201130907 六、發明說明： 【發明所屬之技術領域】 本發明係關於具有經改良的光學及表面性質之以丙嫌 酸系爲底質的摻合物聚合物。 【先前技術】 聚（甲基丙嫌酸甲醋）（PMMA )習知在表面硬度、 光澤度及耐風化性方面具有優點。藉由添加聚丁二嫌改質 劑至PMMA’可以增加耐衝擊性。pMMA及聚丁二燃改質 劑之摻合物已經被製備出，且在其綜合性質方面顯出優點 。然而’這些產物顯出一些由於各成份（諸如得自 EVONIK之Acrylite XT®聚合物或CYROLITE®)間之不相 容性所引起的濁度。對於電子外殼應用而言，有使用透明 顔色之趨勢。 例如PMMA、SAN (苯乙烯及丙烯腈之共聚物）及 MBS (甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物）之組合的 耐衝擊性聚合物產物是已知的。一實例是得自BASF之 Terlux®。 德國專利DE2024940揭示一種組成物，其含有： 1) 10-90重量份之以下物質的共聚物： 70-90重量％之苯乙烯 10-3 0重量％之順丁烯二酸酐 2) 10-90重量份之以下物質的共聚物： 60-100重量❶/〇之甲基丙烯酸甲醋 201130907 30-0重量％之苯乙烯 10_0重量％之丙烯酸C1-C4烷酯 3 ) 0-50重量份之以下物質的共聚物： 60-90重量％之苯乙烯 40-10重量％之丙烯腈。 另外，W098/28365揭示一種也具有良好透明性及低 濁度之由以下共聚物組成之聚合物組成物： a. 5-95重量％之以下物質的共聚物： 90-99.8重量％之甲基丙烯酸甲酯 10-0.2重量％之丙烯酸乙酯及/或丙烯酸甲酯 b. 95-5重量％之以下物質的共聚物： 72-80重量％之苯乙烯 20-2 8重量％之順丁烯二酸酐。 US2 002/0 1 67 1 1 2揭示一種具有改良的光學性質及低溫 耐衝擊性之以丙烯酸系爲底質之共聚物模製及擠出組成物 ，其包含： A ) 55-85重量％之以丙烯酸系爲底質之多聚物，其包 含： 8-12重量％之丙烯腈、3-8重量％之丙烯酸丁酯、 3-5重量％之丙烯酸乙酯、3-8重量％之丙烯酸甲酯 、65-80重量％之甲基丙烯酸甲酯、及15_30重量。/。 之苯乙烯， B) 15-4 5重量％之藉由自由基方法所聚合的甲基丙烯 酸甲酯-丁二烯-苯乙烯（MBS)共聚物改質劑。 201130907 含有丙烯腈之產物是有毒的，且在W098/2 8365中揭 示的產物缺乏適合之表面硬度。 結合固有高光澤表面與高耐刮性及高耐衝擊性之無毒 透明產物特別對於食品包裝及玩具工業而言總是需要的。 【發明內容】 本發明之目的是要提供一種具有高透明度、高表面硬 度、高光澤度及良好耐衝擊性且不含丙烯腈之聚合物組成 物。 此目的藉由提供一種包含以下成份之聚合物組成物達 成：以該聚合物組成物之總重量計， a) 1-90重量％之聚摻物A，其包含聚丁二烯及以甲基 丙烯酸甲酯爲底質之聚合物； ‘ b) 1-90重量％之聚合物B，其爲以甲基丙烯酸甲酯爲 底質之聚合物； c) 1-20重量％之共聚物C，其包含18-35重量％之順丁 烯二酸酐及65-82重量％之苯乙烯， 其中在聚摻物A中之以甲基丙烯酸甲酯爲底質之聚合 物及作爲聚合物B之以甲基丙烯酸甲酯爲底質之聚合物可 以是相同或不同的，分別獨立地爲一種聚合物，其包含以 該以甲基丙烯酸甲酯爲底質之聚合物重量計，50-1〇〇重量 % (較佳65- 1 00重量％ )之甲基丙烯酸甲酯，及〇-5〇重量％ (較佳0-35重量％ )之聚合形式的共聚丙烯酸酯類（ coacrylates) ° 201130907 本發明也提供一種製備本發明之聚合物組成物的方法 ’其中具有不同成份比例之聚合物較佳利用單螺桿或雙螺 桿擠出機，在150-300°C (較佳在190-25(TC )下被熔化及 混煉。 [實施本發明之特定模式] 在本發明中所要之聚合物組成物具有依照ASTM D 1 003所測定之至多1 〇% (較佳至多8 %，且最佳至多5 % ) 之濁度’依照ASTM D3 3 6：3所測定之HB (較佳1H，且最佳 2 Η )的鉛筆硬度，及依照I s 〇 1 7 9在2 3 °C下所測定之> 2 0千 焦耳/平方米（較佳是>40千焦耳/平方米，且最佳>60千 焦耳/平方米）之耐衝擊性。 較佳之聚合物組成物包含以下成份：以該聚合物組成 物總重量計， a) 10-85重量％之聚摻物A，其包含聚丁二烯及以甲基 丙烯酸甲酯爲底質之聚合物； b) 10-85重量％之聚合物B’其爲以甲基丙烯酸甲酯爲 底質之聚合物； c) 5-15重量％之共聚物C，其包含18-35重量％之順丁 烯二酸酐及65 -82重量％之苯乙烯。 在本發明中’在聚摻物A中之“以甲基丙烯酸甲酯爲底 質之聚合物”可以是與聚合物B相同或不同，二者分別獨立 地是一種聚合物’其包含以該以甲基丙烯酸甲酯爲底質之 聚合物重量計’ 50-100重量％ (較佳65-100重量％ )之甲基 201130907 丙烯酸甲酯，及0-5 0重量％ (較佳0-3 5重量％ )之聚合形式 的共聚丙烯酸酯類。 可在以甲基丙烯酸甲酯爲底質之聚合物中被使用的共 聚丙烯酸酯類是廣泛已知的。彼特別包括衍生自飽和醇類 之（甲基）丙烯酸酯類，諸如丙烯酸甲酯、（甲基）丙烯 酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸正丁酯、 (甲基）丙烯酸第三丁酯、（甲基）丙烯酸戊酯、及（甲 基）丙烯酸2-乙基己酯；衍生自不飽和醇類之（甲基）丙 烯酸酯類，諸如（甲基）丙烯酸油酯 '(甲基）丙烯酸2-丙炔酯、（甲基）丙烯酸烯丙酯、（甲基）丙烯酸乙烯酯 :(甲基）丙烯酸芳酯，諸如（甲基）丙烯酸苄酯、或（ 甲基）丙烯酸苯酯，在每一情況中芳基可能未經取代或經 取代最多4次；（甲基）丙烯酸環烷酯，諸如（甲基）丙 烯酸3-乙烯基環己酯、（甲基）丙烯酸冰片酯：（甲基） 丙烯酸羥烷酯，諸如（甲基）丙烯酸3-羥丙酯、（甲基） 丙烯酸3,4-二羥丁酯、（甲基）丙烯酸2-羥乙酯、（甲基 )丙烯酸2-羥丙酯；二醇二（甲基）丙烯酸酯，諸如1，4-丁二醇（甲基）丙烯酸酯；醚醇類之（甲基）丙烯酸酯類 ’諸如（甲基）丙烯酸四氫糠酯、（甲基）丙烯酸乙烯氧 基乙氧基乙酯；（甲基）丙烯酸之醯胺類及腈類，諸如N-(3-二甲胺基丙基）（甲基）丙烯醯胺、N-(二乙基膦基 )(甲基）丙烯醯胺、1-甲基丙烯醯基醯胺基-2·甲基- 2-丙醇；含硫之甲基丙烯酸酯類，諸如（甲基）丙烯酸乙亞 磺醯基乙酯、（甲基）丙烯酸4-硫氰酸基丁酯、（甲基） -9 - 201130907 丙烯酸乙磺醯乙酯' (甲基）丙烯酸硫基氰酸基甲酯、（ 甲基）丙烯酸甲亞磺醯甲酯、雙（甲基）丙烯醯氧乙基） 硫醚：多官能性（甲基）丙烯酸酯類，諸如三羥甲基丙烷 三（甲基）丙烯酸酯。 在這些中，丙烯酸甲酯及（甲基）丙烯酸乙酯是較佳 的。 除了上列之共聚丙烯酸酯類之外，在該以甲基丙烯酸 甲酯爲底質之聚合物中所含之作爲共聚丙烯酸酯類之另外 的不飽和共單體是可與甲基丙烯酸甲酯及與上述（甲基） 丙烯酸酯類共聚合者。此種單體特別包括1-烯類，諸如己-卜烯、庚-1-烯：支鏈型烯類，諸如乙烯基環己烷、3,3-二 甲基-1-丙烯、3-甲基-1-二異丁烯、4-甲基戊-1-烯；乙烯 酯類，諸如乙酸乙烯酯；苯乙烯，在側鏈中具有烷基取代 基之經取代的苯乙烯，諸如[α ]-甲基苯乙烯及[α ]-乙基 苯乙烯；在環上具有烷基取代基之經取代的苯乙烯，諸如 乙烯基甲苯及對-甲基苯乙烯；鹵化苯乙烯類，諸如單氯 苯乙烯類、二氯苯乙烯類、三溴苯乙烯類及四溴苯乙烯類 :雜環乙烯基化合物，諸如2-乙烯基吡啶、3-乙烯基吡啶 、2-甲基-5-乙烯基吡啶、3-乙基-4-乙烯基吡啶、2,3-二甲 基-5-乙烯基吡啶、乙烯基嘧啶、乙烯基哌啶、9-乙烯基咔 唑、3-乙烯基咔唑、4-乙烯基咔唑、卜乙烯基咪唑、2-甲 基-1-乙烯基咪唑、Ν-乙烯基吡咯烷酮、2-乙烯基吡咯烷酮 、Ν -乙烯基吡咯啶、3 -乙烯基吡咯啶、Ν -乙烯基己內醯胺 、Ν-乙烯基丁內醯胺、乙烯基氧雜環茂烷、乙烯基呋喃、 -10- 201130907 乙烯基噻吩、乙烯基硫雜環茂烷（vinyl thiol ane )、乙烯 基噻唑類及氫化的乙烯基噻唑類、乙烯基噁唑類及氫化的 乙烯基噁唑類；乙烯基及異戊二烯基（is〇preny丨）醚；及 二烯類，諸如二乙烯苯。 通常，這些共聚單體用量以該以甲基丙烯酸甲酯爲底 質之聚合物重量計是〇重量％至50重量％ ’較佳是〇重量％至 3 0重量％，該等化合物可能單獨被使用或以混合物形式被 使用。 該聚摻物A包含以聚摻物A重量計1-20重量％ ’較佳地 10-20重量％之聚丁二烯，及80-99重量％’較佳地80-90重 量％之以甲基丙烯酸甲酯爲底質之聚合物。該以甲基丙烯 酸甲酯爲底質之聚合物包含，以該以甲基丙烯酸甲酯爲底 質之聚合物重量計，5 0 - 1 0 0重量％，較佳地6 5 - 1 0 0重量％之 甲基丙烯酸甲酯，及〇-5〇重量％，較佳地〇-3 5重量％之聚合 形式的共聚丙烯酸酯類。 特別地，在本發明中，該以甲基丙烯酸甲酯爲底質之 聚合物包含，以該以甲基丙烯酸甲酯爲底質之聚合物重量 計，65-95重量％之MMA、5-25重量％之苯乙烯、〇-1〇重量 %之丙烯酸乙酯。 該聚摻物A或聚丁二烯與以甲基丙烯酸甲酯爲底質之 聚合物的摻合物（簡稱爲B-PMMA )可選自EV0NIK之 Acrylite XT® 聚合物、C YRO VU® 或 C YR0LITE®，Kaneka 之 KANE ACE®，及 Rohm&Haas 之 BTE 731®。 較佳地，該聚合物B之用量以該聚合物組成物總重量 -11 - 201130907 計是10-40重量％，更佳地20_30重量％。聚合物B之重量平 均分子量較佳是40,0〇〇克/莫耳至4〇〇〇〇〇克/莫耳；更佳 地是80,000克/莫耳至20〇,〇〇〇克/莫耳；且最佳地是 120,000至1 60,000克/莫耳。該聚合物b可選自EVONIK之 標準PLEXGLAS®模製化合物系列，諸如PLEXGLAS@ 6N 、PLEXGLAS® 8N、及其他。 較佳地’該共聚物C之用量以該聚合物組成物總重量 計是3-9重量％，更佳是5_7重量％。共聚物c之重量平均分 子量較佳是1 0,000至5〇〇,〇〇〇克/莫耳；更佳是79 〇〇〇至 175,000克/莫耳。該共聚物c (其爲苯乙烯及順丁烯二酸 酐之共聚物，簡稱爲SMA )可選自P〇lySCOpe P〇iymers B.V. 6161 RA Geleen，Netherland之 XIRAN®。 聚合物組成物除了含有聚摻物A、聚合物B及共聚物C 之外’就已知之方式也含有一般添加劑、及/或輔劑，其 實例是熱安定劑、UV安定劑、UV吸收劑、抗氧化劑、及 /或色素、顏料或有機染料。所存在之一般添加劑及/或 輔劑的量’以聚合物組成物總重量計，較佳不多於10重量 ’特佳是不多於5重量％，特別是不多於2重量％。聚合物 組成物在合適情況下也可完全不包含添加劑及/或輔劑。 若添加劑具有高度酸性，則可另外獲得良好結果。此 確實阻止聚合物組成物中氣泡的形成，此氣泡的形成可能 是由於SMA之分解》 例如硼酸極適合作爲熱安定劑。 由也具有高度酸性之UV安定劑，亦可另外獲得良好 -12- 201130907 結果，該UV安定劑較佳具有最高8之pKa，更佳最高7之 pKa，甚至更佳最高6之pKa，該pKa已在23°C下於50重量％ 之異丙醇及5 0重量％之水的混合物中測定。彼之實例是2 _ (2 ’ -羥基-5，-甲基苯基）-苯並三唑或位阻胺光安定劑（ HALS)化合物，諸如8 -乙醯基-3-十二院基_7,7,9,9 -四甲 基-1，3,8-三氮雜螺（4,5)癸烷-2,4-二酮。 較佳地，U V安定劑用量，以該聚合物組成物總重量 計，是0.005-2.0重量％。 若使用具有高度酸性之UV安定劑（例如上述者之一 )，則可能使用具有較低酸性之第二UV安定劑，只要該 第二UV安定劑存在濃度低於該第一安定劑的濃度。 例如可能結合使用〇.4-1.5重量％之8-乙醯基-3-十二烷 基-7,7,9,9·四甲基-1，3,8-三氮雜螺（4,5)癸烷-2,4-二酮與 0.1-0.5重量％之癸二酸二（2,2,6,6-四甲基-4-哌啶基）酯 〇 苯並三唑衍生物也是合適的UV安定劑，其係選自由2-(2 ’ -羥基-5 ’·甲基苯基）-苯並三唑、三嗪衍生物（例如2 -(4,6-二苯基-1，3,5-三嗪-2-基）-5-己氧基）酚）、位阻胺 光安定劑及其組合所組成之群中。這些苯並三唑衍生物可 由Ciba獲得，名爲TINUVIN®。 對於在本發明中之經聚丁二烯改質之聚合物，使用例 如由Ciba獲得之名爲IRGANOX® 1076的3- ( 3,5-二-第三丁 基-4-羥基苯基）-丙酸十八烷酯抗的氧化劑是較佳的。 對於注射成形方法而言，潤滑劑或脫模劑是特別重要 -13- 201130907 的’且可以降低或完全防止聚合物組成物可能黏合至注射 成形模的程度。另外’很多模製物（特別是注射成形部分 )是不透明的，但具有顏色，因此包含色素、顏料、或有 機染料作爲添加劑。戶外使用之部分通常包含UV安定劑 、UV吸收劑、或抗氧化劑以提供另外之風化防護作用。 潤滑劑因此可作爲輔劑，其實例是選自碳原子數目少 於20 (較佳16至18)之飽和脂肪酸類或選自碳原子數目少 於20 (較佳16至18)之飽和脂肪醇類。存在之定量比例較 佳是極小的，以該聚合物組成物計，最多〇 ·2 5重量％，例 如0.0 5至0 · 2重量％ » 適合之潤滑劑實例是硬脂酸、棕櫚酸、由硬脂酸與棕 櫚酸組成之工業混合物。其他合適的潤滑劑的實例是正十 六醇、正十八醇、及由正十六醇與正十八醇組成之工業混 合物。硬脂醇是特佳之潤滑劑或脫模劑。 在製造本發明聚合物組成物時，較佳以例如聚合物珠 粒或顆粒形式之固體開始，使用緩慢移動之混合裝置，例 如滾筒型混合機、自由下降之混合機、螺旋混合輪、或雙 槽犁型混合機。緩慢移動之混合機產生機械混合卻不消除 相邊界（參見 ’Ullmans Encyklopaedie der technischen Chemie’，4th Ed.，Verlag Chemie Vol. 2，pp.282-3 1 1 )。 這之後是熱塑處理，其是藉由在適合溫度下使用可加熱混 合裝置，在捏合混合機或較佳地在擠出機（例如單螺桿或 雙螺桿或多螺桿擠出機或具有震盪螺桿及切變棒之擠出機 ’例如 Buss Corporation 之 Cokneader Buss®)中使熔體均 14- 201130907 勻混合。然後，乾燥的顆粒被注射成形成爲所述之測試所 需的板狀或其他樣品。 【實施方式】 混煉的成分及其代號摘述於下文。 成份 材料 聚摻物A B-PMMA-1 B-PMMA-2 聚合物B PMMA- 1 PMMA-2 共聚物C SMA-1 SMA-2 B-PMMA-1是一種含有，以聚摻物重量計，15-16重量 %之聚丁二烯及84-85重量％之以甲基丙烯酸甲酯爲底質之 聚合物的聚摻物，其中該以甲基丙烯酸甲酯爲底質之聚合 物包含，以該以甲基丙烯酸甲酯爲底質之聚合物重量計’ 65-70重量％之MMA、20-25重量％之苯乙烯、5-10重量％之 丙烯酸乙酯。B-PMMA-1由EVONIK提供。 B-PMMA-2是一種含有，以聚摻物重量計，20重量％ 之聚丁二烯及80重量％之以甲基丙烯酸甲酯爲底質之聚合 物的聚摻物，其中該以甲基丙烯酸甲酯爲底質之聚合物包 含，以該以甲基丙烯酸甲酯爲底質之聚合物重量計’約94 重量％之MMA、6重量％之苯乙稀。B-PMMA-2由Kaneka提 供。 -15- 201130907 PMMA-l是一種含有90-92重量。/〇之MMA及8-10重量。/〇 之丙烯酸甲酯的聚合物。PMMA-1由EVONIK提供。 PMMA-2是一種含有98-99重量％之MMA及1-2重量％之 丙烯酸甲酯的聚合物。PMMA-2由EVONIK提供。 SMA-1是一種含有26重量％之順丁烯二酸酐及74重量 %之苯乙烯的共聚物，其依照ISO 1628具有0.335分公升/ 克之黏度。SMA-1係由Polyscope提供。 SMA-2是一種含有23重量％之順丁烯二酸酐及77重量 %之苯乙烯的共聚物，其具有110,〇〇〇克/莫耳之分子量 Mw。SMA-2係由 Polyscope提供》 在本發明中，聚合物之重量平均分子量係依照GPC方 法用此技藝中已知的方式測定。 實例a ) 藉由直立式批次混合機（Type SVM-25;得自Shini Machinery)將 70重量％之 B-PMMA-1、24重量 ％2PMMA-1 及6重量％之SMA-1混合3分鐘。 藉由具有30毫米之螺桿直徑的單螺桿擠出機（Type SSE30;得自Ruiya)，以24(TC之熔融溫度及50 rpm之轉 動速度將該混合物混煉。由模具擠出之條狀物經過水槽、 冷卻且九化。 粒子利用乾燥劑—乾燥器MOTAN在8(TC下乾燥2小時 ，然後在注射成形機SUMITOMO SED50中24(TC之熔融溫 度下被注射成形成爲80x1 0x4毫米樣品以供衝擊測試，及 -16- 201130907 成爲3毫米厚之板以供測試光學性質及鉛筆硬度。 鉛筆硬度依照ASTM D3 3 63測試。 該板具有9 0 %之板透射率（依照a S T M D 1 0 0 3 )，5 % 之濁度及87.0千焦耳/平方米之Charpy衝擊強度（依照 ISO 179)。該板如水晶般完全透明。 產物之濁度値依照ASTM D1003藉由Spectrometer GRETAG MCBETH COLOREYE 7000 測量。依照 ASTM D 1 003，具有大於30%濁度値之材料被認爲是漫射的。 產物不含有毒物質及可能引起癌症之物質例如丙烯腈 〇 產物結合低的濁度及高衝擊程度與優越之1H鉛筆硬度 的表面硬度。 比較例1 具有70重量％之B-PMMA-1及30重量％之PMMA-1的混 合物利用直立式批次混合機（Type SVM-25，得自Shini Machinery)混合3分鐘。 之後，混合物如實例a )中所述的被混煉及注射成形 〇 藉由此比較例所製備之板是極渾濁的且看似半透明。 實例bl-3 ) 具有 15/40/68 重量 ％之 PMMA-1、80/50/15 重量 ％之 B-PMMA-1及5/10/17重量％之SMA-1的混合物分別利用直立 -17- 201130907 式批次混合機（Type SVM-25，得自Shini Machinery)混 合3分鐘。 之後，混合物如實例a )中所述的被混煉及注射成形 〇 實例a )、比較例1及實例b〗-3 )之測試結果列於以下 表1中。 表1實例a)、bl-3)及比較例1的測試結果 成份 單位 實例a) 比較例1 實例bl) 實例b2) 實例b3) B-PMMA.1 重量％ 70 70 80 50 15 PMMA-1 重量％ 24 30 15 40 68 SMA-1 重量％ 6 0 5 10 17 性質 透射率 (3毫米,A2) % 90 82 90.2 90 91 濁度(3毫米） % 5 46 4 4 4 鉛筆硬度 1H 1H 2H 2H 3H Charpy 衝擊強度 kJ/m2 87.0 89.0 68 60 40 比較例2 具有67重量％之PMMA-1及33重量％之B-PMMA-2的混 合物利用直立式批次混合機（Type SVM-25，得自Shini Machinery)混合3分鐘。 之後，混合物如實例a )中所述的被混煉及注射成形 實例c ) -18- 201130907 具有50重量％之PMMA-l、33重量％2Β-ρΜΜΑ_2及17 重量％之SMA-2的混合物利用直立式批次混合機（ SVM-25，得自 Shini Machinery)混合 3 分鐘。 之後，混合物如實例a )中所述的被混煉及注射成形 〇 產物不含有毒物質及可能引起癌症之物質’諸如丙烯 腈。 實例d ) 具有74.5重量％之PMMA-2、1 7重量％之B - Ρ Μ Μ A - 2及 8.5重量％之SMA-2的混合物利用直立式批次混合機（Type SVM-25，得自 Shini Machinery )混合 3 分鐘。 之後，混合物如實例a )中所述的被混煉及注射成形 〇 產物不含有毒物質及可能引起癌症之物質，諸如丙烯 腈0 -19 - 201130907 表2實例c)、d)及比較例2的測試結果201130907 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a blend polymer having a modified acrylic and surface properties based on a propylene sulphate. [Prior Art] Poly(methyl methacrylate) (PMMA) is known to have advantages in surface hardness, gloss, and weathering resistance. The impact resistance can be increased by adding a polybutylene sensitizer to PMMA'. Blends of pMMA and polybutadiene fuel reforming agents have been prepared and have advantages in terms of their overall properties. However, these products show some turbidity due to incompatibility between ingredients such as Acrylite XT® polymer from EVONIK or CYROLITE®. For electronic housing applications, there is a tendency to use transparent colors. Impact-resistant polymer products such as PMMA, SAN (copolymer of styrene and acrylonitrile) and MBS (methyl methacrylate-butadiene-styrene copolymer) are known. An example is Terlux® from BASF. German Patent DE 2024940 discloses a composition comprising: 1) a copolymer of 10-90 parts by weight or less: 70-90% by weight of styrene 10-3 0% by weight of maleic anhydride 2) 10-90 Copolymers of the following parts by weight: 60-100% by weight of yttrium methacrylate methacrylate 201130907 30-0% by weight of styrene 10_0% by weight of C1-C4 alkyl acrylate 3) 0-50 parts by weight or less Copolymer of the substance: 60-90% by weight of styrene 40-10% by weight of acrylonitrile. In addition, W098/28365 discloses a polymer composition consisting of the following copolymers which also has good transparency and low haze: a. Copolymer of 5-95% by weight or less: 90-99.8% by weight of methyl group Methyl acrylate 10-0.2% by weight of ethyl acrylate and/or methyl acrylate b. 95-5 wt% of copolymer of the following: 72-80% by weight of styrene 20-2 8% by weight of cis-butene Diacid anhydride. US 2 002/0 1 67 1 1 2 discloses an acrylic substrate-based copolymer molding and extrusion composition having improved optical properties and low temperature impact resistance, comprising: A) 55-85% by weight An acrylic substrate-based polymer comprising: 8-12% by weight of acrylonitrile, 3-8% by weight of butyl acrylate, 3-55% by weight of ethyl acrylate, and 3% by weight of acrylic acid Methyl ester, 65-80% by weight of methyl methacrylate, and 15-30 weight. /. Styrene, B) 15-4 5% by weight of a methyl methacrylate-butadiene-styrene (MBS) copolymer modifier polymerized by a free radical process. 201130907 The product containing acrylonitrile is toxic and the product disclosed in W098/2 8365 lacks a suitable surface hardness. Non-toxic, transparent products that combine an inherently high gloss surface with high scratch resistance and high impact resistance are especially desirable for the food packaging and toy industries. SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer composition having high transparency, high surface hardness, high gloss, and good impact resistance without acrylonitrile. This object is achieved by providing a polymer composition comprising: a) from 1 to 90% by weight, based on the total weight of the polymer composition, of polyaddition A comprising polybutadiene and methyl group a polymer of methyl acrylate as a substrate; 'b) 1-90% by weight of polymer B, which is a polymer based on methyl methacrylate; c) 1-20% by weight of copolymer C, It comprises 18-35 wt% maleic anhydride and 65-82 wt% styrene, wherein the methyl methacrylate-based polymer in the poly blend A and the polymer B The methyl methacrylate-based polymers may be the same or different, each independently being a polymer comprising 50-1 Å based on the weight of the methyl methacrylate-based polymer. % by weight (preferably 65-100% by weight) of methyl methacrylate, and 〇-5 〇 by weight (preferably 0-35 wt%) of a polymerized form of coacrylates ° 201130907 There is also provided a method of preparing a polymer composition of the present invention, wherein the composition has a different ratio of components Preferably, the material is melted and kneaded at 150-300 ° C (preferably at 190-25 (TC)) using a single-screw or twin-screw extruder. [Specific mode for carrying out the invention] The polymer composition has a turbidity of at most 1% (preferably up to 8%, and optimally up to 5%) as determined according to ASTM D 1 003 'HB as determined according to ASTM D3 3 6:3 (preferably 1H) And the pencil hardness of the best 2 Η) and > 20 kJ/m 2 (preferably > 40 kJ/m 2 ) measured according to I s 〇 179 at 2 3 °C. And the best impact resistance of 60 kJ/m2. The preferred polymer composition comprises the following components: a) 10-85% by weight of the polyabsorbent A, based on the total weight of the polymer composition, It comprises polybutadiene and a polymer based on methyl methacrylate; b) 10-85% by weight of polymer B' which is a polymer based on methyl methacrylate; c) 5 -15% by weight of copolymer C comprising 18-35 wt% maleic anhydride and 65-82 wt% styrene. In the present invention, 'the methyl methacrylate-based polymer' in the poly-blend A may be the same as or different from the polymer B, which are each independently a polymer' Methyl 201130907 methyl acrylate of 50-100% by weight (preferably 65-100% by weight) based on the weight of the methyl methacrylate-based polymer, and 0-50% by weight (preferably 0-3) 5 wt%) of a polymeric form of a copolyacrylate. Copolyacrylates which can be used in polymers based on methyl methacrylate are widely known. In particular, it includes (meth) acrylates derived from saturated alcohols such as methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, (methyl) ) tert-butyl acrylate, amyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; (meth) acrylates derived from unsaturated alcohols, such as (meth) acrylate oil Ester '2-propynyl (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate: aryl (meth) acrylate, such as benzyl (meth) acrylate, or (A Phenyl acrylate, in each case aryl may be unsubstituted or substituted up to 4 times; cycloalkyl (meth) acrylate, such as 3-vinylcyclohexyl (meth) acrylate, (methyl) ) borneol acrylate: hydroxyalkyl (meth) acrylate, such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth)acrylate; diol di(meth)acrylate, such as 1, 4-butanediol (meth) acrylate; (meth) acrylates of ether alcohols such as tetrahydrofurfuryl (meth) acrylate, vinyl ethoxy ethoxyethyl (meth) acrylate; Amidoximes and nitriles of methyl)acrylic acid, such as N-(3-dimethylaminopropyl)(meth)acrylamide, N-(diethylphosphino)(meth)acrylamide, 1-methylpropenyl decylamino-2-methyl-2-propanol; sulfur-containing methacrylates such as ethanesulfinyl (meth) acrylate, (meth) acrylate 4 - butyl thiocyanate, (methyl) -9 - 201130907 Ethyl sulfonate ethyl acrylate 'thiocyanyl methyl (meth) acrylate, methyl sulfinate methyl (meth) acrylate, double ( Methyl) propylene oxime oxyethyl) thioether: a polyfunctional (meth) acrylate such as trimethylolpropane tri(meth) acrylate. Among these, methyl acrylate and ethyl (meth) acrylate are preferred. In addition to the copolyacrylates listed above, the additional unsaturated comon as a copolyacrylate in the methyl methacrylate-based polymer is compatible with methyl methacrylate. And those copolymerized with the above (meth) acrylates. Such monomers include, in particular, 1-olefins such as hex-epene, hept-1-ene: branched olefins such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3- Methyl-1-diisobutylene, 4-methylpent-1-ene; vinyl esters such as vinyl acetate; styrene, substituted styrene having an alkyl substituent in the side chain, such as [α] -methylstyrene and [α ]-ethylstyrene; substituted styrenes having an alkyl substituent on the ring, such as vinyl toluene and p-methylstyrene; halogenated styrenes, such as monochloro Styrene, dichlorostyrene, tribromostyrene and tetrabromostyrene: heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinyl Pyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, vinyl imidazole, 2-methyl-1-vinylimidazole, anthraquinone-vinylpyrrolidone, 2-vinylpyrrolidone, anthracene-vinylpyrrolidine, 3-vinylpyrrolidine, anthracene -vinyl Indoleamine, fluorene-vinyl butyrolactam, vinyl oxacyclohexane, vinyl furan, -10- 201130907 vinyl thiophene, vinyl thiol ane, vinyl thiazole And hydrogenated vinyl thiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles; vinyl and isoprene based ethers; and dienes such as divinylbenzene. Usually, these comonomers are used in an amount of from 5% by weight to 50% by weight, based on the weight of the polymer based on methyl methacrylate, preferably from 3% by weight to 30% by weight, and the compounds may be individually Used or in the form of a mixture. The polyaddition A comprises from 1 to 20% by weight, preferably from 10 to 20% by weight, of polybutadiene, and from 80 to 99% by weight, preferably from 80 to 90% by weight, based on the weight of the polyabsorbent A. Methyl methacrylate is a substrate polymer. The methyl methacrylate-based polymer comprises, based on the weight of the methyl methacrylate-based polymer, from 50 to 100% by weight, preferably from 6 5 to 1 0 0 % by weight of methyl methacrylate, and 〇-5 〇 by weight, preferably 〇-3 5% by weight of the polymerized form of the copolyacrylate. Specifically, in the present invention, the methyl methacrylate-based polymer comprises, based on the weight of the methyl methacrylate-based polymer, 65-95% by weight of MMA, 5- 25 wt% of styrene, 〇-1 〇 by weight of ethyl acrylate. The blend of polyaddition A or polybutadiene with methyl methacrylate-based polymer (abbreviated as B-PMMA) may be selected from EV0NIK's Acrylite XT® polymer, C YRO VU® or C YR0LITE®, Kane ACE® from Kaneka, and BTE 731® from Rohm & Haas. Preferably, the amount of the polymer B is 10-40% by weight, more preferably 20-30% by weight, based on the total weight of the polymer composition -11 - 201130907. The weight average molecular weight of the polymer B is preferably from 40,0 g/m to 4 g/m; more preferably from 80,000 g/m to 20 g, gram/mo Ear; and optimally 120,000 to 1 60,000 g/mole. The polymer b can be selected from the EVONIK standard PLEXGLAS® molding compound series, such as PLEXGLAS@6N, PLEXGLAS® 8N, and others. Preferably, the amount of the copolymer C is from 3 to 9% by weight, more preferably from 5 to 7% by weight, based on the total weight of the polymer composition. The weight average molecular weight of the copolymer c is preferably from 10,000 to 5 Å, gram/mole; more preferably from 79 Å to 175,000 g/mole. The copolymer c, which is a copolymer of styrene and maleic anhydride, abbreviated as SMA, may be selected from P〇lySCOpe P〇iymers B.V. 6161 RA Geleen, XIRAN® of Netherland. The polymer composition contains, in addition to the polyadduct A, the polymer B and the copolymer C, a general additive, and/or an auxiliary agent, and examples thereof are a thermal stabilizer, a UV stabilizer, and a UV absorber. , antioxidants, and / or pigments, pigments or organic dyes. The amount of the general additive and/or adjuvant present present is preferably not more than 10% by weight based on the total weight of the polymer composition, particularly preferably not more than 5% by weight, particularly not more than 2% by weight. The polymer composition may also contain no additives and/or adjuvants, as appropriate. If the additive is highly acidic, good results can be obtained otherwise. This does prevent the formation of bubbles in the polymer composition, which may be due to the decomposition of SMA. For example, boric acid is very suitable as a thermal stabilizer. The result of good -12-201130907 can also be obtained additionally from UV stabilizers which are also highly acidic, preferably having a pKa of up to 8, more preferably a pKa of up to 7, even more preferably a pKa of up to 6, the pKa It has been determined at 23 ° C in a mixture of 50% by weight of isopropanol and 50% by weight of water. An example of this is a compound of 2 _(2 '-hydroxy-5,-methylphenyl)-benzotriazole or a hindered amine light stabilizer (HALS), such as 8-ethylenyl-3-tirty-based _7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)nonane-2,4-dione. Preferably, the U V stabilizer is used in an amount of from 0.005 to 2.0% by weight based on the total weight of the polymer composition. If a highly acidic UV stabilizer (such as one of the above) is used, it is possible to use a second UV stabilizer having a lower acidity as long as the concentration of the second UV stabilizer is lower than the concentration of the first stabilizer. For example, it is possible to use 4-.4-1.5% by weight of 8-ethylindolyl-3-dodecyl-7,7,9,9·tetramethyl-1,3,8-triazaspiro (4, 5) decane-2,4-dione and 0.1-0.5% by weight of bis(2,2,6,6-tetramethyl-4-piperidyl) phthalic acid benzotriazole derivative are also A suitable UV stabilizer selected from the group consisting of 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, a triazine derivative (eg 2-(4,6-diphenyl-1) , 3,5-triazin-2-yl)-5-hexyloxy)phenol), a hindered amine light stabilizer, and combinations thereof. These benzotriazole derivatives are available from Ciba under the name TINUVIN®. For the polybutadiene-modified polymer in the present invention, for example, 3-(3,5-di-t-butyl-4-hydroxyphenyl)-derived from Ciba under the name IRGANOX® 1076- An oxidizing agent resistant to octadecyl propionate is preferred. For the injection molding process, the lubricant or release agent is particularly important -13-201130907' and can reduce or completely prevent the polymer composition from sticking to the injection molding die. Further, many moldings (especially injection-molded parts) are opaque but have a color and thus contain a pigment, a pigment, or an organic dye as an additive. The outdoor use portion typically contains a UV stabilizer, a UV absorber, or an antioxidant to provide additional weathering protection. The lubricant can thus be used as an adjuvant, examples of which are selected from saturated fatty acids having a carbon number of less than 20 (preferably 16 to 18) or saturated aliphatic alcohols having a number of carbon atoms of less than 20 (preferably 16 to 18). class. The quantitative proportion present is preferably minimal, based on the polymer composition, up to 22.5% by weight, for example 0.05 to 0. 2% by weight. » Examples of suitable lubricants are stearic acid, palmitic acid, An industrial mixture of stearic acid and palmitic acid. Examples of other suitable lubricants are n-hexanol, n-octadecyl alcohol, and an industrial mixture of n-hexadecanol and n-octadecyl alcohol. Stearyl alcohol is a particularly good lubricant or release agent. In the manufacture of the polymer composition of the invention, it is preferred to start with a solid such as a polymer bead or granule, using a slow moving mixing device such as a drum type mixer, a free-falling mixer, a spiral mixing wheel, or a double Slot plow mixer. Slowly moving mixers produce mechanical mixing without eliminating phase boundaries (see 'Ullmans Encyklopaedie der technischen Chemie', 4th Ed., Verlag Chemie Vol. 2, pp. 282-3 1 1 ). This is followed by a thermoplastic treatment by using a heatable mixing device at a suitable temperature, in a kneading mixer or preferably in an extruder (for example a single or twin or multi-screw extruder or with an oscillating screw) And the shear bar extruder (for example, Busk Corporation's Cokneader Buss®) melts the melt evenly 14-201130907. The dried granules are then injection molded into the desired plate or other sample for the test. [Embodiment] The components of the kneading and their codes are summarized below. Ingredient material polyabsorbent A B-PMMA-1 B-PMMA-2 Polymer B PMMA-1 PMMA-2 Copolymer C SMA-1 SMA-2 B-PMMA-1 is a kind containing, based on the weight of the poly blend, a polyaddition of 15-16% by weight of polybutadiene and 84-85% by weight of a methyl methacrylate-based polymer, wherein the methyl methacrylate-based polymer comprises From the weight of the polymer based on methyl methacrylate, '65-70% by weight of MMA, 20-25% by weight of styrene, and 5-10% by weight of ethyl acrylate. B-PMMA-1 is provided by EVONIK. B-PMMA-2 is a poly blend containing 20% by weight of polybutadiene and 80% by weight of methyl methacrylate-based polymer based on the weight of the poly-blend. The methyl acrylate-based polymer comprises, by weight of the methyl methacrylate-based polymer, about 94% by weight of MMA and 6% by weight of styrene. B-PMMA-2 is supplied by Kaneka. -15- 201130907 PMMA-l is a 90-92 weight. /〇MMA and 8-10 weight. /〇 A polymer of methyl acrylate. PMMA-1 is provided by EVONIK. PMMA-2 is a polymer containing 98 to 99% by weight of MMA and 1-2% by weight of methyl acrylate. PMMA-2 is provided by EVONIK. SMA-1 is a copolymer containing 26% by weight of maleic anhydride and 74% by weight of styrene having a viscosity of 0.335 centiliters per gram in accordance with ISO 1628. The SMA-1 is supplied by Polyscope. SMA-2 is a copolymer containing 23% by weight of maleic anhydride and 77% by weight of styrene having a molecular weight Mw of 110, gram/mol. SMA-2 is provided by Polyscope. In the present invention, the weight average molecular weight of the polymer is determined in accordance with the GPC method in a manner known in the art. Example a) 70% by weight of B-PMMA-1, 24% by weight of 2PMMA-1 and 6% by weight of SMA-1 were mixed for 3 minutes by a vertical batch mixer (Type SVM-25; available from Shini Machinery) . The mixture was kneaded by a single screw extruder (Type SSE30; available from Ruiya) having a screw diameter of 30 mm at a rotational speed of 24 (TC melting temperature and 50 rpm. Strips extruded from a die) After passing through the water tank, cooling and ninth. The particles were dried by a desiccant-dryer MOTAN at 8 (TC for 2 hours, and then injection molded into an 80x1 0x4 mm sample at the melt temperature of TC in the injection molding machine SUMITOMO SED50). Impact test, and -16- 201130907 Become a 3 mm thick plate for testing optical properties and pencil hardness. Pencil hardness is tested in accordance with ASTM D3 3 63. The plate has a 90% plate transmission (according to a STMD 1 0 0 3 ), 5% turbidity and Charpy impact strength of 87.0 kJ/m 2 (according to ISO 179). The plate is completely transparent as crystal. The turbidity of the product is measured according to ASTM D1003 by Spectrometer GRETAG MCBETH COLOREYE 7000. ASTM D 1 003, a material with a turbidity greater than 30% is considered to be diffuse. The product does not contain toxic substances and substances that may cause cancer, such as acrylonitrile oxime products, combined with low turbidity and high impact. Excellent surface hardness of 1H pencil hardness. Comparative Example 1 Mixture of 70% by weight of B-PMMA-1 and 30% by weight of PMMA-1 using a vertical batch mixer (Type SVM-25 from Shini Machinery) The mixture was mixed for 3 minutes. Thereafter, the mixture was kneaded and injection-molded as described in Example a). The plate prepared by this comparative example was extremely turbid and appeared to be translucent. Example bl-3) With 15/40 /68% by weight of PMMA-1, 80/50/15% by weight of B-PMMA-1 and 5/10/17% by weight of SMA-1 mixture using erect -17-201130907 batch mixer (Type SVM-25, available from Shini Machinery, was mixed for 3 minutes. Thereafter, the results of the mixture as described in Example a) were tested and the results of the injection molding of Example )), Comparative Example 1 and Example b-3) were listed in Table 1 below. Table 1 Example a), bl-3) and Comparative Example 1 Test Results Component Unit Example a) Comparative Example 1 Example bl) Example b2) Example b3) B-PMMA.1 Weight % 70 70 80 50 15 PMMA-1 Weight % 24 30 15 40 68 SMA-1 wt% 6 0 5 10 17 Transmittance (3 mm, A2) % 90 82 90.2 90 91 Turbidity (3 mm) % 5 46 4 4 4 Pencil hardness 1H 1H 2H 2H 3H Charpy Impact Strength kJ/m2 87.0 89.0 68 60 40 Comparative Example 2 Mixture of 67% by weight of PMMA-1 and 33% by weight of B-PMMA-2 using a vertical batch mixer (Type SVM-25 from Shini Machinery) Mix for 3 minutes. Thereafter, the mixture was subjected to the kneading and injection molding examples described in the example a). c) -18- 201130907 A mixture having 50% by weight of PMMA-1, 33% by weight of 2Β-ρΜΜΑ_2 and 17% by weight of SMA-2 was utilized. A vertical batch mixer (SVM-25 from Shini Machinery) was mixed for 3 minutes. Thereafter, the mixture is kneaded and injection molded as described in Example a). The product does not contain toxic substances and substances which may cause cancer such as acrylonitrile. Example d) Mixture of 74.5 wt% of PMMA-2, 17 wt% of B-Ρ Μ Μ A - 2 and 8.5 wt% of SMA-2 using a vertical batch mixer (Type SVM-25, available from Shini Machinery ) Mix for 3 minutes. Thereafter, the mixture is as described in Example a). The kneaded and injection-formed mash product does not contain toxic substances and substances which may cause cancer, such as acrylonitrile 0 -19 - 201130907 Table 2 Examples c), d) and Comparative Example 2 Test result
成份 單位 比較例2 實例C) 實例d) B-PMMA-2 雷量％ 33 33 17 PMMA-1 重量％ 67 50 0 PMMA-2 重量％ 0 0 74.5 SMA-2 重量％ 0 17 8.5 性質 透射率(3毫米,A2) % 44.5 89.6 90 濁度，23°C % 47 4.3 5 Charpy衝擊強度 kJ/m2 79.0 75.0 65 鉛筆硬度 B 1H 2H 表3顯示當組成物含有70重量％2B-PMMA-1時，在6 重量％之SMA-1附近達到最佳光學性質（最高之透射率及 最低之濁度），其中在實例e )及f )中，混合物如實例a )中一般地被混煉且注射成形。 表3含有70重量％之B-PMMA-1及不同量之SMA-1的組成物的組成 材料 單位 比較例1 實例e) 實例a) 實例0 B-PMMA-1 重量％ 70 70 70 70 PMMA-1 重量％ 30 25 24 22.5 SMA-1 重量％ 0 5 6 7.5 性質 透射率 (3毫米，A2) % 82.37 89.75 90 89.77 濁度(3毫米） % 46.0 10 5 9.2 MVR(230〇C/3.8kg) (依照 ISO 1133) cm3/10min 5.9 6.0 6.0 5.7 以下表4顯示含有80%之B_PMMA-1之組成物的組成及 測試結果。在此，摻合物之濁度値也顯示在5重量％之 -20- 201130907 S ΜΑ-1附近有最小値，其中在實例g )及h )中，混合物如 實例a )中一般地被混煉且注射成形。 表4:含有80重量％2B-PMMA-1之組成物的組成 材料 單位 實例b) 實例g) 實例h) B-PMMA-1 重量％ 80 80 80 PMMA-1 重量％ 15 16 14 SMA-1 重量％ 5 4 6 性質 透射率(3毫米,A2) % 90.2 89 89.4 濁度(3毫米） % 4 5.0 5.6 溫度對聚摻物之濁度値的影響也被測試。 以SMA- 1爲底質之聚摻物在不同溫度下於爐中調節2 小時，然後立即取出以供濁度測量。表5顯示測試結果。 具有6重量％之SMA-1的化合物的濁度在溫度由4 t增 至50°C時幾乎保値相同。 表5:具有或不具有SMA-1之聚摻物在4°C、23°C、35°C及50°C下退火2小時後之濁度値 預調節 時間[小時] 2 2 2 2 溫度rc] 4 23 35 50 樣品編號 濁度値％] 比較例1憮SMA-1) 60.4 46.0 40.7 28.7 實例 a)(6 重量 °/&SMA-l) 8.9 5.6 6.0 7.3 表5顯示：具有6%之SMA-1之聚摻物的濁度値在退火 過程中仍保持低。 -21 -Component Unit Comparison Example 2 Example C) Example d) B-PMMA-2 Thunder amount % 33 33 17 PMMA-1 Weight % 67 50 0 PMMA-2 Weight % 0 0 74.5 SMA-2 Weight % 0 17 8.5 Property Transmittance ( 3 mm, A2) % 44.5 89.6 90 turbidity, 23 ° C % 47 4.3 5 Charpy impact strength kJ/m2 79.0 75.0 65 Pencil hardness B 1H 2H Table 3 shows that when the composition contains 70% by weight of 2B-PMMA-1, The best optical properties (highest transmittance and lowest turbidity) were achieved in the vicinity of 6% by weight of SMA-1, wherein in examples e) and f), the mixture was generally kneaded and injection molded as in example a) . Table 3 Composition material units of composition containing 70% by weight of B-PMMA-1 and varying amounts of SMA-1 Comparative Example 1 Example e) Example a) Example 0 B-PMMA-1 wt% 70 70 70 70 PMMA- 1 wt% 30 25 24 22.5 SMA-1 wt% 0 5 6 7.5 Transmittance of properties (3 mm, A2) % 82.37 89.75 90 89.77 Turbidity (3 mm) % 46.0 10 5 9.2 MVR (230〇C/3.8kg) (According to ISO 1133) cm3/10min 5.9 6.0 6.0 5.7 Table 4 below shows the composition and test results of the composition containing 80% of B_PMMA-1. Here, the turbidity enthalpy of the blend also shows a minimum enthalpy around 5% by weight of -20-201130907 S ΜΑ-1, wherein in examples g) and h), the mixture is generally mixed as in example a) Refining and injection molding. Table 4: Composition of a composition containing 80% by weight of 2B-PMMA-1. Example of unit b) Example g) Example h) B-PMMA-1 wt% 80 80 80 PMMA-1 wt% 15 16 14 SMA-1 wt % 5 4 6 Property Transmittance (3 mm, A2) % 90.2 89 89.4 Turbidity (3 mm) % 4 5.0 5.6 The effect of temperature on the turbidity 聚 of the polyblend was also tested. The SMA-1 based polymeric admixture was conditioned in the oven for 2 hours at various temperatures and immediately removed for turbidity measurement. Table 5 shows the test results. The turbidity of the compound having 6% by weight of SMA-1 was almost the same when the temperature was increased from 4 t to 50 °C. Table 5: Turbidity 値 preconditioning time [hours] 2 2 2 2 temperature after annealing of polymer blends with or without SMA-1 at 4 ° C, 23 ° C, 35 ° C and 50 ° C for 2 hours Rc] 4 23 35 50 sample number turbidity 値%] Comparative Example 1怃SMA-1) 60.4 46.0 40.7 28.7 Example a) (6 weight °/&SMA-l) 8.9 5.6 6.0 7.3 Table 5 shows: 6% The turbidity 値 of the SMA-1 polyblend remains low during the annealing process. -twenty one -