element composed of two continuous strips parallel to each other. When a batch type component is used, a glass substrate or a metal substrate can be utilized as its substrate, the two substrates can be arranged as two walls separated from each other and as a component, and a soft sealing material which can serve as the remaining four walls of the component. The resin composition is polymerized in the element, that is, in a region surrounded by the two substrates and the soft sealing material, and the distance between the substrates i can be appropriately selected depending on the thickness of the desired plate-like molded article, and may be about 5 mm or more and 30 mm or less, the distance between the substrates can be adjusted by changing the thickness of the soft sealing material, and in addition, it can be adjusted by pressing the two substrates and compressing the soft sealing material. The polymerization of the resin composition in the polymeric element can be carried out by pouring the composition into the polymeric element and heating the resulting element, for example, by maintaining the temperature (eg, the temperature is 30 ° C or higher) at least 5 ° C lower than the first 10-hour half-life temperature of a monofunctional organic peroxide (TJ over 10 hours or longer, and then increasing the temperature to a temperature of at least 5 ° C above the 10-hour of the third monofunctional organic peroxide) The half-life temperature (T3) but lower than, for example, about 140 t, the polymerization temperature may be gradually or continuously increased, and it is preferred to gradually increase the temperature. When the temperature is gradually increased, the polymerization is preferably carried out by maintaining the temperature at least 5 -12-(10) 1285661. °C is lower than the 10-hour half-life temperature of the first monofunctional organic peroxide (TO is 10 hours or longer, and then the temperature is maintained from a temperature below about 5 ° C to above about 10 ° C The 10-hour half-life temperature of the first monofunctional organic peroxide at a temperature (TJ over 1 hour or longer, then the temperature is maintained from a temperature below about 10 °C to a temperature above about 1 (TC) Second monofunctional organic peroxidation The 10-hour half-life temperature (T2) is 1 hour or longer, and finally the temperature is increased to at least 5 ° C higher than the 10-hour half-life temperature (τ 3 ) of the third monofunctional organic peroxide, increasing the temperature In the present invention, hot water, hot air or steam may be used. In the present invention, the first monofunctional organic peroxide of the resin composition, the second monofunctional organic peroxide, and the third monofunctional organic The peroxide is decomposed by heating to generate a group which polymerizes the resin composition to form a molded article. After the polymerization is carried out in the polymerization member, the impact-resistant methacrylic resin cast molded article can be taken out by separating the polymerized member, The impact-resistant methacrylic resin cast molded article obtained in this manner has sufficient impact resistance and excellent transparency, and therefore, the molded article can be used for, for example, a sheet for providing an indoor partition panel, a soundproof panel for a road. , bulletproof board, etc. According to the present invention, it is possible to manufacture an impact resistant methacrylic resin having a small residual monomer, sufficient impact resistance and excellent transparency. Molded article. It is obvious that the invention can be modified in various ways, and such changes are considered to be within the spirit and scope of the invention, and all such modifications as understood by those skilled in the art are deemed to be in the following applications. In the scope of the patent. -13- (11) 1285661 The entire description of Japanese Patent Application No. 2002-227032, filed on Aug. 5, 2002, including the specification, the patent application, the The present invention is illustrated in more detail by the following examples which are not intended to limit the scope of the invention. The amount of residual monomers contained in the molded articles obtained in each example was measured by the following method: Samples were cut from each molded article. (〇. 1 g) and dissolved in 20 ml of dichloromethane, 15 μl of methyl isobutyl ketone (as an internal standard) was added to the obtained solution, and the monomer contained in the solution was quantitatively measured by gas chromatography. Ingredients. The molded article was kept at a temperature of 23 ° C in a thermostat for 1 hour, and the turbidity 値 of the molded article was measured in accordance with JIS K7 136. The Charpy impact strength of the molded article was measured in accordance with JIS K71 1 1 using the sample type 1. Example 1 Preparation of Resin Composition: Methyl methacrylate resin (13.5 parts by weight) of methyl methacrylate (77.5 parts by weight), 95% by weight of methyl methacrylate unit and 5% by weight of methyl acrylate unit copolymer; The elastic particles having a viscosity average molecular weight of about 1 10,000 and a three-layer structure (9 parts by weight; the particle size is 〇·3 μm) are mixed and stirred at 60 ° C for 2 hours, and after cooling, in the resulting mixture - 14 - (12) 1285661 adding a third butyl peroxypivalate (0.014 parts by weight; (T (10-hour half-life temperature) is 55 ° C) a solution dissolved in a saturated aliphatic hydrocarbon solvent (concentration is 70% by weight; 0.02 parts by weight), tert-butyl peroxy-2-ethylhexanoate (〇. 〇 2 parts by weight, purity is 97% by weight or more; about 0.0 2 parts by weight of pure components; T is 72 ° C), tert-butyl peroxy isopropyl carbonate (〇. 〇 3 weight component; T is 99 ° C) dissolved in a hydrocarbon solvent solution (concentration is 75% by weight; 0.04 parts by weight), UV Absorbent (0.01 parts by weight; trade name "Sumisorb 200"; sold by Sumitomo Chemical Co., Ltd. And a release agent (0.05 parts by weight; trade name "Sanseparer"; sold by Sanyo Chemical Industries, Ltd.), after stirring for another hour, the resulting mixture was degassed at 87 kPa (absolute pressure) for 30 minutes to obtain Resin composition. Polymerization: The resin composition obtained above is injected into a polymer element composed of two glass plates (30 cm x 30 cm, thickness 10 mm) and a sealing material composed of soft polyvinyl chloride. The resin composition in the polymerization element was heated and maintained at a temperature of 46 ° C for 16 hours, reheated to a temperature of 5 1 ° C at a temperature increase rate of 0.25 ° C / minute, and maintained at a temperature of 51 ° C for 4 hours. , reheating to a temperature of 60 ° C at a temperature increase rate of 0.45 ° C / min, maintaining at a temperature of 60 ° C for 3 hours, and then heating at a temperature increase rate of 0.5 ° C / min until the temperature is 70 ° C, kept at 70 ° C for 3 hours, then reheated to a temperature of 85 ° C at a temperature increase rate of 5 5 ° C / min, at a temperature of 85 ° C for 3 hours, and finally at 〇.5 °C / min - 15 - (13) Temperature increase rate of 1285661 Reheat until the temperature is 12 (TC, and maintain at a temperature of 120 ° C for 2 hours, and maintain the temperature range from 120 ° C to 125 ° C for 3 hours, using a hot air circulation type heating furnace, heating, and then making The obtained composition was cooled, and then the polymerization element was opened to obtain an impact-resistant methacrylic resin cast molded article (sheet shape, size: 30 cm X 30 cm X 10 mm (thickness)) as a result of polymerization of the resin composition. Evaluation: The sample was cut out from the obtained molded article, and the sample was used to measure the residual monomer content, turbidity Char and Charpy impact strength of the molded article, and as a result, the residual monomer content was 〇·9 wt%, and the turbidity 値 was The 0.7% and Charpy impact strength is 36 kJ/m 2 and the results are shown in Table i. Example 2 A plate-like impact-resistant methacrylic resin was obtained in the same manner as in Example 1 except that the methyl methacrylate, the methacrylic resin, and the three-layered elastic particles were mixed at a temperature of 60 ° C for 13 hours. The molded articles were cast, and the evaluation results of the obtained molded articles are shown in Table 1. EXAMPLES Comparative 1 In addition to the use of 0.08 by weight of 2,2-azobisisobutyronitrile (an azo compound; T is 65 ° C) instead of the third butyl peroxypivalate solution, peroxy-2- A plate-like impact-resistant A-16-(14) 1285661-based acrylic resin cast molded article was obtained in the same manner as in Example 1 except that a solution of the third butyl hexanoate solution and a solution of the third butyl peroxy propylene carbonate was obtained. The evaluation results of the obtained molded articles are shown in Table 1. EXAMPLE COMPARISON 2 In addition to the use of 0. 0 8 by weight of component (about 〇. 8 parts by weight of pure component) of peroxy-2-ethylhexanoic acid tert-butyl ester (purity is 97% by weight or more) A plate-like resistance was obtained in the same manner as in Example 1 except that a solution of a third butyl peroxypivalate solution, a solution of a third butyl peroxy-2-ethylhexanoate, and a solution of a third butyl peroxy isopropyl carbonate. Impact molded methacrylic resin cast molded articles, and the evaluation results of the obtained molded articles are shown in Table 1. Example comparison 3 In addition to using 2,2'-azobis(2,4-dimethylvaleronitrile) (an azo compound; T is 51t) of the weight component of 〇·〇2 instead of peroxypivalic acid A plate-like impact-resistant methacrylic resin cast molded article was obtained in the same manner as in Example 1 except for the butyl ester solution, and the evaluation results of the obtained molded article are shown in Table 1. EXAMPLES Comparative 4 In addition to the use of 0.23 by weight component (about 0.115 parts by weight of the pure component) of peroxytrimethyl adipate di-t-butyl ester (a polyfunctional organic peroxide) dissolved in isoparaffins The solution (concentration is 50% by weight) is the same as the solution of the third butyl peroxypivalate solution, the third butyl peroxy-2-ethylhexanoate solution and the third butyl peroxy isopropyl carbonate solution. The plate-like impact-resistant methacrylic resin cast molded article was obtained by the method of -17-(15) 1285661 of Example 1, and the evaluation results of the obtained molded article are shown in Table 1.
-18- (16) 1285661 [表1] 1 0-小時 半衰期 溫度 實例1 實例2 實例 比較1 實例 比較2 實例 比較3 實例 比較4 過氧特戊 酸第三丁 酯 5 5〇C 0.014 0.014 - - - 過氧-2-乙 基己酸第 三丁酯 72〇C 0.02 0.02 麵 0.08 0.02 - 過氧異丙 基碳酸第 三丁酯 99〇F 0.03 0.03 議 0.03 师 過氧三甲基己二酸 二第三丁酯 - - - - - 0.115 2,2-偶氮雙 異丁腈 65〇C - - 0.08 - - 2,2’-偶氮 雙（2,4-二 甲基戊腈） 5 1°C - - 義 0.02 _ 殘留的單體含量（％) 0.9 0.8 1.5 2.7 0.9 1.2 濁度値（％) 0.7 0.9 1.4 5.2 3.7 0.5 Charpy衝擊強度 (千焦耳/平方米） 36 37 48 35 24 45 -19--18- (16) 1285661 [Table 1] 1 0-hour half-life temperature Example 1 Example 2 Example comparison 1 Example comparison 2 Example comparison 3 Example comparison 4 Peroxypivalic acid tert-butyl ester 5 5〇C 0.014 0.014 - - - peroxy-2-ethylhexanoic acid tert-butyl ester 72 〇 C 0.02 0.02 surface 0.08 0.02 - peroxyisopropyl phthalic acid tert-butyl ester 99 〇 F 0.03 0.03 Discussion 0.03 Division of peroxytrimethyl adipate II Third butyl ester - - - - - 0.115 2,2-azobisisobutyronitrile 65〇C - - 0.08 - - 2,2'-azobis(2,4-dimethylvaleronitrile) 5 1° C - - 0.02 _ Residual monomer content (%) 0.9 0.8 1.5 2.7 0.9 1.2 Turbidity 値 (%) 0.7 0.9 1.4 5.2 3.7 0.5 Charpy impact strength (kJ/m 2 ) 36 37 48 35 24 45 -19 -