201139470 六、發明說明： 【發明所屬之技術領域】 本發明係關於在分支末端具有聚合性雙鍵之多分支巨 單體及苯乙烯系單體及丙烯酸酯的共聚物。更進一步而言 ’係關於在進行成形加工時具有優異的成形加性、生產性 良好的苯乙烯系樹脂組成物、二軸延伸該等而獲得苯乙烯 系樹脂片及其二次成形品。 【先前技術】 苯乙烯·（甲基）丙烯酸系樹脂有優異的高剛性、尺寸安 定性、透明性等，可廣泛使用作爲成形材料。然而，苯乙 烯·（甲基）丙烯酸系樹脂作爲滿足各種用途的要求，平衡的 優異之成形材料還不充分，則要求提高各種性能。 例如’光學系構件爲了抑制成形品的變形（彎曲、變 形）的原因即吸濕性’藉由使用高比例的苯乙烯的共聚物 來對應，但導致成形品的強度降低，而未達到實用水準。 就解決該課題之方法而言，尤其著眼於成形品的彎曲能量 ’爲了獲得大的該彎曲能量之成形品，因此藉由將多分支 巨單體、苯乙烯系單體與（甲基）丙烯酸系單體共聚合，而 獲得多分支狀的苯乙燦-(甲基）丙烯酸共聚合物（例如參照 專利文獻1)。 然而’近年來’尤其從對環境的負荷減輕的觀點，也 逐漸有要求提高生產性’在不損壞成形品之強度，進一步 提供成形加工性也優異的材料。 201139470 又，二軸延伸苯乙烯系樹脂而獲得苯乙烯系樹脂薄片 ，由於其透明性的提高因此被形成爲可看見內容物之容器 而廣泛被使用。現況爲二軸延伸苯乙烯系樹脂時，爲了防 止加熱時的應力所導致的收縮而使用以熱板夾住薄片而成 形之接觸加熱式壓空成形法。 然而，近年來，隨著外帶型食品的增加，市場有一直 強烈需求透明的食品容器蓋，以往主流的接觸加熱式壓空 成形法，因爲二軸延伸苯乙烯系樹脂薄片與熱板接觸而加 熱，因此有將熱板的凹凸或附著於熱板之防霧劑等轉印於 薄片上，而損壞成形品的透明性之問題，故要求可以輻射 加熱式壓空真空成形法成形的二軸延伸苯乙烯系樹脂。 就可以輻射加熱式壓空真空成形法成形的二軸延伸苯 乙烯系樹脂而言，有提出例如將苯乙烯丁二烯共聚物橡膠 分散於苯乙烯系樹脂中之苯乙烯系樹脂以在二軸方向加熱 收縮應力約 2~4kg/cm2(0.196〜0.392MPa)延伸配向之薄片（ 例如，參照專利文獻2)。 又，改善苯乙烯丁二烯共聚物的擠出加工時的熱安定 性不完全所導致的凝膠狀物質的產生之方法，提出例如由 不含橡膠成分之苯乙烯系樹脂、由苯乙烯系單體及不飽和 羧酸酯系單體所構成之共聚物、礦物油、無機或有機粒子 所構成，且其加熱收縮應力爲MD(縱方向）〇.20MPa以上 、TD(橫方向）爲2_00MPa以下，TD與MD之差（TD-MD) 爲〇.22MPa以上之二軸延伸苯乙烯系樹脂薄片（例如參照 201139470 專利文獻3 )。 然而，在前述專利文獻2至3中所提供的二軸延伸苯 乙烯系樹脂薄片，係在以調整加熱收縮應力之輻射加熱式 壓空真空成形法中，提升成形品的厚度均一性者，雖然對 厚度均一性有一定效果，但所獲得良好的成形品之加熱時 間的範圍有非常狹小之問題。即，在輻射加熱式壓空真空 成形法中，一般加熱時間短時，模具再現性不充分，又， 爲了獲得充分的模具再現性，因此若增加加熱時間，容易 產生成形品厚度之問題。防止該等問題產生，當使用前述 專利文獻2及3的組成物時，可獲得良好成形品之最適加 熱時間範圍在係小於1秒。因爲該等在工程管理上非常困 難’從生產性之觀點，實質上在輻射加熱式壓空真空成形 法適用該等二軸延伸苯乙烯系樹脂薄片是困難的，因此逐 漸沒有進行以該成形法將二軸延伸苯乙烯系樹脂片成形之 工業上的生產。 [先前技術文獻] [專利文獻] [專利文獻1]特開2007-284591號公報 [專利文獻2]特開昭59-7 1 829號公報 [專利文獻3]特開2003-238703號公報 【發明內容】 [發明欲解決之課題] 本發明係鑑於如上述之問題而完成者，本發明的課題 201139470 係提供~種可維持使用苯乙烯-丙烯酸系樹脂組成物而獲 得成形品的實用的強度，同時在各種成形方法中可提高成 形加工性之苯乙烯系樹脂組成物，尤其，使用該等之苯乙 稀系樹脂片，可獲得具有優異的光學特性，在輻射加熱式 壓空真空成形法中模具再現性或成形品的沖孔性充分，而 且沒有厚度不均之良好的成形品，可獲得加熱時間的範圍 爲1秒以上，二次加工時的生產性亦優異的二軸延伸苯乙 烯系樹脂薄片。 [用以解決課題之手段] 本發明者用以解決上述之課題而專心致力於硏究檢討 之結果，本發明者以特定比例將獨自開發的多分支狀巨單 體、苯乙烯系單體及丙烯酸酯共聚合而獲得，具有特定的 重量平均分子量與分子量分布之苯乙烯系樹組成物可解決 上述課題，而達到完成本發明。 即，本發明係提供苯乙烯系樹脂組成物、使用該等而 獲得之成形品、二軸延伸薄片及該二次成形品。該苯乙烯 系樹脂組成物特徵爲：將苯乙烯系單體（al)、丙烯酸酯（a2) 與具有複數的分支且在該先端部具有聚合性雙鍵之重量平 均分子量爲1，〇〇〇〜1 5,000的多分支狀巨單體（a3)共聚合而 含有所獲得多分之狀共聚合物（A)之苯乙烯系樹脂組成物 ，該組成物的藉由該GPC-MALS法求出之重量平均分子 量（Mw)爲30萬至60萬，重量平均分子量（Mw)與數量平 均分子量（Μη)之比(Mw/ Μη)爲2.7至4.0，且前述苯乙烯 201139470 系單體（al)與前述丙烯酸酯（a2)的使用比例（ai)/(a2)爲 87/1 3至96/4(質量比）。 [發明的效果] 在本發明所獲得的苯乙烯系樹脂組成物係較以往的線 狀苯乙烯系樹脂組成物具有更廣泛分子量分布範圍者，由 此即使含有超高分子量成分仍有優異成形加工性。再者， 適合使用模具之各種成形方法時，因爲從模具具有良好的 脫模性，因此經由添加劑的倂用而不需要脫模，因爲表面 也沒有污物，因此同時具有成本/時間良好的同時生產性 亦良好，可降低不良品的產生。又，所獲得的成形品也具 有與以往相同或該等以上的機械強度。又，二軸延伸該等 而獲得的薄片係在輻射加熱式壓空真空形成法中，可獲得 模具再現性充分且無厚度不均之良好成形品。以輻射加熱 式壓空真空成形法來進行二次加工時，由於不與熱板接觸 ，因此不產生熱板污物，不損壞苯乙烯系樹脂的透明性而 具有優異的影像清晰性。因此，可進一步適用於大型化、 厚度變薄的各種外殼或光學元件大量生產之各種包裝材料 等。 【實施方式】 [用以實施發明之形態] 以下，詳細描述本發明。 本發明的苯乙烯系樹脂組成物係含有多分支共聚物 (A)之苯乙烯系樹脂組成物，該多分支共聚物（A)係將苯乙 201139470 稀系單體（al)、丙烯酸酯（a2)、具有複數分支且在其先端 具有聚合性雙鍵之重量平均分子量爲1，〇〇〇至15,〇〇〇之多 分支巨單體（a3)共聚合而獲得，該組成物的藉由GPC-MALS法求得之重量平均分子量（Mw)爲30萬至60萬，前 述本乙稀系單體（al)與前述丙烯酸酯（a2)的使用比例 (al)/(a2)爲87/1 3至96M(質量比），且重量平均分子量 (Mw)與數量平均分子量（Mn)的比（Mw/Mn)爲2 7至4 〇之 範圍者。 GPC-MALS法係藉由多角度光散射偵測器來測定分子 量之方法’且係在高度分支之聚合物中有用的分子量測定 。本發明中苯乙烯系樹脂組成物的 GPC-MALS測定在 Shodex HPLC、檢測器 Wyatt Technology DAWN EOS 、 Shodex RI-101、管柱 Shodex KF-806L><2、溶齊!I THF (四 氫呋喃）、流量1.0ml/分鐘的條件下來進行。又，GPC-MALS的測定解析係藉由 Wyatt公司的解析軟體 ASTRA 來進行，並算出苯乙烯系樹脂組成物之重量平均分子量/ 數量平均分子量，經由該値來限定苯乙烯系樹脂組成物者 〇 本發明的苯乙烯系樹脂組成物的藉由前述方法所求得 的重量平均分子量（Mw)必須爲30萬至60萬。該分子量圍 小於3 0萬，所獲得的成形品的強度不足’並降低模具成 形時的脫模性。此外，以輻射加熱式壓空真空成形法將二 軸延伸薄片進行二次成形時的最適加熱時間有時會變短。 201139470 又’若超過60萬，即使分子量分佈廣泛，但成形性不完 全且變得容易產生厚度不均。 又’苯乙嫌系樹脂組成物的藉由GPC-MALS法所求 得的重量平均分子量（Mw)與數量平均分子量（Mn)的比 (Mw/Mn)必須爲2.7至4.0的範圍。Mw/Mn較2.7小者， 與以往本發明者一直所提供之具有多分支構造之苯乙烯系 樹脂組成物相等，係適用各種成形法時的成形加工性不足 者且不適合提牙生產性。又，Mw/Mn超過4.0者，難以後 述的製造方法來獲得。 又’從透明性等的光學特性之觀點，本發明的苯乙嫌 系樹脂組成物的熔融流動率（Melt Flow Rate)(以下稱爲「 MFR」）較佳爲2.0g/10分以上。此外，熔融流動率的測定 條件爲 J I S K 7 2 1 0、條件 Η (2 0 0 °C、5 k g)。 就在本發明可使用的苯乙嫌系單體（al)而言，可列舉 例如苯乙烯及其衍生物，例如苯乙烯、甲基苯乙烯、二甲 基苯乙烯、三甲基苯乙烯、乙基苯乙烯 '二乙基苯乙燦、 三乙基苯乙烯、丙基苯乙烯、丁基苯乙烯、己基苯乙烯、 庚基苯乙烯、辛基苯乙烯等之烷基苯乙烯、氟苯乙烯、氯 苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯等之鹵化苯乙 烯，此外，硝基苯乙烯、乙醯基苯乙烯、甲氧基苯乙烯等 ，該等可以單獨使用也可混合2種以上使用。其中，因爲 通用性大，與後述的丙烯酸酯（a2)的反應性優異，因此使 用苯乙烯爲較佳。 -10- 201139470 就在本發明可使用的丙烯酸酯（a2)而言，沒有 ’例如碳數1至6之烷基或具有取代烷基之丙烯酸 較佳。即，就取代烷基而言，意指烷基的氫原子的 或全部以鹵原子、羥基取代之烷基，就鹵原子而言 舉氟、氯、溴、碘。就具體例而言，可列舉丙烯酸 丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯 丁酯、丙烯酸正己酯、丙烯酸環己酯、丙烯酸羥基 丙烯酸羥基丙酯等，可以單獨使用也可以2種以上 用爲佳。其中，所獲得的多分支狀共聚物（A)中， 當地配置分支構造，含有該等之苯乙烯系樹脂組成 成形加工性較優異者之觀點，丙烯酸丁酯爲適當。 又，只要不損及本發明的效果，可倂用具有其 性雙鍵之單體。就前述單體而言，可列舉例如各種 丙烯酸系化合物或乙烯基醚、乙烯基酯等。 在本發明使用前述其他之單體時，相對於前述 系單體（al)與前述丙烯酸酯（a2)的合計質量而言， 使用5質量％以下。 就本發明中所使用的多分支狀巨單體（a3)而言 是具有複數分支且在該先端部具有聚合性雙鍵之重 分子量爲1,〇〇〇至15,000之巨單體即可，則該結構 特別限制。從工業上獲得容易性之觀點，較佳爲例 發明者在特開2003-292707號公報中所揭示之使用 狀巨單體。 特限制 院醋爲 —部分 ，可列 甲酯、 酸第三 乙酯、 混合使 從可適 物成爲 他聚合 (甲基） 苯乙烯 較佳爲 ，只要 量平均 中沒有 如即本 多分支 -11 - 201139470 就則述多分支狀巨單體而言，可列舉例如藉由下記 (1)至（5)中任一項之方法而獲得者。 (1) 1分子中將具有活性甲基、溴、氯、甲基磺醯氧基 或甲苯擴酸氧基等之AB2型單體進行親核取代反應而獲得 多分支狀的自縮合型聚縮合物做爲前驅物，藉由將該聚縮 合體中所殘存未反應的活性亞甲基或次甲基與氯甲基苯乙 稀、溴甲基苯乙烯等進行親核取代，而導入聚合性雙鍵以 獲得多分支狀巨單體； (2) 在具有1個以上的羥基之化合物中，鄰接於羧基 之碳原子爲飽和碳原子且藉由將該碳原子上的氫原子完全 取代’且具有2個以上羥基之單羧酸進行反應製爲多分支 狀聚合物，將此與丙烯酸、甲基丙烯酸、含有異氰酸醋之 丙嫌酸系化合物' 4_氯甲基苯乙烯等進行反應，而導入聚 合性雙鍵以獲得多分支巨單體； (3) 具有1個以上的羥基之化合物中，經由將具有1 個以上羥基之環狀醚化合物進形反應製爲多分支狀聚合物 ，接者’將該聚合物的末端基即羥基與丙烯酸、甲基丙稀 酸、含有異氰酸酯之丙烯酸系化合物' 4 -氯甲基苯乙烯等 進行反應，而導入聚合性雙鍵以獲得多分支巨單體； (4) 經由將具有1個以上的羥基之化合物與含有2個 以上的羥基、鹵原子、-S020CH3-、-0S02CH3 -等之化合 物進行反應製爲多分支狀聚合物，接著，使該聚合物的末 端基即羥基，與丙烯酸、甲基丙烯酸、含有異氰酸酯之丙 -12- 201139470 烯酸系化合物、4 -氯甲基苯乙烯等進行反應，而導入聚合 性雙鍵以獲得多分支巨單體； (5)將醯胺鍵透過氮原子而成爲重複構造之PAM AM樹 枝狀高分子（dendrimer)’與丙燃酸、甲基丙嫌酸、含有錢 氰酸酯之丙烯酸系化合物、4-氯甲基苯乙烯等進行反應， 而導入聚合性雙鍵以獲得多分支巨單體； 在前述（1)中，1分子中具有活性亞甲基、溴、氯、甲 基磺醯氧基或甲苯磺醯氧基等之AB2型之單體，可列舉例 如鹵化烷氧基-苯基乙腈類或具有甲苯磺醯氧基之苯基乙 腈類。 在前述（2)中’就鄰接於羧基之碳原子爲飽和碳原子 且該碳原子上的氫原子被完全取代、且具有2個以上羥基 之單羧酸而言’可列舉例如二羥甲基丙酸、α，α一雙（經 基甲基）丁酸、α’ α，α —參（羥基甲基）乙酸、α，α—雙（羥 基甲基）戊酸或α，α —雙（羥基甲基）丙酸等。 在前述（3)中，就具有1個以上的羥基之環狀醚化合 物而言，可列舉例如3_乙基-3_(羥基甲基）氧雜環丁烷、 2,3_環氧-1-丙醇、2,3-環氧-1-丁醇或3,4-環氧1_丁醇等。 在前述（4)中’就含有2個以上的羥基、鹵原子、_ S020CH3-、-0S02CH3-等之化合物而言，可列舉例如5_( 溴甲基）-1，3 -二羥基苯、2 -乙基-(溴甲基）-i，3 -丙二醇、 2-甲基- 2-(溴甲基）-i，3_丙二醇、2_(溴甲基）_2_(羥基甲 基）-1,3-丙二醇等。 201139470 在前述（5)中’就PAMAM樹枝狀高分子而言，例如可 經由特公平6-070132號公報及特公平7-042352號公報所 示之手法來製造。 又，多分支狀巨單體（a3)之重量平均分子量必須爲 1，000至15,000者。該分子量藉由 GPC-MALS測定法 (Shodex HPLC、檢測器 Wyatt Technology DAWN EOS、 Shodex RI-101、管柱 Shodex KF-806L><2、溶齊Ij THF (四 氫呋喃）、流量l.〇ml/分鐘的條件）來進行。又，GPC_ MALS測定的解析係經由 Wyatt公司的解析軟體 ASTRA 來進行，而求得重量平均分子量。該分子量小於1，〇〇〇， 則分支構造的導入量不足’會變爲與先前的線狀苯乙烯一 丙烯酸共聚物相近的物性，而難以得到具有本發明所規定 之廣泛分子量分布寬度的苯乙烯系樹脂組成物，又製得之 成形品的實用上的強度亦不足。又，若該分子量超過 1 5，000’則多分支狀巨單體的處理變得困難，變得難以將 苯乙烯系單體（al)與丙烯酸酯〇2)進行均勻共聚合。更佳 分子量爲2,500至7,000 。 又，就前述多分支狀巨單體（a3)而言，每lg含有聚 合性雙鍵0.1微莫耳至5.5微莫耳爲較佳。若爲該範圍， 則可抑制所獲得的多分支狀共聚物（A)中的分支構造的導 入量’而防止製造時的凝膠化，因此變得容易獲得適度地 含有所期望的高分子量成分，且具有廣泛的分子量分布之 苯乙烯系樹脂組成物。更佳含量爲丨.0至3.5微莫耳之範 -14- 201139470 圍。此外，例如該含量係根據甲基丙烯酸及其衍生物，雙 鍵之條件爲在甲基丙稀酸甲酯之式量中，含有1莫耳的雙 鍵而求得者，根據苯乙烯或其類似化合物雙鍵的條件爲在 苯乙烯的式量中含有1莫耳的雙鍵而求得的値。 本發明的苯乙烯系樹脂組成物需要將前述苯乙烯系單 體（al)、前述丙烯酸酯（a2)、前述多分支巨單體（a3)共聚 合而獲得多分支共聚合物’但合成該共聚物時，可獲得含 有同時完全不含苯乙烯系單體（al)與丙烯酸酯（a2)之線狀 共聚物或多分支狀巨單體（a3)衍生構造之低分支度的共聚 合物之混合物。本發明中’因爲需要前述多分支狀聚合物 (A)則佳，因此除去這樣的線狀共聚物或低分支度的共聚 物不疋必要的’若爲則述所規定的M w、及M w / Μ η比例， 則本發明的苯乙烯系樹脂組成物可直接使用。又，在1段 的製造’在不滿足前述所規定之Mw、Mw/Mn時，可另外 混合使苯乙烯系單體（al)與丙烯酸酯（a2)進行共聚合而成 之樹脂來調整。 此外，本發明的苯乙烯系樹脂組成物必須爲苯乙烯系 單體〇1)與丙烯酸酯（a2)之使用比例（ai)/(a2)爲87/13至 96/4(質量比）。如前述’即使在另外混合苯乙烯系單體 (a 1)與丙烯酸酯（a2)進行共聚合而成之樹脂，並調整時， 在苯乙烯系樹脂組成物中’苯乙烯系單體衍生成分的含有 率與丙烯酸酯（a2)衍生成分的含有率的質量比必須在該範 圍內。丙烯酸酯的使用比例比4 ·小者，適用各種成形法時 -15- 201139470 之成形加工性不足，會難以展現賦予本發明的目的之成形 加工性的效果。此外，從薄片的低溫成形性及像鮮明性之 觀點，丙烯酸酯的使用比例較佳爲4以上。又，丙烯酸酯 的使用比例超過 13.0，則會降低維卡軟化溫度（Vicat softening temperature)，又，成形品的耐熱性會低於實用 的範圍。從所獲得的成形品的物性平衡優異的觀點，使用 丙烯酸丁酯做爲丙烯酸酯（a2)，就與苯乙烯系單體（al)的 使用比例而言，（al) /丙烯酸丁酯較佳爲92/8至96/4(質量 比）。 此外，相對於前述丙烯酸單體（al)與前述丙烯酸酯 (a2)的合計，以質量基準，前述多分支巨單體（a3)較佳使 用 100 至 l,000ppm。 就在本發明中所使用的多分支共聚合物的製造方法而 言，將前述苯乙烯系單體（al)、前述丙烯酸酯（a2)與前述 多分支狀巨單體（a3)共聚合，含有該多分支狀共聚物（A)之 苯乙烯系樹脂組成物若成爲本案所特定的分子量/分子量 分布範圍，就沒有特別限制。從在1段的反應可更有效製 造苯乙烯系樹脂組成物做爲目的之觀點，由本發明者採用 即在特開2 00 5 - 05 3 93 9號公報中所提供的製造方法爲較佳 〇 具體而言’藉由將含有前述原料（al)至（a3)之混合物 進行溶液聚合法或熔融聚合法（塊狀聚合法）而反應爲較佳 。此時’不添加有機溶劑也可進行反應，但較佳爲藉由倂 -16- 201139470 用少量的有機溶劑來降低反應物的黏性’則控制聚合物的 分子量變得容易。 就所使用的有機溶劑而言，鏈轉移常數（chain transfer constant)爲 5 至 4 爲較佳 ’ 〇.2χ1〇 至0.8χ1(Γ5爲更佳。其它例子’較佳爲甲苯、乙基苯、二 甲苯、乙腈、苯、氯苯、二氯苯、苯甲醚、氰基苯、二甲 基甲醯胺、Ν，Ν -二甲基甲醯胺、甲基乙基酮等。關於其使 用量，相對於原料單體的合計100質量份而言’較佳爲5 質量份至50質量份，更佳爲6質量份至20質量份。另外 ，若使用有機溶劑進行聚合，則容易抑制有機溶劑之不溶 成分的生成，故爲較佳。 尤其，多分支狀巨單體（a3)的添加量多時，從抑制凝 膠化的觀點，也必須使用上述有機溶劑。因此，可增加先 前所示的多分支狀巨單體的添加量。 至於聚合開始，可使用自由基聚合引發劑。就該引發 劑而言，較佳爲半衰期爲1 0小時、溫度爲7 5至1 4 0 °C， 更佳爲溫度8 5至1 3 5小時。可列舉例如1，1 -雙（三級丁基 過氧基）環己烷、2,2 -雙（三級丁基過氧基）丁烷、2，2-雙 (4,4-二-丁基過氧基環己基）丙烷等之過氧基縮酮類；異丙 苯氫過氧化物、三級丁基氫過氧化物等之氫過氧化物類； 二-三級丁基過氧化物、二異丙苯基過氧化物、二-三級己 基過氧化物等之二烷基過氧化物類；苯甲醯基過氧化物、 二桂皮酿基過氧化物等之二醯基過氧化物類；過氧基苯甲 •17- 201139470 酸三級丁酯、過氧基間苯二甲酸二-三級丁酯、過氧基異 丙基單碳酸-三級丁酯等之過氧基酯類；N，N’-偶氮雙異丁 基腈' N，N’-偶氮雙（環己烷-1-甲腈）、N，N’-偶氮雙（2-甲 基丁腈）、N，N’-偶氮雙（2,4_二甲基戊腈）、N，N’-偶氮雙 [2 -(羥基甲基）丙腈]，可以使用該等的1種或組合2種 以上。 就該等的使用量而言，相對於原料的單體合成質量， 以質量爲基準，較佳爲50ppm至l，000ppm’更佳爲1〇〇 至 5 0 0 p p m ° 此外，讓含有該多分支狀共聚物（A)之苯乙烯系樹脂 組成物的分子量不致於變得過大，亦可添加鏈轉移劑。就 鏈轉移劑而言，可使用具有1個鏈轉移基之單官能鏈轉移 劑，或者也可使用具有複數鏈轉移劑之多官能鏈轉移劑。 就單官能鏈轉移劑而言，可列舉烷基硫醇類、硫乙醇酸醋 類等。 就多官能鏈轉移劑而言，可列舉以硫乙醇酸或3 -氫硫 基丙酸將甘醇、新戊二醇、三羥甲基丙烷、新戊四醇、二 新戊四醇、三新戊四醇、山梨醇等之多元醇羥基進行醋化 者。 以往，已知經由倂用苯乙稀系單體（al)與丙稀酸醋 (a2)，使用所獲得的共聚合物之成形品顯示具有柔軟性（可 撓性）。然而，該情況經由降低該共聚物的軟化點，耐熱 性會不足、機械強度未達實用的程度。另一方面，已知經 -18 - 201139470 由倂用多分支狀巨單體（a3)，雖然含有 物’但可獲得流動性優異的共聚合物。 多分支巨單體時，該流動性與具有相同 線狀樹脂比較到底也不過是良好，隨等 大型化/薄厚度化/高設計等），又，隨著 ’變得要求具有進一步的加工性。此外 點’在較低溫的成形性也是必要的，在 法中’爲了提升生產性，則用以防止對 之脫模性也是必要的項目。本發明可以 提供該等性能平衡優異之苯乙烯系樹脂 本發明中所使用的苯乙烯系樹脂組 分支共聚物（A)之苯乙烯系樹脂組成物 GPC-MALS法可求得重量平均分子量子 60萬’且右重量平均分子量（Mw)與數 的比（Mw/ Μη)爲2.7至4.0即可，可 聚物（Α)所構成者’也可爲由多分支狀； 分所構成者。即，就此處之其他成分而 成分時’右爲本乙稀系樹脂組成物的重 量平均分子量不會從上述範圍偏離，且 則沒有特別限制’但根據用途可使用各 狀的共聚物等闻分子化合物等。 就前述添加劑而言，可列舉例如各 劑、抗靜電劑、潤滑劑、防霧劑、抗菌 高分子量的共聚合 然而，即使在倂用 重量平均分子量之 I成形品的多樣化（ 成形方法的多樣化 ，從能量縮減之觀 使用模具之成形方 該模具的樹脂污物 解決這樣的要求， 組成物。 成物如前述具有多 ，藉由該組成物的 量（Mw)爲30萬至 量平均分子量（Μη) 爲僅由多分支狀共 电聚物（Α)與其他成 言，在使用該其他 量平均分子量與數 不妨礙本案效果者 種添加劑或上述線 種安定劑、防阻塞 劑·、抗氧化劑、染 • 19 - 201139470 料、紫外線吸收劑等。但’在本發明所使用的苯乙嫌系樹 脂組成物因爲即使不使用以往爲了賦予脫模性或成形力口工 性而使用的礦物油等，也有優異的該等性能，在添加劑的 使用必須留意與以往的苯乙烯-(甲基）丙烯酸系共聚物中添 加劑的使用方法的不同點。 本發明的成形品除了使用前述本發明的苯乙燃系樹脂 組成物之外，沒有任何限制，例如適用射出、擠壓、吹塑 、壓縮等之成形方法，而形成射出成形品、板、薄片、薄 膜等。尤其，從本發明的苯乙烯系樹脂組成物具有優異的 成形加工性或脫模性等之生產性優異之觀點，可適用於可 大量生產之用途例如透明大型射出成形品等。 尤其，本發明的苯乙烯樹脂組成物可適用於二軸延伸 苯乙烯系樹脂薄片。在該延伸方法沒有特別限制，但以輻 射加熱式壓空真空成形法的二次加工性優異之觀點，所獲 得的薄片的縱方向及橫方向其中之一的加熱收縮應力爲 0.2MPa至0.45MPa的範圍爲較佳》 前述加熱收縮應力如前述專利文獻2及專利文獻3之 記載’在該技術領域通常使用物性値，具體而言，係以 A S TM D- 1 5 04爲基準所測定之値。在本發明中，二軸延伸 薄片的縱方向（MD)及與該等正交之橫方向（TD)共同經由比 較低値的範圍即0.20MPa至0.45MPa的加熱收縮應力，在 沒有固定薄片，而適用成形的輻射加熱式壓空真空成形時 沒有引起厚度不均等，則成形品的厚度均勻性優異。在輻 -20- 201139470 射加熱式壓空真空成形中，如此低的加熱收縮應力爲較佳 ，已見於前述專利文獻2中，但本發明不損壞苯乙烯系樹 脂本來具有的透明性，爲了確保如前述實用的問題之最適 加熱時間，因此必須使用具有多分支構造且具有特定分子 量/分子量分布範圍之苯乙烯樹脂組成物。 加熱收縮應力可根據延伸溫度/延伸倍率做調整，但 由於即使進一步根據薄片的擠壓速度/擠壓時（延伸前）的薄 片寬度仍會變動，因此規定特定的製造條件爲困難的。然 而，在一般的製造條件中，就延伸溫度而言，前述的苯乙 烯系樹脂組成物的維卡軟化點+(〇〜40) °C爲較佳，就延伸 倍率而言，一方向中1.5〜5.0倍爲較佳。該等之値如果在 該範圍內，則輻射加熱式壓空真空成形可容易製造具有可 能較佳的範圍的加熱收縮應力之薄片。 又，即使二軸延伸所獲得的薄片的厚度也沒有特別限 制，但若爲〇 · 1至1 mm之範圍，以對通用的輻射加熱式 壓空真空成形機可適用之觀點爲較佳者。 本發明的二軸延伸苯乙烯系樹脂薄片的製造方法沒有 沒有特別限制’以往的延伸薄片的製造中，可以利用先前 的延伸薄片的製造中所使用的方法來進行。其中一個例子 ，將苯乙烯系樹脂組成物供應至擠壓機，熔融混鍊後，以 T -鑄模或圓形鑄模等連續擠壓’將薄片以拉幅機法 '氣泡 法等連續地依次或同時地進行二軸延伸之方法。 此外，本發明的二軸延伸苯乙烯系樹脂薄片可在至少 -21- 201139470 一面或兩面上塗布防霧劑或脫模劑。亦可倂用防霧劑及脫 模劑。就防霧劑而言’可使用例如山梨醇酐脂肪酸酯、蔗 糖脂肪酸酯、聚甘油脂肪酸酯、聚氧乙烯衍生物等之非離 子系界面活性劑等，此等可以單獨或以混合物使用。就脫 模劑而言，例如聚矽氧油或其乳化液等。此外，可塗布各 種非離子系界面活性劑、陽離子系界面活性劑、陰離子系 界面活性劑等做爲抗靜電劑。就該等塗布方法而言，可列 舉噴塗塗布機、輥塗布機、凹版輪轉輥塗布機、氣動刮刀 式塗布機、氣刀塗布機、噴盤式均句給濕（rotor damping) 塗布機、施塗器（applicator)方式等。 本發明的二軸延伸苯乙烯系樹脂薄片爲了在不破壞本 發明的效果的範圍內，賦予設計性及機能性等，因此可在 薄片的表面上進行印刷或也可以在具有屏障性、抗菌性、 熔接性等之機能性之樹脂在薄片的表面上進行積層。此外 ，可在發泡薄片上積層本發明的二軸延伸苯乙烯樹脂薄片 等做爲容器的一部分來使用。 本發明的二軸延伸苯乙烯系樹脂薄片由於具有防阻塞 效果，因此可含有各種微粒子。就前述微粒子而言，可列 舉例如苯乙烯系樹脂交聯粒子、（甲基）丙烯酸酯系樹脂交 聯粒子、聚胺基甲酸酯系樹脂交聯粒子等之樹脂交聯粒子 :二氧化矽、疏水化處理二氧化矽、球狀二氧化矽、輕質 碳酸鈣、氧化鈦、滑石等之無機微粒子；苯乙烯接枝二烯 橡膠等之橡膠微粒子等。尤其，因爲二軸延伸苯乙烯系樹 -22- 201139470 脂薄片與使用該等之成形品的強度、防阻塞性及剝離性提 升，因此特佳爲苯乙烯接枝二烯橡膠。即，就苯乙烯接枝 二烯橡膠而言，因爲可獲得二軸延伸苯乙烯系樹脂薄片與 使用該等之成形品的強度與外觀的平衡優異者，因此在二 軸延伸苯乙烯系樹脂薄片上含有平均粒徑成爲0.1〜5.0 μηι 而且二烯成分成爲0.05〜3.0質量％的範圍者爲佳。若要獲 得更高的透明性較佳爲含有〇.〇5~〇.5質量％。 此外，因爲提升二軸延伸苯乙烯系樹脂薄片製膜時的 延伸性、成形爲容器的二次成形時的深引伸（deep d r a w i n g)成形性與低溫成形性，因此本發明的二軸延伸苯 乙烯樹脂薄片可含有礦物油。但是，熔融擠出時所產生礦 物油的揮發成分凝結附著於薄片製造裝置上，將該等轉印 在薄片上時，爲了防止二軸延伸苯乙烯系樹脂薄片的外觀 不良，因此較佳爲0.5質量％以下》藉由前述方法，可將 上述各種粒子或礦物油添加至所獲得的二軸延伸前苯乙烯 系樹脂組成物中’且可含於二軸延伸苯乙烯系樹脂薄片中 〇 就將前述二軸延伸苯乙烯系樹脂薄片進行二次加工之 成形方法而言’較佳爲輻射加熱式壓空真空成形。就成形 品的形狀/用途而固’沒有特殊限制，可列舉例如食品容 器的蓋子、盤子 '食品包裝袋、氣泡包裝袋、其他各種包裝 袋、盒子等。尤其’使用本發明的二軸延伸苯乙烯系樹脂 組成物以輻射加熱式壓空真空成形而獲得的成形品，係因 -23- 201139470 爲與熱板沒有接觸，沒有爲了壓力調整而將設置於熱板上 的微細孔轉印，將來自塗布於薄片的表面上的防霧劑等之 熱板污物轉印，因此變成具有優異的透明性。 [實施例] 以下列舉實施例用來更詳細說明本發明，但本發明不 侷限於該等之實施例。此外，只要沒有特別限定，「％」 表示爲「質量％」。 下述爲評估方法等。 [GPC-MALS測定條件] 苯乙烯系樹脂組成物的 GPC-MALS測定在 Shodex HPLC、檢測器 Wyatt Technology DAWN EOS、Shodex RI-101、管柱 Shodex KF-806LX2、溶劑 THF、流量 1.0ml/分 鐘的條件來進行。此外，GPC-MALS的測定解析係藉由 Wyatt公司的解析軟體ASTRA來進行，來算出苯乙烯系 樹脂組成物之重量平均分子量、數量平均分子量等。 [熔融流動率（MFR)測定法] 根據 JIS K7210來測定。再者，測定條件爲溫度 200 °C、荷重 49N。 [夏式衝擊強度]:根據JIS K71 1 1來測定。 [維卡軟化溫度]:根據JIS Κ7206··99來測定。 [射出成形加工性] 藉由日本製鋼所製造150噸射出成形機來形成布丁型 容器，根據下述評估基準做評估。 -24- 201139470 容器形成容易且沒有厚度不均’· ◎ 容器形成相對上容易、沒有厚度不均：〇 容器形成相對上容易、有厚度不均：△ 容器形成困難且有厚度不均：X [薄片成形加工性] 使用薄片擠壓機（螺旋直徑3 0mm)，在熔融樹脂溫度 爲210 °C至230 °C、擠壓速度爲0.8至lm/分鐘下擠壓樹脂 九粒，而製作厚度〇.4mm之薄片樣品。接者，將該薄片 樣品使用真空成形機在加熱溫度2 9 0 °C至3 0 0 °C、加熱時 間1 0秒至3 0秒下加熱之後，測定以薄片加熱前的薄片面 作爲基準之薄片中央部的下垂長度，由薄片的下垂長度相 對於加熱時間，根據下述評估基準評估成形加工性》 加熱時間2 0秒時，下垂量小於2 0 m m爲◎、2 0至小 於40mm爲o' 40mm以上爲X » 加熱時間3 0秒時，下垂量小於3 0 m m爲◎、3 0至小 於60mm爲〇、60mm以上爲X。 但，相對於任何一面的加熱時間，評估爲X時，另一 面爲〇或是◎時，評估爲八。 [脫模性] 藉由日本製鋼所製造150噸射出成形機來形成 2 0 cmx 1 5cm M cm的箱形，根據下述評估基準做評估。 ◎:在連續5 0注塑量以上脫模容易 〇:在連續30注塑量以上脫模容易 -25- 201139470 △:在連續10注塑量以上產生脫模困難 X :在連續1至2注塑量脫模困難 [實用耐熱性] 藉由日本製鋼所製造150噸射出成形機來形成 20cmxl5cmx4cm的箱形，該成形品在環境溫度爲70°C、 放置1小時，成形品沒有變形時評估爲◎，少量變形時評 估爲〇，明顯變形且該程度大時評估爲x。[Technical Field] The present invention relates to a multi-branched macromonomer having a polymerizable double bond at a branch end, and a copolymer of a styrene monomer and an acrylate. Furthermore, the styrene resin sheet and the secondary molded article thereof are obtained by the styrene resin composition having excellent moldability and productivity, and biaxial stretching. [Prior Art] The styrene-based (meth)acrylic resin is excellent in high rigidity, dimensional stability, transparency, etc., and can be widely used as a molding material. However, styrene-based (meth)acrylic resins are required to improve various properties because they are not sufficient for a balanced and excellent molding material as required for various applications. For example, 'the optical component is used to suppress the deformation (bending, deformation) of the molded article, that is, the hygroscopic property is matched by using a copolymer of a high proportion of styrene, but the strength of the molded article is lowered, and the practical level is not achieved. . In order to solve the problem, in particular, attention is paid to the bending energy of the molded article. In order to obtain a molded article having a large bending energy, a multi-branched macromonomer, a styrene monomer, and a (meth)acrylic acid are used. The monomer is copolymerized to obtain a multi-branched styrene-(meth)acrylic acid copolymer (for example, see Patent Document 1). However, in recent years, in particular, from the viewpoint of reducing the load on the environment, there has been a demand for improvement in productivity. The material is excellent in moldability without damaging the strength of the molded article. 201139470 Further, a styrene-based resin sheet is obtained by biaxially stretching a styrene-based resin, and since it is improved in transparency, it is widely used as a container in which a content can be seen. In the case of a biaxially stretched styrene-based resin, a contact-heating forming method in which a sheet is sandwiched by a hot plate is used in order to prevent shrinkage due to stress during heating. However, in recent years, with the increase in take-away type foods, there has been a demand for transparent food container lids in the market. In the past, the mainstream contact heating type pressure forming method was heated because the biaxially stretched styrene resin sheet was in contact with the hot plate. Therefore, there is a problem that the unevenness of the hot plate or the antifogging agent attached to the hot plate is transferred onto the sheet to impair the transparency of the molded article, so that the biaxial stretching which can be formed by the radiant heating vacuum forming method is required. Styrene resin. In the case of the biaxially stretched styrene resin which can be formed by the radiant heating type vacuum forming method, for example, a styrene resin in which a styrene butadiene copolymer rubber is dispersed in a styrene resin is proposed in the two axes. The direction-heating shrinkage stress is about 2 to 4 kg/cm 2 (0.196 to 0.392 MPa) of the stretched sheet (for example, see Patent Document 2). Further, a method for improving the generation of a gel-like substance due to incomplete thermal stability during extrusion processing of a styrene-butadiene copolymer is proposed, for example, from a styrene-based resin containing no rubber component and a styrene-based resin. a copolymer composed of a monomer and an unsaturated carboxylic acid ester monomer, a mineral oil, an inorganic or organic particle, and a heating shrinkage stress of MD (longitudinal direction) 20 20 MPa or more, and TD (lateral direction) 2 00 MPa. In the following, the difference between TD and MD (TD-MD) is a biaxially stretched styrene resin sheet of 2222 MPa or more (see, for example, Patent No. 201139470 Patent Document 3). However, the biaxially stretched styrene-based resin sheet provided in the above-mentioned Patent Documents 2 to 3 is used to enhance the thickness uniformity of the molded article in the radiant heating type vacuum forming method in which the heating shrinkage stress is adjusted, although There is a certain effect on the thickness uniformity, but the range of the heating time of the obtained molded article is very narrow. In other words, in the radiant heating type vacuum forming method, when the heating time is short, the mold reproducibility is insufficient, and in order to obtain sufficient mold reproducibility, if the heating time is increased, the thickness of the molded article tends to occur. In order to prevent such problems, when the compositions of the above Patent Documents 2 and 3 are used, the optimum heating time range in which a good molded article can be obtained is less than 1 second. Because these are very difficult in engineering management, it is difficult to apply these biaxially stretched styrene resin sheets in the radiant heating type vacuum forming method from the viewpoint of productivity, and thus the forming method is gradually not carried out. Industrial production of a biaxially stretched styrene resin sheet. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2003-284703 (Patent Document 3) JP-A-2003-238703 [Problem to be Solved by the Invention] The present invention has been made in view of the above problems, and the problem of the present invention is to provide a practical strength for obtaining a molded article by using a styrene-acrylic resin composition. At the same time, in the various molding methods, the styrene resin composition which can improve the formability, in particular, the use of the styrene resin sheet can obtain excellent optical properties in the radiant heating type vacuum forming method. The mold reproducibility and the punchability of the molded article are sufficient, and there is no molded article having a good thickness unevenness, and the biaxially stretched styrene system having a heating time range of 1 second or more and excellent productivity in secondary processing can be obtained. Resin sheet. [Means for Solving the Problem] The inventors of the present invention have focused on the above-mentioned problems and have devoted themselves to the results of the review. The present inventors have independently developed multi-branched macromonomers, styrene monomers, and The styrene-based tree composition having a specific weight average molecular weight and a molecular weight distribution which is obtained by copolymerization of an acrylate can solve the above problems, and the present invention has been accomplished. In other words, the present invention provides a styrene resin composition, a molded article obtained by using the above, a biaxially stretched sheet, and the secondary molded article. The styrene-based resin composition is characterized in that the styrene-based monomer (al), the acrylate (a2), and a plurality of branches and having a polymerizable double bond at the tip end have a weight average molecular weight of 1, 〇〇〇 a styrene-based resin composition containing ~15,000 multi-branched macromonomer (a3) and containing the obtained multi-component copolymer (A), which is obtained by the GPC-MALS method The weight average molecular weight (Mw) is from 300,000 to 600,000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (?η) (Mw / Μη) is 2.7 to 4.0, and the aforementioned styrene 201139470 monomer (al) and The use ratio (ai)/(a2) of the aforementioned acrylate (a2) is from 87/1 3 to 96/4 (mass ratio). [Effect of the Invention] The styrene resin composition obtained by the present invention has a broader molecular weight distribution range than the conventional linear styrene resin composition, and thus excellent molding processing even if the ultrahigh molecular weight component is contained. Sex. Further, when various molding methods of the mold are suitable, since the mold has good mold release property, it is not required to be demolded by the use of the additive, since the surface is free from dirt, and at the same time, it has a good cost/time. Good productivity is also good, which can reduce the production of defective products. Further, the obtained molded article has the same or higher mechanical strength as the conventional one. Further, in the radiant heating type vacuum forming method, the sheet obtained by biaxially stretching the film can obtain a good molded article having sufficient mold reproducibility and no thickness unevenness. When the secondary processing is performed by the radiant heating type vacuum forming method, since it is not in contact with the hot plate, no hot plate dirt is generated, and the transparency of the styrene resin is not impaired, and excellent image clarity is obtained. Therefore, it can be further applied to various kinds of packaging materials, such as various casings or optical components which are large in size and thin in thickness, and which are mass-produced. [Embodiment] [Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The styrene-based resin composition of the present invention contains a styrene-based resin composition of a multi-branched copolymer (A) which is a styrene monomer (al) or an acrylate (hereinafter referred to as phenylethyl 201139470). A2) obtained by copolymerization of a multi-branched macromonomer (a3) having a complex branch having a polymerizable double bond at its apex and having a weight average molecular weight of 1, 〇〇〇 to 15, and 〇〇〇 The weight average molecular weight (Mw) determined by the GPC-MALS method is 300,000 to 600,000, and the ratio (al)/(a2) of the above-mentioned ethylenic monomer (al) to the aforementioned acrylate (a2) is 87. /1 3 to 96 M (mass ratio), and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 27 to 4 Torr. The GPC-MALS method is a method for determining the molecular weight by a multi-angle light scattering detector and is useful for molecular weight determination in highly branched polymers. The GPC-MALS measurement of the styrene resin composition in the present invention is carried out in Shodex HPLC, detector Wyatt Technology DAWN EOS, Shodex RI-101, column Shodex KF-806L><2,dissolved; I THF (tetrahydrofuran), flow rate of 1.0 ml/min. In addition, the measurement analysis of GPC-MALS is performed by Wyatt's analytical software ASTRA, and the weight average molecular weight/number average molecular weight of the styrene resin composition is calculated, and the styrene resin composition is limited by the enthalpy. The weight average molecular weight (Mw) obtained by the above method of the styrene resin composition of the present invention must be 300,000 to 600,000. The molecular weight is less than 30,000, and the obtained molded article has insufficient strength and reduces the mold release property when the mold is formed. Further, the optimum heating time for secondary forming of the biaxially stretched sheet by the radiant heating type vacuum forming method may be shortened. 201139470 In addition, if it exceeds 600,000, even if the molecular weight distribution is wide, the formability is incomplete and thickness unevenness is likely to occur. Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained by the GPC-MALS method of the styrene resin composition must be in the range of 2.7 to 4.0. When the Mw/Mn is smaller than 2.7, it is equivalent to the styrene-based resin composition having a multi-branched structure which has been provided by the inventors of the present invention, and is insufficient for moldability in various molding methods and is not suitable for tooth productivity. Further, those having a Mw/Mn of more than 4.0 are difficult to obtain by the production method described later. Further, the melt flow rate (hereinafter referred to as "MFR") of the styrene-based resin composition of the present invention is preferably 2.0 g/10 minutes or more from the viewpoint of optical properties such as transparency. Further, the measurement conditions of the melt flow rate were J I S K 7 2 1 0, and the conditions Η (200 ° C, 5 k g). As the styrene monomer (al) which can be used in the present invention, for example, styrene and derivatives thereof such as styrene, methyl styrene, dimethyl styrene, trimethylstyrene, Alkyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, etc. Halogenated styrene such as ethylene, chlorostyrene, bromostyrene, dibromostyrene, iodine styrene, etc., in addition, nitrostyrene, ethyl styrene styrene, methoxy styrene, etc., which can be used alone It can be used in combination of 2 or more types. Among them, styrene is preferred because it has high versatility and is excellent in reactivity with an acrylate (a2) to be described later. -10-201139470 In the case of the acrylate (a2) which can be used in the present invention, it is preferred that there is no, for example, an alkyl group having 1 to 6 carbon atoms or an acrylic acid having a substituted alkyl group. Namely, the substituted alkyl group means an alkyl group in which all or a hydrogen atom of the alkyl group is substituted with a halogen atom or a hydroxyl group, and as the halogen atom, fluorine, chlorine, bromine or iodine is used. Specific examples thereof include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, and hydroxypropyl acrylate acrylate. These may be used alone or in combination. More than the above is preferred. In the obtained multi-branched copolymer (A), a branched structure is locally disposed, and the styrene-based resin composition is excellent in the formability, and butyl acrylate is suitable. Further, as long as the effects of the present invention are not impaired, a monomer having a double bond can be used. Examples of the monomer include various acrylic compounds, vinyl ethers, and vinyl esters. When the other monomer is used in the present invention, it is used in an amount of 5% by mass or less based on the total mass of the above-mentioned monomer (al) and the acrylate (a2). The multi-branched macromonomer (a3) used in the present invention may be a macromonomer having a plurality of branches and having a polymerizable double bond at the terminal end and having a molecular weight of 1, from 1 to 15,000. Then the structure is particularly limited. From the viewpoint of the ease of industrial use, it is preferred to use the macromonomers disclosed in Japanese Laid-Open Patent Publication No. 2003-292707. The vinegar is limited to a part, and the methyl ester and the third ester of the acid can be mixed, so that it is preferable to make the polymer (meth) styrene from the achievable substance, as long as the amount is not as large as that of the present branch -11 - 201139470 The multi-branched macromonomer is, for example, obtained by the method according to any one of (1) to (5) below. (1) A nucleophilic substitution reaction of an AB2 type monomer having an active methyl group, a bromine, a chlorine, a methylsulfonyloxy group or a toluene acid extension oxy group in one molecule to obtain a multi-branched self-condensation type polycondensation The product is used as a precursor, and the polymerizable property is introduced by nucleophilic substitution of the unreacted active methylene or methine remaining in the polycondensate with chloromethylstyrene or bromomethylstyrene. Double bond to obtain a multi-branched macromonomer; (2) in a compound having one or more hydroxyl groups, a carbon atom adjacent to a carboxyl group is a saturated carbon atom and is completely substituted by a hydrogen atom on the carbon atom' A monocarboxylic acid having two or more hydroxyl groups is reacted to prepare a multi-branched polymer, and this is reacted with acrylic acid, methacrylic acid, and a polyacrylic acid-containing acrylic acid compound, 4-chloromethylstyrene. And introducing a polymerizable double bond to obtain a multi-branched macromonomer; (3) a compound having one or more hydroxyl groups, which is formed into a multi-branched polymer by a cyclic reaction of a cyclic ether compound having one or more hydroxyl groups , the end of the polymer, the hydroxyl group Acrylic acid, methacrylic acid, an isocyanate-containing acrylic compound '4-chloromethylstyrene, etc. are reacted, and a polymerizable double bond is introduced to obtain a multi-branched macromonomer; (4) There will be one or more via The compound of a hydroxyl group is reacted with a compound containing two or more hydroxyl groups, a halogen atom, -S020CH3-, -Os02CH3 - or the like to form a multi-branched polymer, and then the terminal group of the polymer, that is, a hydroxyl group, and acrylic acid, A Acrylic acid, isocyanate-containing C--12-201139470 enoic acid compound, 4-chloromethylstyrene, etc. are reacted, and a polymerizable double bond is introduced to obtain a multi-branched macromonomer; (5) a guanamine bond is transmitted through the nitrogen A PAM AM dendrimer which is a repeating structure of an atom reacts with a propionic acid, a methyl propylene acid, an acrylic compound containing a cyanate ester, 4-chloromethylstyrene, etc., and is introduced. a polymerizable double bond to obtain a multi-branched macromonomer; in the above (1), an AB2 type having an active methylene group, a bromine, a chlorine, a methylsulfonyloxy group or a toluenesulfonyloxy group in one molecule Body, for example, halogen Alkoxy-phenylacetonitriles or phenylacetonitriles having a tosyloxy group. In the above (2), 'a monocarboxylic acid having a carbon atom adjacent to a carboxyl group which is a saturated carbon atom and a hydrogen atom on the carbon atom is completely substituted and having two or more hydroxyl groups' may, for example, be a dimethylol group. Propionic acid, α, α-bis(transmethyl)butyric acid, α'α, α-gin (hydroxymethyl)acetic acid, α,α-bis(hydroxymethyl)pentanoic acid or α,α-double ( Hydroxymethyl) propionic acid and the like. In the above (3), examples of the cyclic ether compound having one or more hydroxyl groups include, for example, 3-ethyl-3-(hydroxymethyl)oxetane and 2,3-epoxy-1. -propanol, 2,3-epoxy-1-butanol or 3,4-epoxy-1-butanol. In the above (4), 'a compound containing two or more hydroxyl groups, a halogen atom, _S020CH3-, -0S02CH3-, etc., for example, 5-(bromomethyl)-1,3-dihydroxybenzene, 2 -ethyl-(bromomethyl)-i,3-propanediol, 2-methyl-2-(bromomethyl)-i, 3-propanediol, 2-(bromomethyl)_2-(hydroxymethyl)-1, 3-propanediol and the like. In the above-mentioned (5), the PAMAM dendrimer can be produced, for example, by the method disclosed in Japanese Patent Publication No. Hei 6-070132 and Japanese Patent Publication No. Hei 7-042352. Further, the multi-branched macromonomer (a3) must have a weight average molecular weight of 1,000 to 15,000. The molecular weight was determined by GPC-MALS (Shodex HPLC, detector Wyatt Technology DAWN EOS, Shodex RI-101, column Shodex KF-806L><2, dissolved in Ij THF (tetrahydrofuran), flow rate: 〇ml/min conditions). Further, the analysis of the GPC_MALS measurement was carried out by Wyatt's analytical software ASTRA, and the weight average molecular weight was determined. When the molecular weight is less than 1, 〇〇〇, the amount of introduction of the branched structure is insufficient to change to a physical property similar to that of the previous linear styrene-acrylic acid copolymer, and it is difficult to obtain benzene having a broad molecular weight distribution width as defined in the present invention. The practical strength of the molded article obtained from the vinyl resin composition is also insufficient. Further, when the molecular weight exceeds 1 5,000', the treatment of the multi-branched macromonomer becomes difficult, and it becomes difficult to uniformly copolymerize the styrene-based monomer (al) and the acrylate oxime 2). More preferably, the molecular weight is from 2,500 to 7,000. Further, in the case of the above-mentioned multi-branched macromonomer (a3), it is preferred to contain 0.1 micromolar to 5.5 micromolar per lg of the polymeric double bond. When it is in this range, the amount of introduction of the branched structure in the obtained multi-branched copolymer (A) can be suppressed, and gelation at the time of production can be prevented, so that it is easy to obtain a desired high-molecular-weight component. And a styrene resin composition having a broad molecular weight distribution. The better content is from 丨.0 to 3.5 micro-mole -14- 201139470. Further, for example, the content is based on methacrylic acid and a derivative thereof, and the condition of the double bond is obtained by containing 1 mol of a double bond in the formula of methyl methacrylate, according to styrene or its The conditions of the compound-like double bond are those obtained by containing a 1 molar double bond in the formula of styrene. The styrene resin composition of the present invention needs to copolymerize the styrene monomer (al), the acrylate (a2), and the multi-branched macromonomer (a3) to obtain a multi-branched copolymer. In the case of a copolymer, a low-branched copolymer having a linear copolymer or a multi-branched macromonomer (a3) derived structure containing no styrene monomer (al) and acrylate (a2) at the same time can be obtained. a mixture. In the present invention, since the above-mentioned multi-branched polymer (A) is required, it is not necessary to remove such a linear copolymer or a low-branched copolymer, and the M w and M w specified as described above are not required. / η η ratio, the styrene resin composition of the present invention can be used as it is. In addition, when the manufacturing of the first stage is not satisfied with the above-mentioned Mw and Mw/Mn, the resin obtained by copolymerizing the styrene monomer (al) and the acrylate (a2) may be additionally adjusted. Further, the styrene resin composition of the present invention must have a ratio (ai)/(a2) of the styrene monomer 〇1) to the acrylate (a2) of 87/13 to 96/4 (mass ratio). As described above, even when a resin obtained by copolymerizing a styrene monomer (a1) and an acrylate (a2) is additionally mixed and adjusted, a styrene-based monomer derivative component is formed in a styrene resin composition. The mass ratio of the content rate to the content ratio of the acrylate (a2)-derived component must be within this range. When the ratio of use of acrylate is smaller than 4, the molding processability of -15 to 201139470 is insufficient, and it is difficult to exhibit the effect of imparting workability to the object of the present invention. Further, from the viewpoint of low-temperature moldability and sharpness of the sheet, the use ratio of the acrylate is preferably 4 or more. Further, when the use ratio of the acrylate exceeds 13.0, the Vicat softening temperature is lowered, and the heat resistance of the molded article is lower than the practical range. From the viewpoint of excellent physical property balance of the obtained molded article, butyl acrylate is used as the acrylate (a2), and (al) / butyl acrylate is preferable in terms of the ratio of use of the styrene monomer (al). It is 92/8 to 96/4 (mass ratio). Further, the multi-branched macromonomer (a3) is preferably used in an amount of from 100 to 10,000 ppm based on the total mass of the acrylic monomer (al) and the acrylate (a2). In the method for producing a multi-branched copolymer used in the present invention, the styrene monomer (al), the acrylate (a2), and the multi-branched macromonomer (a3) are copolymerized. The styrene resin composition containing the multi-branched copolymer (A) is not particularly limited as long as it has a molecular weight/molecular weight distribution range specified in the present invention. From the viewpoint of the purpose of producing a styrene-based resin composition more efficiently in the reaction of the first stage, it is preferred that the present invention adopts the production method provided in the Japanese Patent Publication No. 2000- 05 3 93 9 Specifically, it is preferred to carry out the reaction by a solution polymerization method or a melt polymerization method (block polymerization method) of the mixture containing the above raw materials (al) to (a3). At this time, the reaction can be carried out without adding an organic solvent, but it is preferred to control the molecular weight of the polymer by using a small amount of an organic solvent to reduce the viscosity of the reactant by 倂 -16-201139470. With respect to the organic solvent to be used, a chain transfer constant of 5 to 4 is preferably '〇.2χ1〇 to 0.8χ1 (Γ5 is more preferable. Other examples are preferably toluene, ethylbenzene, Xylene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, anisole, cyanobenzene, dimethylformamide, hydrazine, hydrazine-dimethylformamide, methyl ethyl ketone, etc. The amount is preferably from 5 parts by mass to 50 parts by mass, more preferably from 6 parts by mass to 20 parts by mass, based on 100 parts by mass of the total of the raw material monomers. Further, when the polymerization is carried out using an organic solvent, it is easy to suppress the organic compound. In particular, when the amount of the multi-branched macromonomer (a3) to be added is large, it is necessary to use the above-mentioned organic solvent from the viewpoint of suppressing gelation. The amount of addition of the multi-branched macromonomer is shown. As for the initiation of the polymerization, a radical polymerization initiator can be used. In terms of the initiator, the half life is preferably 10 hours and the temperature is 75 to 140 °C. More preferably, the temperature is 8 5 to 1 3 5 hours. For example, 1,1 - double (three Butylperoxy)cyclohexane, 2,2-bis(tri-butylperoxy)butane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, etc. Peroxy ketals; hydroperoxides such as cumene hydroperoxide and tertiary butyl hydroperoxide; di-tertiary butyl peroxide, dicumyl peroxide, Dialkyl peroxides such as di- or tertiary hexyl peroxide; bismuthinoyl peroxides such as benzammonium peroxide and bismuthinoyl peroxide; and peroxybenzoic acid - 201139470 Peroxyesters such as tertiary butyl acid ester, di-tertiary butyl peroxy isophthalate, peroxyisopropyl monocarbonate-tertiary butyl ester; N, N'-azo Diisobutyl nitrile 'N,N'-azobis(cyclohexane-1-carbonitrile), N,N'-azobis(2-methylbutyronitrile), N,N'-azo double (2,4-dimethyl dimethyl nitrile) and N,N'-azobis[2-(hydroxymethyl)propanenitrile] may be used alone or in combination of two or more. In terms of mass, the mass of the monomer synthesized relative to the raw material is preferably from 50 ppm to 1,000 ppm based on the mass. Further, the molecular weight of the styrene resin composition containing the multi-branched copolymer (A) is not excessively increased, and a chain transfer agent may be added. In general, a monofunctional chain transfer agent having one chain transfer group may be used, or a polyfunctional chain transfer agent having a plurality of chain transfer agents may also be used. Examples of the monofunctional chain transfer agent include alkyl mercaptans, Glycolic acid vinegar, etc. In terms of the polyfunctional chain transfer agent, glycerol, neopentyl glycol, trimethylolpropane, and neopentyl alcohol are exemplified by thioglycolic acid or 3-hydrothiopropionic acid. A polyol having a hydroxyl group such as dipentaerythritol, tripentenol or sorbitol is subjected to acetification. Conventionally, it has been known that a molded article obtained by using the obtained styrene monomer (al) and acrylic acid vinegar (a2) has flexibility (flexibility). However, in this case, by lowering the softening point of the copolymer, heat resistance is insufficient and mechanical strength is not practical. On the other hand, it is known that a multi-branched macromonomer (a3) is used in -18 - 201139470, and a copolymer having excellent fluidity can be obtained although it contains a substance'. In the case of multi-branched macromonomers, the fluidity is not only better than that of the same linear resin, but also with the large-scale/thin thickness/high design, and further, as it becomes required to have further processability. . In addition, the point 'the formability at a lower temperature is also necessary, and in order to improve the productivity, it is also necessary to prevent the mold release property. The present invention can provide a styrene resin having excellent balance of properties. The styrene resin composition of the styrene resin group branched copolymer (A) used in the present invention can be obtained by a GPC-MALS method to obtain a weight average molecular weight of 60. The ratio (Mw/Μη) of the weight average molecular weight (Mw) to the number of the right weight is 2.7 to 4.0, and the composition of the polymer (Α) may be composed of a plurality of branches; In other words, in the case of the other components herein, the weight-average molecular weight of the composition of the right-handed ethylene resin is not deviated from the above range, and is not particularly limited. However, various copolymers such as copolymers may be used depending on the application. Compounds, etc. For the above-mentioned additives, for example, each agent, an antistatic agent, a lubricant, an antifogging agent, and an antibacterial high molecular weight copolymerization can be used, however, the diversification of the molded article of the weight average molecular weight (the various molding methods) From the viewpoint of energy reduction, the mold of the mold is used. The resin stain of the mold solves such a demand, and the composition has a large amount as described above, and the amount (Mw) of the composition is 300,000 to the average molecular weight. (Μη) is a multi-branched co-electropolymer (Α) and other idioms, the use of the other amount of average molecular weight and number does not hinder the effect of the case of the additive or the above-mentioned line stabilizer, anti-blocking agent, anti- Oxidizing agent, dyeing, 19-201139470, ultraviolet absorber, etc. However, the benzene-based resin composition used in the present invention is a mineral oil used in order to impart mold release property or moldability to workability. Etc., there are also such excellent properties, and the use of additives must be noted differently from the use of additives in conventional styrene-(meth)acrylic copolymers. The molded article of the present invention is not limited to the above-described styrene-ethylene-based resin composition of the present invention, and is, for example, a molding method such as injection, extrusion, blow molding, compression, or the like, to form an injection molded article, a sheet, In particular, the styrene-based resin composition of the present invention is excellent in productivity such as excellent moldability and mold release property, and can be suitably used for mass-produced applications such as transparent large-size injection molded articles. In particular, the styrene resin composition of the present invention can be suitably used for a biaxially stretched styrene resin sheet. The stretching method is not particularly limited, but the radiant heating type vacuum forming method is excellent in secondary workability. The heat shrinkage stress of one of the longitudinal direction and the transverse direction of the obtained sheet is preferably in the range of 0.2 MPa to 0.45 MPa. The heat shrinkage stress is as described in the above-mentioned Patent Document 2 and Patent Document 3, and is generally in the technical field. The physical properties of the crucible are determined based on ASTM D-105. In the present invention, the longitudinal direction of the biaxially oriented sheet is used. The radiant-heated vacuum forming of the shape is applied to the (MD) and the transverse direction (TD) which are orthogonal to each other via a relatively low-lying range of 0.20 MPa to 0.45 MPa. When the thickness unevenness is not caused, the thickness uniformity of the molded article is excellent. Such a low heat shrinkage stress is preferable in the spoke-20-201139470 shot-heating vacuum forming, which has been found in the aforementioned Patent Document 2, but The present invention does not impair the transparency originally possessed by the styrene resin, and in order to secure the optimum heating time as the above-mentioned practical problem, it is necessary to use a styrene resin composition having a multi-branched structure and having a specific molecular weight/molecular weight distribution range. The stress can be adjusted according to the extension temperature/stretching ratio, but it is difficult to specify specific manufacturing conditions even if the sheet width is further varied depending on the extrusion speed of the sheet/before extrusion (before stretching). However, in general production conditions, the above-mentioned styrene resin composition has a Vicat softening point + (〇 40 ° C) in terms of elongation temperature, and in terms of stretching ratio, 1.5 in one direction. ~5.0 times is preferred. If the enthalpy is within this range, the radiant heating type vacuum forming can easily produce a sheet having a heat shrinkage stress in a range which is likely to be preferable. Further, the thickness of the sheet obtained by the biaxial stretching is not particularly limited, but it is preferably from the viewpoint of being applicable to a general radiant heating type vacuum forming machine in the range of 〇 1 to 1 mm. The method for producing the biaxially stretched styrene resin sheet of the present invention is not particularly limited. In the production of the conventional stretch sheet, it can be carried out by a method used in the production of the conventional stretch sheet. In one example, the styrene resin composition is supplied to an extruder, and after melt-mixing, continuous extrusion is performed by a T-die or a circular mold, etc., and the sheet is continuously subjected to a tenter method, a bubble method, or the like. The method of biaxial stretching is performed simultaneously. Further, the biaxially stretched styrene resin sheet of the present invention may be coated with an antifogging agent or a releasing agent on one side or both sides of at least -21 to 201139470. Antifogging agents and release agents can also be used. As the antifogging agent, for example, a nonionic surfactant such as a sorbitan fatty acid ester, a sucrose fatty acid ester, a polyglycerin fatty acid ester or a polyoxyethylene derivative can be used, and these may be used singly or in a mixture. use. As the release agent, for example, a polyoxygenated oil or an emulsion thereof or the like. Further, various nonionic surfactants, cationic surfactants, anionic surfactants, and the like can be applied as an antistatic agent. Examples of such coating methods include a spray coater, a roll coater, a gravure roll coater, a pneumatic blade coater, an air knife coater, and a rotary-rotor coater. Applicator method, etc. The biaxially stretched styrene-based resin sheet of the present invention can be printed on the surface of the sheet or can have barrier properties and antibacterial properties in order to impart designability, functionality, and the like within a range that does not impair the effects of the present invention. The functional resin such as weldability is laminated on the surface of the sheet. Further, a biaxially stretched styrene resin sheet of the present invention or the like may be laminated on the foamed sheet to be used as a part of the container. Since the biaxially stretched styrene resin sheet of the present invention has an anti-blocking effect, it can contain various fine particles. Examples of the fine particles include resin crosslinked particles such as styrene resin crosslinked particles, (meth)acrylate resin crosslinked particles, and polyurethane resin crosslinked particles: cerium oxide Hydrophobized inorganic fine particles such as cerium oxide, spherical cerium oxide, light calcium carbonate, titanium oxide, and talc; rubber fine particles such as styrene grafted diene rubber. In particular, since the biaxially stretched styrene tree-22-201139470 fat sheet and the molded article using the same have high strength, anti-blocking property and peeling property, it is particularly preferable to be a styrene-grafted diene rubber. In other words, in the styrene-grafted diene rubber, since the biaxially stretched styrene resin sheet can be obtained and the balance between the strength and the appearance of the molded article using the same is excellent, the biaxially stretched styrene resin sheet is used. It is preferable that the average particle diameter is in the range of 0.1 to 5.0 μm and the diene component is in the range of 0.05 to 3.0% by mass. In order to obtain higher transparency, it is preferable to contain 〇.〇5~〇.5 mass%. Further, the biaxially stretched styrene of the present invention is improved in the elongation at the time of film formation of the biaxially stretched styrene resin sheet, the deep drawing formability at the time of secondary molding of the container, and the low temperature formability. The resin sheet may contain mineral oil. However, the volatile component of the mineral oil generated during the melt extrusion adheres to the sheet manufacturing apparatus, and when it is transferred onto the sheet, it is preferably 0.5 in order to prevent the appearance of the biaxially stretched styrene resin sheet from being poor. 5% by mass or less. The above various particles or mineral oils may be added to the obtained biaxially stretched styrene resin composition by the above method' and may be contained in the biaxially stretched styrene resin sheet. In the forming method of the secondary processing of the biaxially stretched styrene resin sheet, it is preferable to use radiant heating type vacuum forming. The shape and use of the molded article are not particularly limited, and examples thereof include a lid for a food container, a tray, a food packaging bag, a bubble wrap, various other packaging bags, a box, and the like. In particular, the molded article obtained by the radiant heating type vacuum forming using the biaxially stretched styrene resin composition of the present invention is not in contact with the hot plate in -23-201139470, and is not provided for pressure adjustment. The fine pores on the hot plate are transferred, and the hot plate dirt from the antifogging agent or the like applied on the surface of the sheet is transferred, so that it has excellent transparency. [Examples] The following examples are given to illustrate the invention in more detail, but the invention is not limited to the examples. In addition, "%" means "% by mass" unless otherwise specified. The following are evaluation methods and the like. [GPC-MALS measurement conditions] GPC-MALS measurement of styrene resin composition in Shodex HPLC, detector Wyatt Technology DAWN EOS, Shodex RI-101, column Shodex KF-806LX2, solvent THF, flow rate 1.0 ml/min Conditions to proceed. Further, the measurement analysis of GPC-MALS was carried out by Wyatt's analytical software ASTRA to calculate the weight average molecular weight, the number average molecular weight, and the like of the styrene resin composition. [Melt flow rate (MFR) measurement method] Measured in accordance with JIS K7210. Further, the measurement conditions were a temperature of 200 ° C and a load of 49 N. [Charpy impact strength]: Measured in accordance with JIS K71 1 1. [Vicat softening temperature]: Measured according to JIS Κ7206··99. [Injection Forming Processability] A pudding type container was formed by a 150-ton injection molding machine manufactured by Nippon Steel Co., Ltd., and evaluated according to the following evaluation criteria. -24- 201139470 The container is easy to form and has no thickness unevenness. · ◎ The container is relatively easy to form and has no thickness unevenness: the container is relatively easy to form and has uneven thickness: △ The container is difficult to form and has uneven thickness: X [ Sheet forming workability] Using a sheet extruder (spiral diameter of 30 mm), the resin was extruded at a temperature of 210 ° C to 230 ° C and a pressing speed of 0.8 to lm / min to produce a thickness of 〇. .4mm sheet sample. Then, the sheet sample was heated using a vacuum forming machine at a heating temperature of 290 ° C to 300 ° C for a heating time of 10 seconds to 30 seconds, and then the sheet surface before heating of the sheet was measured as a reference. The sag length of the center portion of the sheet is evaluated by the following evaluation criteria based on the sag length of the sheet with respect to the heating time. When the heating time is 20 seconds, the sag amount is less than 20 mm, ◎, 20 to less than 40 mm. '40mm or more is X» When the heating time is 30 seconds, the sag amount is less than 30 mm, ◎, 30 to less than 60 mm is 〇, and 60 mm or more is X. However, when the heating time was evaluated as X with respect to either side and the other side was 〇 or ◎, the evaluation was eight. [Release property] A box shape of 20 cm x 15 cm cm was formed by a 150-ton injection molding machine manufactured by Nippon Steel Co., Ltd., and evaluated according to the following evaluation criteria. ◎: It is easy to release the mold at a continuous injection volume of 50 or more. It is easy to release the mold at a continuous injection volume of 30 - 2011-39470. △: It is difficult to release the mold over a continuous injection volume of X. X: The mold release amount is 1 to 2 consecutive shots. Difficult [Practical Heat Resistance] A 150-ton injection molding machine manufactured by Nippon Steel Co., Ltd. was used to form a box shape of 20 cm x 15 cm x 4 cm. The molded article was placed at an ambient temperature of 70 ° C for 1 hour, and when the molded article was not deformed, it was evaluated as ◎, and a small amount of deformation was observed. The time is evaluated as 〇, which is obviously deformed and is evaluated as x when the degree is large.
在苯乙烯系樹脂組成物中添加 2 %高衝擊聚苯乙烯 DICK STYRENE GH-8 3 00- 5，並供應至具有φ30ι\η直徑的 螺旋之二軸擠壓機（日本製鋼所股份有限公司製造 TEX30a — 3 1.5BW-5V)，熔融混練，經由 Τ-鑄模擠壓，以 輥冷卻，再加熱後，經由輥群的速度差，在薄片流動方向 (稱爲MD)延伸之後，以拉幅機在相對薄片流動方向爲正 交的方向（稱爲TD)進行延伸，製作厚度爲0.25mm之薄片 。此外，延伸倍率記載於表中。延伸溫度調整成爲如表中 的加熱收縮應力。經由下述來評估關於薄片影像清晰性、 耐折強度、輻射熱式壓空真空成形法中最適加熱時間。 [像顯明度] JIS K73 74在柵間隔0.5mm進行評估，50%以上爲合 格（〇 )。此外，7 0 %以上爲◎。 [耐折強度] JIS P8115縱方向與橫方向的平均6次以上爲合格（〇 -26 - 201139470 )。此外，1 〇次以上爲◎。 [加熱收縮應力] 根據ASTM D-1504來測定。 [最適加熱時間] 使用淺野硏究所股份有限公司製造FK-CM3 1-1 熱器在溫度 3 7 (TC時改變加熱時間，用正面 1 Ocm XI Ocm、收縮比0.3的模具形成薄片，在同一力 間，所獲得的成形品重量差變成± 1 0 %以上之時間估 形上限値。此外，以5mm(p的穴之模具中成形，突走 度變成1 . 5 mm以上之時間做爲下限値。該成形範圍 以上者爲合格（〇 )。 (參考例1)多分支狀巨單體（a3-l)之合成 <多分支聚醚多元醇的合成> 在具備攪拌器、溫度計、滴液漏斗及冷凝器之2 燒瓶中，在室溫下添加 50.5g之乙氧基化新戊四醇 耳-氧化乙烯加成新戊四醇）、lg BF3二乙基醚溶液 ，加熱至ll〇°C。至此，將450g之3 -乙基- 3- (羥基 氧雜環丁烷在2 5分鐘內慢慢加入的同時，控制反历 致的放熱。放熱結束時，在120 °C將反應混合物另夕 拌3小時，之後，冷卻至室溫。所獲得的多分支聚国 醇的重量平均分子量爲3,000、羥基價爲530。 <具有甲基丙烯醯基及乙醯基之多分支狀巨單| 成> 〇，加 寬度 口熱時 k爲成 已的高 1秒 公升 (5莫 (50%) 甲基） I所導 卜再攪 I多元 I的合 -27- 201139470 在具備攪拌機、溫度計、冷凝器之具備迪安斯塔克傾 析離心機（Dean Stark Decanter)及氣體導入管之反應器中 ，加入利用上述的 < 多分支聚醚多元醇1的合成 >而獲得的 多分支聚醚多元醇50g、甲基丙烯酸I3.8g、甲苯150g、 氫醌〇.〇6g、對甲苯磺酸lg，一邊以3毫升/分鐘的速度將 7%含有氧氣的氮氣（v/v)吹入混合溶液中，一邊在常壓下 攪拌、加熱。調節加熱量使對傾析離心機的餾出量1小時 變爲30g ’脫水量到達2.9g爲止繼續加熱。反應終了之後 ’一次冷卻，加入醋酸酐3 6 g、胺磺酸5.7 g，在6 CTC攪拌 1 〇小時。之後，爲了除去殘餘的醋酸及氫醌，因此以5 % 氫氧化鈉水溶液5 0 g清洗4次，另外以1 %硫酸水溶液 5〇g清洗1次’以水50g清洗2次。在獲得的有機層上加 入氫醌單甲醚0.02g，在減壓下一邊導入7 %含有氧氣之氮 氣（v/v)—邊餾除溶劑，而獲得具有異丙烯基及乙醯基之多 分支狀巨單體（a3-l)60g。所獲得的多分支狀巨單體 的重量平均分子量爲3,900，對多分支聚醚多元醇的異丙 烯基及乙醯基之導入率分別爲30莫耳％及62莫耳％。所 以，聚合性雙鍵的導入量爲1.5〇微莫耳/克。 (參考例2)多分支狀巨單體（a3_2)的合成 <具有苯乙烯基及乙醯基之多分支狀巨單體的合成> 在具備攪拌機、乾燥管之具備冷凝器、滴液漏斗及溫 度計之反應器中，加入利用上述的 < 多分支聚醚多元醇1 的合成 > 而獲得的多分支聚醚多元醇50g、四氫呋喃i〇0g -28- 201139470 及氫化鈉4.3g，在室溫下攪拌。對此，將4_氯甲基苯乙 稀26.7g花費！小時逐滴加入，所獲得的反應混合物在5〇 °C另外再攪拌4小時。反應終了之後，暫予冷卻，加入醋 酸酐3 4 g '胺磺酸5 ·4 g ’在6 〇亡攪拌1 〇小時。之後，在 減壓下飽除四氫呋喃，將所獲得的混合物溶解於l5〇g甲 苯中’爲了除去殘餘的醋酸，因此以5 %氫氧化鈉水溶液 5〇g清洗4次’另外以1%硫酸水溶液5〇g清洗i次，以 水5 0g清洗2次。在減壓下從所獲得的有機層餾除溶劑， 而獲得具有苯乙烯基及乙醯基之多分支狀巨單體（a3-2)70g 。所獲得的多分支狀巨單體（a3-2)的重量平均分子量爲 4,800 ’對多分支聚醚多元醇的苯乙烯基及乙醯基之導入 率分別爲3 8莫耳％及5 7莫耳％。所以，聚合性雙鍵的導 入量爲1.31微莫耳/克。 (參考例3)多分支狀巨單體（a3-3)的合成 <具有甲基丙烯醯基及乙醯基之多分支狀巨單體的合 成> 將攪拌器、壓力計、冷卻器及淺盤安裝於4 口燒瓶上 ，對此，添加3 0 8.9g的乙氧基化新戊四醇與〇.46g的硫酸 。之後，加溫至140°C，在10分鐘內添加460.5g的2,2-二（羥基甲基）丙酸。將2,2-二（羥基甲基）丙酸完全溶解， 因爲變成透明溶液，因此減壓至30~40mmHg，一邊攪拌 ，一邊進行4小時反應將酸價變成7_OmgKOH/g爲止。之 後，在該反應液中花費15分鐘添加921g的2,2 _二（羥基 -29- 201139470 甲基）丙酸與〇.92g的硫酸，變成透明溶液之後，減壓至 30〜40mmHg，一邊攪拌，一邊進行反應3小時，而獲得聚 酯多元醇。在具備7%氧氣導入管、溫度計、冷凝器之具 備迪安斯塔克傾析離心機及攪拌機之反應器中，添加以上 述所產生的聚酯多元醇l〇g、二丁基氧化錫1.25g、具有 異丙烯基之甲基丙烯酸甲酯l〇〇g及氫醌0.05g，在混合溶 液中一邊以3ml/分鐘的速度吹入7%氧氣，一邊在攪拌下 加熱。調節加熱量使對傾析離心機的餾出量1小時變爲 15〜2 0g，每1小時取出傾析離心機內的餾出液，對此，一 邊添加相當量的甲基丙烯酸甲酯，一邊進行反應4小時。 反應終了之後，在減壓下餾除甲基丙烯酸甲酯，爲了封阻 殘餘的羥基，因此添加醋酸酐l〇g、胺磺酸2g，在室溫攪 拌1〇小時。以過濾除去胺磺酸，在減壓下濾除醋酸酐及 醋酸之後，在醋酸乙酯7 0g中溶解殘餘物，爲了除去氫醌 ，因此以5%氫氧化鈉水溶液20g清洗4次。另外以7%硫 酸水溶液20g清洗2次，以水20g清洗2次。在所獲得的 有機層中添加〇.〇〇45g之氫醌單甲醚，在減壓下一邊導入 7 %氧氣一邊餾除溶劑，可獲得具有異丙烯基及乙醯基之 多分支狀巨單體llg。所獲得的多分支狀巨單體（a3·3)的 重量平均分子量爲3,000，數量平均分子量爲2,100，異丙 烯基及乙醯基之導入率分別爲5 5莫耳％及3 6莫耳％。所 以，聚合性雙鍵的導入量爲2.00微莫耳/克。 (參考例4)多分支狀巨單體（a3-4)的合成 -30- 201139470 <具有苯乙烯基之PAMAM樹枝狀高分子的合成> 在具備攪拌機、乾燥管之具備冷凝器' 滴液漏斗及溫 度計之反應器中加入 50gPAMAM 樹枝狀高分子 (generation 2.0: Dentritech 公司製造）的甲醇溶液（2〇%)， 在減壓下’ ~邊攪拌—邊餾除甲醇。接者，添加50g之四 氫呋喃及3.〇g微粉化之氫氧化鉀，在室溫下攪拌。對 此’將7.0g之4 -氯甲基苯乙烯花費1〇分鐘逐滴加入，所 獲得的反應混合物在5 Ot另外攪拌3小時。反應終了之 後’冷卻並過濾固體之後，減壓下將四氫呋喃餾除，而獲 得具有苯乙烯基之PAMAM樹枝狀高分子l3g。所獲得的 樹枝狀高分子的苯乙烯基含有率（聚合性雙鍵的導入量）爲 2.7微莫耳/克。所獲得的多分支狀巨單體（a3_4)的重量平 均分子量爲4,050。 (參考例5)多分支狀巨單體（a3-5)的合成 <具有苯乙烯基及乙醯基之多分支狀聚醚多元醇> 在具備攪拌機、冷凝器、遮光性滴液漏斗及溫度計且 可氮氣密封之遮光性反應容器中，在氮氣氣流下，添加 〇.5g之1，3,5-三羥基苯、29g之碳酸鉀、2.7g之18-冠-6 及180g之丙酮，此外，一邊攪拌，一邊花費2小時逐滴 加入由21.7g之5-(溴甲基）-1，3-二羥基苯及l80g之丙酮 所構成之溶液。之後，在攪拌下、加熱、回流，直到.5_( 溴甲基）-1,3-二羥基苯消失爲止。之後，添加9g之4_氯 甲基苯乙烯’進一步在攪拌下、加熱、回流，直到該等消 -31- 201139470 失爲止。之後，在反應混合物中添加4g之醋酸酐及0.6 g 之胺磺酸，在室溫下攪拌一晚。冷卻後’以過濾去除反應 物中之固體，在減壓下餾除溶劑。將所獲得的混合物溶解 於二氯甲烷中，以水清洗3次之後，在己烷中逐滴加入二 氯甲烷溶液，使生成物沉澱。過濾該等並乾燥’而獲得具 有苯乙烯基及乙醯基之多分狀巨單體（a3-5)12g。重量平均 分子量爲3,200及苯乙烯基的含有率爲3.5微莫耳/克。 實施例1 在本實施例中，使用如第1圖所示之配列裝置。將含 有苯乙烯、丙烯酸丁酯及溶劑等混合溶液經由柱塞泵 (plunger bump)(l)供應至攪拌式反應器（2)中。其後，經由 齒輪栗（3 )供應至循環聚合線（I)上。循環聚合線（I)係由用 以從入口開始依序使內徑2.5吋管狀反應器（瑞士、Brewer gains Sulzer公司製造SMX靜態混合器）（4)、（5)、（6)及混 合溶液循環之齒輪泵（7)所構成。（4)至（6)的反應容積約爲 20L。管狀反應器（6)與齒輪泵（7)之間設置有連接至非循環 聚合線（II)的出口。非循環聚合線（II)從入口依序與上述同 樣的管狀反應器（8)、（9)、（10)與齒輪泵（11)串聯連接， (8)至（10)的反應容積爲i6L。 將由苯乙烯93.5份、丙烯酸丁酯6.5份、乙基苯7份 、參考例1的多分支狀巨單體（a3-l)相對於苯乙烯與丙烯 酸丁酯的合計100份而言之300ppm、聚合引發劑[2,2-雙 (4,4 - 一 -二級丁基過氧基環己基）丙院]相對於苯乙嫌與 -32- 201139470 丙嫌酸丁酯的合計100份而言之15〇ppm構成之混合液進 行調整’使用第1圖所示之裝置以下述之條件連續地進行 聚合。 混合溶液的供給量：9.0公升/小時 在攪拌式反應器的反應溫度：116 °C 在循環聚合線（I)的反應溫度：1 2 0 °C 在非循環聚合線（11)的反應溫度：1 5 5至1 7 01 進行聚合而獲得的混合液以2 6 0 t的熱交換器來加熱 ’在5kPa的減壓下除去揮發性成分後，九粒化而獲得苯 乙烯系樹脂組成物。聚合平均分子量Mw爲38萬、MFR 爲4.0g/10分鐘。此外，重量平均分子量與數量平均分子 量的比Mw/Mn爲2.8.。 實施例2 · 除了使用多分支狀巨單體（a3-2)代替實施例1中多分 支狀巨單體（a3-l)之外’與實施例1相同而獲得苯乙烯系 樹脂組成物。聚合平均分子量Mw爲35萬、MFR爲 3.9g/10分鐘。此外’重量平均分子量與數量平均分子量 的比Mw/Mn爲2.8。 實施例3 除了使用多分支狀巨單體（a3·3)代替實施例1中多分 支狀巨單體（a3-l)之外’與實施例1相同而獲得苯乙烯系 樹脂組成物。聚合平均分子量Mw爲39萬、MFR爲 4.0g/10分鐘。此外’重量平均分子量與數量平均分子量 -33- 201139470 的比Mw/Mn爲2.8。 實施例4 除了使用多分支狀巨單體（a3-4)代替實施例1中多分 支狀巨單體（a3-l)之外，與實施例1相同而獲得苯乙烯系 樹脂組成物。聚合平均分子量Mw爲36萬、MFR爲 4.〇g/10分鐘。此外，重量平均分子量與數量平均分子量 的比Mw/Mn爲2.8。 實施例5 除了使用多分支狀巨單體（a3-5)代替實施例i中多分 支狀巨單體（a3-l)之外’與實施例1相同而獲得苯乙嫌系 樹脂組成物。聚合平均分子量 Mw爲 32萬、MFR爲 3.9g/10分鐘。此外’重量平均分子量與數量平均分子量 的比Mw/Mn爲2.9。 實施例6 除了使實施例1中多分支狀巨單體（a3-l)的添加量爲 1 0 0 p p m之外，與實施例1相同而獲得苯乙烯系樹脂組成 物。聚合平均分子量Mw爲34萬、MFR爲4.3g/l〇分鐘 。此外，重量平均分子量與數量平均分子量的比Mw/Mn 爲 2.8。 實施例7 除了使實施例1中多分支狀巨單體（a3-l)的添加量爲 5 OOppm之外，與實施例1相同而獲得苯乙烯系樹脂組成 物。聚合平均分子量Mw爲46萬、MFR爲3.6g/10分鐘 -34- 201139470 。此外，重量平均分子量與數量平均分子量的比Mw/Mn 爲 2_9。 實施例8 . 除了使實施例2中多分支狀巨單體（a3_2)的添加量爲 1 OOppm之外’與實施例2相同而獲得苯乙烯系樹脂組成 物。聚合平均分子量Mw爲3 1萬、MFR舄4 4g/10分鐘 。此外’重量平均分子量與數量平均分子量的比Mw/Mn 爲 2.7。 實施例9 除了使實施例2中多分支狀巨單體（a3_2)的添加量爲 5 OOppm之外，與實施例2相同而獲得苯乙烯系樹脂組成 物。聚合平均分子量Mw爲43萬'MFR馬3.5 g/10分鐘 。此外’重量平均分子量與數量平均分子量的比Mw/Mn 爲 2.9。 實施例1 0 除了使實施例3中多分支狀巨單體（a3_3)的添加量爲 1 OOppm之外’與實施例3相同而獲得苯乙烯系樹脂組成 物。聚合平均分子量Mw爲36萬、MFR爲4.6g/10分鐘 。此外’重量平均分子量與數量平均分子量的比Mw/Mn 爲 2.8。 實施例1 1 除了使實施例3中多分支狀巨單體（a3_3)的添加量爲 5 OOppm之外’與實施例3相同而獲得苯乙烯系樹脂組成 •35- 201139470 物。聚合平均分子量Mw爲51萬、MFR爲3.3g/10分鐘 。此外，重量平均分子量與數量平均分子量的比 Mw/Mn 爲 3.0。 實施例1 2 除了使實施例4中多分支狀巨單體（a3-4)的添加量爲 1 〇〇Ppm之外，與實施例4相同而獲得苯乙烯系樹脂組成 物。聚合平均分子量Mw爲33萬、MFR爲4_3g/10分鐘 。此外，重量平均分子量與數量平均分子量的比Mw/Mn 爲 2.8。 實施例1 3 除了使實施例4中多分支狀巨單體（a3-4)的添加量爲 5 0 〇 P P m之外，與實施例4相同而獲得苯乙烯系樹脂組成 物。聚合平均分子量Mw爲44萬、MFR爲3.2g/10分鐘 。此外，重量平均分子量與數量平均分子量的比Mw/Mn 爲 2.9。 實施例1 4 除了使實施例5中多分支狀巨單體（a3-5)的添加量爲 1 〇〇ppm之外，與實施例5相同而獲得苯乙烯系樹脂組成 物。聚合平均分子量Mw爲31萬、MFR爲4.4g/10分鐘 。此外，重量平均分子量與數量平均分子量的比Mw/Mn 爲 2.8。 實施例1 5 除了使實施例5中多分支狀巨單體（a3_5)的添加量爲 -36- 201139470 5 0 Oppm之外，與實施例5相同而獲得苯乙烯系樹脂組成 物。聚合平均分子量Mw爲40萬、MFR爲3.4g/10分鐘 。此外，重量平均分子量與數量平均分子量的比Mw/Mn 爲 3 3。 實施例1 6 除了使實施例1中丙烯酸丁酯的添加量爲4.5份之外 ，與實施例1相同而獲得苯乙烯系樹脂組成物。聚合平均 分子量Mw爲33萬、MFR爲4.2g/10分鐘。此外，重量 平均分子量與數量平均分子量的比Mw/Mn爲2.9。 實施例1 7 除了使實施例1中丙烯酸丁酯的添加量爲12.5份之 外，與實施例1相同而獲得苯乙烯系樹脂組成物。聚合平 均分子量Mw爲44萬、MFR爲4.0g/10分鐘。此外，重 量平均分子量與數量平均分子量的比Mw/Mn爲2.8。 實施例1 8 除了使實施例2中丙烯酸丁酯的添加量爲4.5份之外 ，與實施例2相同而獲得苯乙烯系樹脂組成物。聚合平均 分子量Mw爲32萬、MFR爲4.0g/10分鐘。此外，重量 平均分子量與數量平均分子量的比Mw/Mn爲2.7。 實施例1 9 除了使實施例2中丙烯酸丁酯的添加量爲12.5份之 外，與實施例2相同而獲得苯乙烯系樹脂組成物。聚合平 均分子量Mw爲43萬、MFR爲4.2g/10分鐘。此外，重 -37- 201139470 量平均分子量與數量平均分子量的比Μw/Mn爲2.8。 實施例2 0 除了使實施例3中丙烯酸丁酯的添加量爲4.5份之外 ，與實施例3相同而獲得苯乙烯系樹脂組成物。聚合平均 分子量M.w爲36萬' MFR爲4.0g/10分鐘》此外，重量 平均分子量與數量平均分子量的比Mw/Μη爲2.8。 實施例2 1 除了使實施例3中丙烯酸丁酯的添加量爲12.5份之 外，與實施例3相同而獲得苯乙烯系樹脂組成物。聚合平 均分子量Mw爲47萬、MFR爲4.2g/10分鐘。此外，重 量平均分子量與數量平均分子量的比Mw/Mn爲2.9。 實施例2 2 除了使實施例4中丙烯酸丁酯的添加量爲4.5份之外 ，與實施例4相同而獲得苯乙烯系樹脂組成物。聚合平均 分子量Mw爲33萬、MFR爲3.9 g/10分鐘。此外，重量 平均分子量與數量平均分子量的比Mw/Mn爲2.7。 實施例2 3 _ 除了使實施例4中丙烯酸丁酯的添加量爲12.5份之 外，與實施例4相同而獲得苯乙烯系樹脂組成物。聚合平 均分子量Mw爲44萬、MFR爲4.1g/10分鐘。此外’重 量平均分子量與數量平均分子量的比Mw/Mn爲2.8。 實施例24 除了使實施例5中丙烯酸丁酯的添加量爲4.5份之外 -38- 201139470 ，與實施例5相同而獲得苯乙烯系樹脂組成物。聚合平均 分子量Mw爲31萬、MFR爲3.7g/l〇分鐘。此外，重量 平均分子量與數量平均分子量的比Mw/Mn爲2.9。 實施例2 5 除了使實施例5中丙烯酸丁酯的添加量爲12.5份之 外，與實施例5相同而獲得苯乙烯系樹脂組成物。聚合平 均分子量Mw爲46萬、MFR爲4.6 g/10分鐘。此外，重 量平均分子量與數量平均分子量的比Mw/Mn爲3.6。 實施例2 6 除了使實施例6中丙烯酸丁酯的添加量爲4.5份之外 ，與實施例6相同而獲得苯乙烯系樹脂組成物。聚合平均 分子量Mw爲31萬、MFR爲3.8g/10分鐘。此外，重量 平均分子量與數量平均分子量的比Mw/Mn爲2.7。 實施例2 7 除了使實施例6中丙烯酸丁酯的添加量爲12.5份之 外’與實施例6相同而獲得苯乙烯系樹脂組成物。聚合平 均分子量Mw爲40萬、MFR爲4.4 g/10分鐘。此外，重 量平均分子量與數量平均分子量的比Mw/Mn爲2.8。 實施例2 8 除了使實施例7中丙烯酸丁酯的添加量爲4.5份之外 ’與實施例7相同而獲得苯乙烯系樹脂組成物。聚合平均 分子量Mw舄4〇萬、MFR爲3.5g/10分鐘。此外，重量 平均分子量與數量平均分子量的比Mw/Mn爲2.8。 -39- 201139470 實施例2 9 除了使實施例7中丙烯酸丁酯的添加量爲12.5份之 外，與實施例7相同而獲得苯乙烯系樹脂組成物。聚合平 均分子量Mw爲58萬、MFR爲4.1 g/1〇分鐘。此外，重 量平均分子量與數量平均分子量的比Mw/Mn爲3.0。 實施例3 0 除了使實施例1中多分支狀巨單體（a3-l)的添加量爲 6 OOppm之外’與實施例1相同而獲得苯乙烯系樹脂組成 物。聚合平均分子量Mw爲52萬、MFR爲1.8g/10分鐘 。此外，重量平均分子量與數量平均分子量的比Mw/Mn 爲 2 · 9。 比較例1 使用與實施例1相同的反應裝置，將由苯乙烯98份 、丙烯酸丁酯2份、乙基苯6份、參考例1的多分支狀巨 單體U3-1)相對於苯乙烯與丙烯酸丁酯的合計100份而言 之lOOppm、聚合引發劑（2,2-雙（4,4-二-三級丁基過氧基 環己基）丙烷）相對於苯乙烯與丙烯酸丁酯的合計100份 而言之1 5 0Ppm構成之混合液進行調整，以與實施例i相 同條件來進行聚合。 進行聚合而獲得的混合溶液以2 5 0 t的熱交換器來加 熱’在5kPa的減壓下除去揮發性成分後，九粒化而獲得 苯乙Μ系樹脂組成物。所獲得的苯乙烯系樹脂組成物之重 量平均分子量Mw爲37萬、MFR爲1.5g/10分鐘、重量 -40- 201139470 平均分子量與數量平均分子量的比Μw/Mn爲3.2。 比較例2 使用與實施例1相同的反應裝置，將由苯乙烯98份 、丙烯酸丁酯2份、乙基苯7份、參考例1的多分支狀巨 單體（a3-l)相對於苯乙烯與丙烯酸丁酯的合計丨〇〇份而言 之lOOppm、聚合引發劑三級-過氧苯甲酸丁酯相對於苯乙 烯與丙烯酸丁酯的合計100份而言之300ppm構成之混合 液進行調整’使用第1圖所示之裝置以下述之條件連續地 進行聚合。 混合溶液的供給量：9 · 0公升/小時 在攪拌式反應器的反應溫度：1 3 Ot 在循環聚合線（I)的反應溫度：1 3 0 °C 在非循環聚合線（II)的反應溫度：130至145t 進行聚合而獲得的混合液以2 6 0 °C的熱交換器來加熱 ，在5kPa的減壓下除去揮發性成分後，九粒化而獲得苯 乙烯系樹脂組成物。所獲得的苯乙烯系樹脂組成物之重量 平均分子量Mw爲27萬、MFR爲3.5g/10分鐘、重量平 均分子量與數量平均分子量的比Mw/Mn爲2.2。 比較例3 將由苯乙烯100份、乙基苯7份、參考例1的多分支 狀巨單體（a3-l)相對於苯乙嫌1〇〇份而言之300ppm、聚合 引發劑（2,2-雙（4,4-二-三級丁基過氧基環己基）丙烷）相 對於苯乙烯100份而言之150pPm構成之混合液進行調整 -41 - 201139470 ，除了使在非循環聚合線（II)的反應溫度爲145至155°c的 範圍之外，以與實施例1相同的條件進行聚合。進行聚合 而’獲得的混合液以260°C的熱交換器來加熱，在5kPa的減 壓下除去揮發性成分後，九粒化而獲得苯乙烯系樹脂組成 物。所獲得的苯乙烯系樹脂組成物之重量平均分子量Mw 爲28萬、MFR爲2.7g/10分鐘、重量平均分子量與數量 平均分子量的比Mw/Mn爲2.4。 比較例4 將由苯乙烯87.5份、丙烯酸丁酯12.5份、乙基苯7 份、參考例1的多分支狀巨單體（a3-l)相對於苯乙烯與丙 烯酸丁酯的合計100份而言之3 00ppm、聚合引發劑（2,2-雙（4,4-二-三級丁基過氧基環己基）丙烷）相對於苯乙烯 1〇〇份而言之150PPm構成之混合液進行調整，除了使在 非循環聚合線（II)的反應溫度爲1 4 5至1 5 5。(：的範圍之外， 以與實施例1相同的條件進行聚合。進行聚合而獲得的混 合液以260 °C的熱交換器來加熱，在5kPa的減壓下除去揮 發性成分後’九粒化而獲得苯乙烯系樹脂組成物。所獲得 的苯乙烯系樹脂組成物之重量平均分子量Mw爲61萬、 MFR爲3.8 g/10分鐘、重量平均分子量與數量平均分子量 的比Mw/Mn爲2.8。 比較例5 將由苯乙烯85份、丙烯酸丁酯15份、乙基苯7份、 參考例1的多分支狀巨單體（a-3)相對於苯乙烯與丙烯酸丁 -42- 201139470 醋的合計i〇〇份而言之300PPm、聚合引發劑（2,2· 4,4-二-三級丁基過氧基環己基）丙烷）相對於苯乙烯 份而言之15〇ppm構成之混合液進行調整’除了使在 環聚合線（Π)的反應溫度爲145至155°C的範圍之外， 實施例1相同的條件進行聚合。進行聚合而獲得的混 以260 °C的熱交換器來加熱，在5kPa的減壓下除去揮 成分後，九粒化而獲得苯乙烯系樹脂組成物。所獲得 乙烯系樹脂組成物之重量平均分子量Mw爲59萬、 爲3.2 g/1〇分鐘、重量平均分子量與數量平均分子量 Mw/Mn 爲 2.9。 雙（ 100 非循 以與 合液 發性 的苯 MFR 的比 -43- 201139470 [表i] 實施例1 實施例2 實施例3 實施例4 巨單體種 a3-l a3-2 a3-3 a3-4 巨單體添加量 300 300 300 300 BuA使用量 6.5 6.5 6.5 6.5 MFR(g/10 分） 4.0 3.9 4.0 4.0 重量平均分子量(χιό4) 38 35 39 36 Mw/Mn 2.8 2.8 2.8 2.8 夏式衝撃強度(MPa) 2.4 2.4 2.4 2.4 維卡軟化温度 90 90 90 90 射出成形加工性 〇 〇 〇 〇 壓出薄膜成形加工性 〇 〇 〇 〇 脫模性 〇 〇 〇 〇 實用耐熱性 ◎ ◎ ◎ ◎ MD/TD MD/TD MD/TD MD/TD 延伸倍率(倍） 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 i 加熱收縮應力 MD/TD MD/TD MD/TD MD/TD 伸 (MPa) 0.24/0.42 0.27/0.40 0.27/0.42 0.27/0.42 片 影像清晰性 ◎ ◎ ◎ ◎ 耐折強度 〇 〇 〇 〇 最適加熱時間 〇 〇 〇 〇 -44 - 201139470 [表2] 實施例5 實施例6 實施例7 實施例8 巨單體種 a3-5 a3-l a3-l a3-2 巨單體添加量 300 100 500 100 BuA使用量 6.5 6.5 6.5 6.5 MFR(g/10 分） 3.9 4.3 3.6 4.4 重量平均分子量〇1〇4) 32 34 46 31 Mw/Mn 2.9 2.8 2.9 2.7 夏式衝撃強度(MPa) 2.4 2.3 2.9 2.3 維卡軟化温度 90 90 90 90 射出成形加工性 〇 ◎ 〇 ◎ 壓出薄膜成形加工性 〇 〇 ◎ 〇 脫模性 〇 〇 〇 〇 實用耐熱性 ◎ ◎ ◎ ◎ 軸 延 伸 延伸倍率(倍） MD/TD 2.3/3.1 MD/TD 2.3/3.1 MD/TD 2.3/3.1 MD/TD 2.3/3.1 加熱收縮應力(MPa) MD/TD 0.25/0.39 MD/TD 0.27/0.39 MD/TD 0.27/0.43 MD/TD 0.24/0.38 薄 片 影像清晰性 ◎ ◎ ◎ ◎ 耐折強度 〇 〇 〇 〇 最適加熱時間 〇 〇 〇 〇 -45- 201139470 [表3] 實施例9 實施例10 實施例11 實施例12 巨單體種 a3-2 a3-3 a3-3 a3-4 巨單體添加量 500 100 500 100 BuA使用量 6.5 6.5 6.5 6.5 MFR(g/10 分） 3.5 4.6 3.3 4.3 重量平均分子量(X104) 43 36 51 33 Mw/Mn 2.9 2.8 3.0 2.8 夏式衝撃強度(MPa) 2.7 2.3 2.7 2.4 維卡軟化温度 90 90 90 90 射出成形加工性 〇 ◎ 〇 ◎ 壓出薄膜成形加工性 〇 〇 ◎ 〇 脫模性 〇 〇 〇 〇 實用耐熱性 ◎ ◎ ◎ ◎ 延伸倍率(倍） MD/TD 2.3/3.1 MD/TD 2.3/3.1 MD/TD 2.3/3.1 MD/TD 2.3/3.1 加熱收縮應力 MD/TD MD/TD MD/TD MD/TD 延 伸 (MPa) 0.27/0.42 0.25/0.40 0.27/0.43 0.26/0.41 片 影像清晰性 ◎ ◎ ◎ ◎ 耐折強度 〇 〇 ◎ 〇 最適加熱時間 〇 〇 〇 〇 -46- 201139470 [表4] 實施例13 實施例Η 實施例15 實施例16 巨單體種 a3-4 a3-5 a3-5 a3-l 巨單體添加量 500 100 500 300 BuA使用量 6.5 6.5 6.5 4.5 MFR(g/10 分） 3.2 4.4 3.4 4.2 重量平均分子量(XI 〇4) 44 31 40 33 Mw/Mn 2.9 2.8 3.3 2.9 夏式衝撃強度(MPa) 2.7 2.3 2.5 2.4 維卡軟化温度 90 90 90 94 射出成形加工性 〇 ◎ 〇 〇 壓出薄膜成形加工性 〇 〇 〇 〇 脫模性 〇 ◎ 〇 〇 實用耐熱性 ◎ ◎ ◎ ◎ MD/TD MD/TD MD/TD MD/TD 延伸倍率(倍） 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 軸 加熱收縮應力 MD/TD MD/TD MD/TD MD/TD 延 伸 薄 (MPa) 0.28/0.44 0.23/0.37 0.27/0.42 0.27/0.45 片 影像清晰性 ◎ ◎ ◎ ◎ 耐折強度 〇 〇 〇 〇 最適加熱時間 〇 〇 〇 〇 -47- 201139470 [表5] 實施例17 實施例18 實施例19 實施例20 巨單體種 a3-l a3-2 a3-2 a3-3 巨單體添加量. 300 300 300 300 BuA使用量 12.5 4.5 12.5 4.5 MFR(g/10 分） 4.0 4.0 4.2 4.0 重量平均分子量(χιό4) 44 32 43 36 Mw/Mn 2.8 2.7 2.8 2.8 夏式衝撃強度(MPa) 2.7 2.3 2.7 2.3 維卡軟化温度 80 94 80 94 射出成形加工性 ◎ 〇 ◎ 〇 壓出薄膜成形加工性 〇 〇 〇 〇 脫模性 〇 〇 〇 〇 實用耐熱性 〇 ◎ 〇 ◎ MD/TD MD/TD MD/TD MD/TD 延伸倍率(倍） 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 軸 加熱收縮應力 MD/TD MD/TD MD/TD MD/TD 延 伸 (MPa) 0.20/0.35 0.29/0.44 0.22/0.36 0.30/0.44 片 影像清晰性 ◎ ◎ ◎ ◎ 耐折強度 〇 〇 〇 〇 最適加熱時間 〇 〇 〇 〇 -48 - 201139470 [表6] 實施例21 實施例22 實施例23 實施例24 巨單體種 a3-3 a3-4 a3-4 a3-5 巨單體添加量 300 300 300 300 BuA使用量 12.5 4.5 12.5 4.5 MFR(g/10 分） 4.2 3.9 4.1 3.7 重量平均分子量(χιό4) 47 33 44 31 Mw/Mn 2.9 2.7 2.8 2.9 夏式衝撃強度(MPa) 2.6 2.5 2.7 2.3 維卡軟化温度 80 94 80 94 射出成形加工性 ◎ 〇 ◎ 〇 壓出薄膜成形加工性 ◎ 〇 〇 〇 脫模性 〇 〇 〇 〇 實用耐熱性 〇 ◎ 〇 ◎ 延伸倍率(倍） MD/TD MD/TD MD/TD MD/TD 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 軸 加熱收縮應力 MD/TD MD/TD MD/TD MD/TD 延 伸 薄 片 (MPa) 0.22/0.37 0.30/0.46 0.23/0.37 0.27/0.42 影像清晰性 ◎ ◎ ◎ ◎ 耐折強度 ◎ 〇 〇 〇 最適加熱時間 〇 〇 〇 〇 -49- 201139470 [表7] 實施例25 實施例26 實施例27 實施例28 巨單體種 a3-5 a3-l a3-l a3-l 巨單體添加量 300 100 100 500 BuA使用量 12.5 4.5 12.5 4.5 MFR(g/10 分） 4.6 3.8 4.4 3.5 重量平均分子量(χιό4) 46 31 40 40 Mw/Mn 3.6 2.7 2.8 2.8 夏式衝撃強度(MPa) 2.8 2.3 2.8 2.7 維卡軟化温度 80 94 80 94 射出成形加工性 ◎ 〇 ◎ 〇 壓出薄膜成形加工性 〇 〇 〇 〇 脫模性 ◎ 〇 〇 〇 實用耐熱性 〇 ◎ 〇 ◎ MD/TD MD/TD MD/TD MD/TD 延伸倍率(倍） 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 軸 加熱收縮應力 MD/TD MD/TD MD/TD MD/TD 延 伸 (MPa) 0.20/0.35 0.29/0.45 0.20/0.35 0.30/0.45 片 影像清晰性 ◎ 〇 ◎ ◎ 耐折強度 ◎ 〇 〇 〇 最適加熱時間 〇 〇 〇 〇 -50- 201139470 [表8] 實施例29 實施例30 巨單體種 a3-l a3-l 巨單體添加量 500 600 BuA使用量 12.5 6.5 MFR(g/10 分） 4.1 1.8 重量平均分子量(X104) 58 52 Mw/Mn 3.0 2.9 夏式衝撃強度(MPa) 3.1 2.8 維卡軟化温度 80 90 射出成形加工性 ◎ Δ 壓出薄膜成形加工性 ◎ Δ 脫模性 ◎ 〇 實用耐熱性 〇 ◎ MD/TD MD/TD 延伸倍率(倍） 2.3/3.1 2.3/2.8 軸 加熱收縮應力 MD/TD MD/TD 延 伸 (MPa) 0.22/0.38 0.27/0.42 薄 片 影像清晰性 ◎ 〇 耐折強度 ◎ ◎ 最適加熱時間 〇 〇 -51- 201139470 [表9] 比較例1 比較例2 比較例3 比較例4 比較例5 巨單體種 a3-l a3-l a3-l a3-l a3-l 巨單體添加量 100 100 300 300 300 BuA使用量 2.0 2.0 12.5 15.0 MFR(g/10 分） 1.5 3.5 2.7 3.8 3.2 重量平均分子量(χΐ〇4) 37 27 28 61 59 Mw/Mn 3.2 2.2 2.4 2.8 2.9 夏式衝撃強度(MPa) 2.8 2.3 2.2 2.9 3.1 維卡軟化温度 97 98 103 78 75 射出成形加工性 X Δ 0 Δ 〇 壓出薄膜成形加工性 Δ X Δ Δ △ 脫模性 Δ X X 〇 o 實用耐熱性 ◎ ◎ ◎ o X 延伸倍率(倍） MD/TD MD/TD MD/TD MD/TD MD/TD 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 軸 加熱收縮應力 MD/TD MD/TD MD/TD MD/TD MD/TD 延 伸 薄 片 (MPa) 0.25/0.40 0.22/0.45 0.24/0.42 0.27/0.40 0.24/0.45 影像清晰性 X Ο X o o 耐折強度 Ο ο X o o 最適加熱時間 〇 X X X 〇 [產業上的利用可能性] $ ψ發明所獲得的苯乙烯系樹脂組成物較以往的線狀 苯乙ϋ系樹脂組成物具有更廣泛分子量分布範圍，因此， -52- 201139470 即使含有超高分子量成分也具有優異的成形加工性。此外 ，進一步適用使用模具之各種成形方法時，因爲從模具的 脫模性良好，因此不需經由倂用添加劑等而脫膜，因爲表 面沒有污物’因此成本/時間良好的同時生產性亦良好， 可降低不良品產生的程度。又，所獲得的成形品與以往相 同’或也具有該等以上的機械強度。又，二軸延伸該等而 獲得的薄片在輻射加熱式壓空真空成形法中模具再現性充 分且可獲得沒有厚度不均之良好成形品。以輻射加熱式壓 空真空成形法進行二次加工時，因爲與熱板未接觸因此沒 有產生熱板污物，沒有損壞苯乙烯系樹脂的透明性，而具 有優異的影像清晰性。因此，可適用於進一步大型化、厚 度變薄的各種外殼或光學元件、大量生產之各種包裝材料 等。 【圖式簡單說明】 第1圖顯示嵌入具有靜態混合元件之管狀反應器之連 續聚合線的1個例子之步驟圖。 【主要元件符號說明】 1 柱塞泵 2 攪拌式反應器 3 齒輪泵 4 具有靜態混合元件之管狀反應器 5 具有靜態混合元件之管狀反應器 6 具有靜態混合元件之管狀反應器 -53- 201139470 7 齒輪泵 8 具有靜態混合元件之管狀反應器 9 具有靜態混合元件之管狀反應器 10 具有靜態混合元件之管狀反應器 11 齒輪泵 (I) 循環聚合線 (II) 非循環聚合線 -54-2% high-impact polystyrene DICK STYRENE GH-8 3 00-5 was added to the styrene resin composition, and supplied to a two-axis extruder with a diameter of φ30 ιηη (manufactured by Nippon Steel Works Co., Ltd.) TEX30a — 3 1.5BW-5V), melt-kneading, squeezing through a sputum-mold, cooling with a roll, heating, and then passing through the speed difference of the roll group, after the sheet flow direction (called MD) is extended, the tenter is used The sheet was stretched in a direction orthogonal to the sheet flow direction (referred to as TD) to form a sheet having a thickness of 0.25 mm. Further, the stretching ratio is described in the table. The extension temperature is adjusted to the heat shrinkage stress as shown in the table. The optimum heating time in the sheet image clarity, the folding strength, and the radiant heat type vacuum forming method was evaluated by the following. [Image clarity] JIS K73 74 is evaluated at a grid spacing of 0.5 mm, and more than 50% is qualified (〇). In addition, 70% or more is ◎. [Fold-resistance] JIS P8115 is more than 6 times in the vertical direction and the horizontal direction (〇 -26 - 201139470). In addition, more than 1 time is ◎. [Heating shrinkage stress] Measured in accordance with ASTM D-1504. [Optimum heating time] FK-CM3 1-1 heat exchanger manufactured by Asano Research Institute Co., Ltd. was used to change the heating time at a temperature of 3 7 (TC), and the sheet was formed by a mold having a front surface of 1 Ocm XI Ocm and a shrinkage ratio of 0.3. Between the forces, the difference in the weight of the molded product obtained becomes an upper limit of the estimated time of ± 10% or more. In addition, the time is 5 mm (p-shaped in the mold of the hole, and the time when the sag becomes 1.5 mm or more is used as the lower limit).値. The above forming range is acceptable (〇). (Reference Example 1) Synthesis of multi-branched macromonomer (a3-l) <Synthesis of Multibranched Polyether Polyol> In a flask equipped with a stirrer, a thermometer, a dropping funnel, and a condenser, 50.5 g of ethoxylated pentaerythritol-ethylene oxide was added at room temperature. Add neopentyl alcohol), lg BF3 diethyl ether solution, and heat to ll ° ° C. At this point, 450g of 3-ethyl-3-(hydroxyoxetane) was slowly added in 25 minutes, and the exothermic heat was controlled. At the end of the exotherm, the reaction mixture was further stirred at 120 °C. After mixing for 3 hours, it was cooled to room temperature. The obtained multi-branched polyalcohol had a weight average molecular weight of 3,000 and a hydroxyl value of 530. <Multi-branched giant single with methacryl fluorenyl group and acetamidine group | & 〇 〇 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加In the reactor with a mixer, a thermometer, a condenser and a Dean Stark Decanter and a gas introduction tube, the above-mentioned <Synthesis of Multibranched Polyether Polyol 1> 50 g of a multi-branched polyether polyol, 3.8 g of methacrylic acid, 150 g of toluene, 6 g of hydroquinone, lg of p-toluenesulfonate, and 3 At a rate of cc/min, 7% nitrogen gas (v/v) containing oxygen was blown into the mixed solution while stirring and heating under normal pressure. The amount of heating was adjusted so that the amount of distillation in the decanter centrifuge became 30 g. The amount of dehydration reached 2.9 g, and heating was continued. After the completion of the reaction, the mixture was cooled once, and acetic anhydride (3 6 g, 5.7 g of aminesulfonic acid) was added, and the mixture was stirred at 6 CTC for 1 hour. Thereafter, in order to remove residual acetic acid and hydroquinone, it was washed four times with 50 g of a 5 % aqueous sodium hydroxide solution, and once with 5 g of a 1% aqueous sulfuric acid solution, and washed twice with 50 g of water. 0.02 g of hydroquinone monomethyl ether was added to the obtained organic layer, and 7 wt% of nitrogen gas (v/v) containing oxygen was introduced under reduced pressure, and the solvent was distilled off to obtain an isopropenyl group and an ethylidene group. Branched macromonomer (a3-l) 60g. The weight average molecular weight of the obtained multi-branched macromonomer was 3,900, and the introduction rates of isopropenyl and ethylidene groups of the multi-branched polyether polyol were 30 mol% and 62 mol%, respectively. Therefore, the introduction amount of the polymerizable double bond was 1.5 Å micromoles/gram. (Reference Example 2) Synthesis of multi-branched macromonomer (a3_2) <Synthesis of a multi-branched macromonomer having a styryl group and an ethenyl group> In a reactor equipped with a condenser, a dropping funnel, and a thermometer provided with a stirrer or a drying tube, the above-mentioned <Synthesis of Multibranched Polyether Polyol 1> The obtained multi-branched polyether polyol 50 g, tetrahydrofuran i 〇 0 g -28-201139470 and 4.3 g of sodium hydride were stirred at room temperature. For this, 4_chloromethyl phenyl bromide 26.7g is spent! The reaction mixture was added dropwise at 5 ° C for an additional 4 hours. After the end of the reaction, the mixture was temporarily cooled, and acetic anhydride (3 4 g 'aminesulfonic acid 5 · 4 g ' was added and stirred at 6 Torr for 1 hr. Thereafter, tetrahydrofuran was saturated under reduced pressure, and the obtained mixture was dissolved in 15 g of toluene. 'In order to remove residual acetic acid, it was washed 4 times with 5 g of a 5 % aqueous sodium hydroxide solution. 5 μg was washed for 1 time and washed twice with water 50 g. The solvent was distilled off from the obtained organic layer under reduced pressure to obtain 70 g of a multi-branched macromonomer (a3-2) having a styryl group and an ethyl fluorenyl group. The weight average molecular weight of the obtained multi-branched macromonomer (a3-2) is 4,800 ', and the introduction rates of the styryl group and the ethyl sulfonyl group of the multi-branched polyether polyol are 3 8 mol% and 5 7 mo, respectively. ear%. Therefore, the amount of the polymerizable double bond introduced was 1.31 μm/g. (Reference Example 3) Synthesis of multi-branched macromonomer (a3-3) <Synthesis of a multi-branched macromonomer having a methacrylinyl group and an ethenyl group> A stirrer, a pressure gauge, a cooler, and a shallow pan were attached to a 4-necked flask, and 3 0 8.9 g was added thereto. Ethoxylated pentaerythritol with 46.46g of sulfuric acid. Thereafter, the mixture was heated to 140 ° C, and 460.5 g of 2,2-bis(hydroxymethyl)propionic acid was added over 10 minutes. The 2,2-bis(hydroxymethyl)propionic acid was completely dissolved, and since it became a transparent solution, the pressure was reduced to 30 to 40 mmHg, and the reaction was carried out for 4 hours while stirring to adjust the acid value to 7_OmgKOH/g. Thereafter, 921 g of 2,2-di(hydroxy-29-201139470 methyl)propionic acid and ruthenium (92 g) of sulfuric acid were added to the reaction solution for 15 minutes to form a transparent solution, and then the mixture was stirred under reduced pressure to 30 to 40 mmHg. The reaction was carried out for 3 hours to obtain a polyester polyol. In the reactor equipped with a 7% oxygen introduction tube, a thermometer, a condenser and a Dean Stark decanter centrifuge and a mixer, the above-mentioned polyester polyol l〇g, dibutyltin oxide 1.25 was added. g. Methyl methacrylate having an isopropenyl group and 0.05 g of hydroquinone were heated while stirring at a rate of 3 ml/min in a mixed solution while blowing 7% oxygen. The amount of heating was adjusted so that the amount of distillation in the decanter centrifuge was changed to 15 to 20 g for 1 hour, and the distillate in the decanter centrifuge was taken out every hour, and a considerable amount of methyl methacrylate was added thereto. The reaction was carried out for 4 hours. After the completion of the reaction, methyl methacrylate was distilled off under reduced pressure, and in order to block the residual hydroxyl group, 1 g of acetic anhydride and 2 g of aminesulfonic acid were added, and the mixture was stirred at room temperature for 1 hour. The amine sulfonic acid was removed by filtration, and acetic anhydride and acetic acid were filtered off under reduced pressure. The residue was dissolved in 70 g of ethyl acetate. To remove hydroquinone, it was washed four times with 20 g of a 5% aqueous sodium hydroxide solution. Further, it was washed twice with 20 g of a 7% sulfuric acid aqueous solution and twice with water of 20 g. To the obtained organic layer, 45 g of hydroquinone monomethyl ether was added, and the solvent was distilled off while introducing 7% oxygen gas under reduced pressure to obtain a multi-branched giant single crystal having isopropenyl group and ethyl fluorenyl group. Body llg. The obtained multi-branched macromonomer (a3·3) had a weight average molecular weight of 3,000, a number average molecular weight of 2,100, and an introduction ratio of isopropenyl group and ethylidene group of 5 5 mol% and 3 6 mol%, respectively. . Therefore, the introduction amount of the polymerizable double bond was 2.00 μm/g. (Reference Example 4) Synthesis of multi-branched macromonomer (a3-4) -30- 201139470 <Synthesis of PAMAM dendrimer having a styrene group> 50 g of PAMAM dendrimer (generation 2.0: manufactured by Dentritech Co., Ltd.) was added to a reactor equipped with a condenser and a dropping funnel and a thermometer equipped with a stirrer and a drying tube. The methanol solution (2% by weight) was dehydrated under reduced pressure while stirring. Next, 50 g of tetrahydrofuran and 3. 〇g of micronized potassium hydroxide were added and stirred at room temperature. For this, 7.0 g of 4-chloromethylstyrene was added dropwise over 1 minute, and the obtained reaction mixture was further stirred at 5 Ot for 3 hours. After the completion of the reaction, after cooling and filtering the solid, tetrahydrofuran was distilled off under reduced pressure to obtain a PAMAM dendrimer having a styryl group of 13 g. The styrene group content (introduction amount of the polymerizable double bond) of the dendrimer obtained was 2.7 μm/g. The obtained multi-branched macromonomer (a3_4) had a weight average molecular weight of 4,050. (Reference Example 5) Synthesis of multi-branched macromonomer (a3-5) <Multi-branched polyether polyol having a styryl group and an ethenyl group> In a light-shielding reaction container having a stirrer, a condenser, a light-shielding dropping funnel, and a thermometer, which is nitrogen-tight, under a nitrogen gas stream, Add 5 g of 1,3,5-trihydroxybenzene, 29 g of potassium carbonate, 2.7 g of 18-crown-6 and 180 g of acetone, and, while stirring, take 2 hours to add 21.7 g of 5 dropwise. a solution of -(bromomethyl)-1,3-dihydroxybenzene and 1880 g of acetone. Thereafter, the mixture was heated and refluxed with stirring until the .5-(bromomethyl)-1,3-dihydroxybenzene disappeared. Thereafter, 9 g of 4_chloromethylstyrene was added, and further, under stirring, heating and refluxing until the disappearance of -31-201139470 was lost. Thereafter, 4 g of acetic anhydride and 0.6 g of aminesulfonic acid were added to the reaction mixture, and the mixture was stirred at room temperature overnight. After cooling, the solid in the reaction was removed by filtration, and the solvent was evaporated under reduced pressure. The obtained mixture was dissolved in dichloromethane and washed with water three times, and then a dichloromethane solution was added dropwise to hexane to precipitate a product. The particles were filtered and dried to obtain 12 g of a multi-particulate macromonomer (a3-5) having a styryl group and an ethenyl group. The weight average molecular weight was 3,200 and the content of the styryl group was 3.5 μm/g. Embodiment 1 In this embodiment, an arrangement device as shown in Fig. 1 is used. A mixed solution containing styrene, butyl acrylate, and a solvent is supplied to the agitated reactor (2) via a plunger pump (1). Thereafter, it is supplied to the circulating polymerization line (I) via the gear pump (3). The circulating polymerization line (I) consists of a tubular reactor having an inner diameter of 2.5 从 from the inlet (SMX static mixer manufactured by Brewer gains Sulzer, Switzerland) (4), (5), (6) and a mixed solution. The circulating gear pump (7) is composed of. The reaction volume of (4) to (6) is about 20L. An outlet connected to the non-circulating polymerization line (II) is disposed between the tubular reactor (6) and the gear pump (7). The non-circulating polymerization line (II) is connected in series from the inlet to the same tubular reactor (8), (9), (10) and the gear pump (11), and the reaction volume of (8) to (10) is i6L. . The mixture of 93.5 parts of styrene, 6.5 parts of butyl acrylate, 7 parts of ethylbenzene, and the multi-branched macromonomer (a3-1) of Reference Example 1 in terms of 100 parts of 100 parts of styrene and butyl acrylate, The polymerization initiator [2,2-bis(4,4-di-butylperoxycyclohexyl)propyl] is relative to 100 parts of the total of butyl benzene and -32-201139470 The mixture of 15 〇 ppm was adjusted. The polymerization was carried out continuously using the apparatus shown in Fig. 1 under the following conditions. Supply of mixed solution: 9.0 liter / hr in the stirred reactor reaction temperature: 116 ° C in the circulating polymerization line (I) reaction temperature: 1 2 0 ° C in the non-circulating polymerization line (11) reaction temperature: 1 5 5 to 1 7 01 The mixed liquid obtained by the polymerization was heated by a heat exchanger of 2600 t. After removing the volatile component under a reduced pressure of 5 kPa, the mixture was granulated to obtain a styrene resin composition. The polymerization average molecular weight Mw was 380,000 and the MFR was 4.0 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. Example 2 A styrene-based resin composition was obtained in the same manner as in Example 1 except that the multi-branched macromonomer (a3-2) was used instead of the multi-branched macromonomer (a3-1) in Example 1. The polymerization average molecular weight Mw was 350,000 and the MFR was 3.9 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. (Example 3) A styrene-based resin composition was obtained in the same manner as in Example 1 except that the multi-branched macromonomer (a3·3) was used instead of the multi-branched macromonomer (a3-1) in Example 1. The polymerization average molecular weight Mw was 390,000 and the MFR was 4.0 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight -33 to 201139470 was 2.8. (Example 4) A styrene-based resin composition was obtained in the same manner as in Example 1 except that the multi-branched macromonomer (a3-4) was used instead of the multi-branched macromonomer (a3-1) in Example 1. The polymerization average molecular weight Mw was 360,000 and the MFR was 4. 〇g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. Example 5 A styrene-based resin composition was obtained in the same manner as in Example 1 except that the multi-branched macromonomer (a3-5) was used instead of the multi-branched macromonomer (a3-1) in Example i. The polymerization average molecular weight Mw was 320,000 and the MFR was 3.9 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.9. (Example 6) A styrene resin composition was obtained in the same manner as in Example 1 except that the amount of the multi-branched macromonomer (a3-1) in Example 1 was changed to 100 p p m . The polymerization average molecular weight Mw was 340,000 and the MFR was 4.3 g/l 〇 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. (Example 7) A styrene resin composition was obtained in the same manner as in Example 1 except that the amount of the multi-branched macromonomer (a3-1) added in Example 1 was changed to 50,000 ppm. The polymerization average molecular weight Mw was 460,000 and the MFR was 3.6 g/10 min -34 - 201139470. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight is 2-9. (Example 8) A styrene-based resin composition was obtained in the same manner as in Example 2 except that the amount of the multi-branched macromonomer (a3_2) added in Example 2 was changed to 10,000 ppm. The polymerization average molecular weight Mw was 310,000 and MFR 舄 4 4 g/10 min. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.7. (Example 9) A styrene resin composition was obtained in the same manner as in Example 2 except that the amount of the multi-branched macromonomer (a3_2) added in Example 2 was 5,000 ppm. The polymerization average molecular weight Mw was 430,000 'MFR horses 3.5 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.9. (Example 1) A styrene-based resin composition was obtained in the same manner as in Example 3 except that the amount of the multi-branched macromonomer (a3_3) was changed to 10,000 ppm in Example 3. The polymerization average molecular weight Mw was 360,000 and the MFR was 4.6 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. (Example 1) A styrene resin composition was obtained in the same manner as in Example 3 except that the amount of the multi-branched macromonomer (a3_3) was changed to 5 OO ppm in Example 3, and 35-201139470 was obtained. The polymerization average molecular weight Mw was 510,000 and the MFR was 3.3 g/10 minutes. Further, the ratio of the weight average molecular weight to the number average molecular weight, Mw/Mn, was 3.0. (Example 1) A styrene resin composition was obtained in the same manner as in Example 4 except that the amount of the multi-branched macromonomer (a3-4) in Example 4 was changed to 1 〇〇Ppm. The polymerization average molecular weight Mw was 330,000 and the MFR was 4 to 3 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. (Example 1) A styrene resin composition was obtained in the same manner as in Example 4 except that the amount of the multi-branched macromonomer (a3-4) in Example 4 was changed to 50 〇 P P m . The polymerization average molecular weight Mw was 440,000 and the MFR was 3.2 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.9. (Example 1) A styrene-based resin composition was obtained in the same manner as in Example 5 except that the amount of the multi-branched macromonomer (a3-5) in Example 5 was changed to 1 〇〇 ppm. The polymerization average molecular weight Mw was 310,000 and the MFR was 4.4 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. (Example 1) A styrene-based resin composition was obtained in the same manner as in Example 5 except that the amount of the multi-branched macromonomer (a3_5) in Example 5 was changed to -36 - 201139470 5 0 ppm. The polymerization average molecular weight Mw was 400,000 and the MFR was 3.4 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 3 3 . Example 1 6 A styrene resin composition was obtained in the same manner as in Example 1 except that the amount of the butyl acrylate added in Example 1 was 4.5 parts. The polymerization average molecular weight Mw was 330,000 and the MFR was 4.2 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.9. (Example 1) A styrene resin composition was obtained in the same manner as in Example 1 except that the amount of butyl acrylate added in Example 1 was 12.5 parts. The polymerization average molecular weight Mw was 440,000 and the MFR was 4.0 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. Example 1 8 A styrene resin composition was obtained in the same manner as in Example 2 except that the amount of butyl acrylate added in Example 2 was 4.5 parts. The polymerization average molecular weight Mw was 320,000 and the MFR was 4.0 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.7. (Example 1) A styrene resin composition was obtained in the same manner as in Example 2 except that the amount of butyl acrylate added in Example 2 was 12.5 parts. The polymerization average molecular weight Mw was 430,000 and the MFR was 4.2 g/10 minutes. Further, the ratio Μw/Mn of the weight average molecular weight to the number average molecular weight of ～37-201139470 was 2.8. Example 2 0 A styrene resin composition was obtained in the same manner as in Example 3 except that the amount of butyl acrylate added in Example 3 was 4.5 parts. The polymerization average molecular weight M.w was 360,000' MFR was 4.0 g/10 min. Further, the ratio Mw/Μη of the weight average molecular weight to the number average molecular weight was 2.8. [Example 2] A styrene resin composition was obtained in the same manner as in Example 3 except that the amount of butyl acrylate added in Example 3 was 12.5 parts. The polymerization average molecular weight Mw was 470,000 and the MFR was 4.2 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.9. Example 2 2 A styrene resin composition was obtained in the same manner as in Example 4 except that the amount of butyl acrylate added in Example 4 was 4.5 parts. The polymerization average molecular weight Mw was 330,000 and the MFR was 3.9 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.7. Example 2 3 _ A styrene resin composition was obtained in the same manner as in Example 4 except that the amount of butyl acrylate added in Example 4 was 12.5 parts. The polymerization average molecular weight Mw was 440,000 and the MFR was 4.1 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. Example 24 A styrene-based resin composition was obtained in the same manner as in Example 5 except that the amount of butyl acrylate added in Example 5 was 4.5 parts to -38 to 201139470. The polymerization average molecular weight Mw was 310,000 and the MFR was 3.7 g/l〇. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.9. [Example 2] A styrene resin composition was obtained in the same manner as in Example 5 except that the amount of butyl acrylate added in Example 5 was 12.5 parts. The polymerization average molecular weight Mw was 460,000 and the MFR was 4.6 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 3.6. Example 2 6 A styrene resin composition was obtained in the same manner as in Example 6 except that the amount of butyl acrylate added in Example 6 was 4.5 parts. The polymerization average molecular weight Mw was 310,000 and the MFR was 3.8 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.7. [Example 2] A styrene resin composition was obtained in the same manner as in Example 6 except that the amount of butyl acrylate added in Example 6 was 12.5 parts. The polymerization average molecular weight Mw was 400,000 and the MFR was 4.4 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. [Example 2] A styrene resin composition was obtained in the same manner as in Example 7 except that the amount of butyl acrylate added in Example 7 was 4.5 parts. The polymerization average molecular weight was Mw 舄 4 million and the MFR was 3.5 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.8. -39-201139470 Example 2 9 A styrene resin composition was obtained in the same manner as in Example 7 except that the amount of butyl acrylate added in Example 7 was 12.5 parts. The polymerization average molecular weight Mw was 580,000 and the MFR was 4.1 g/1 minute. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 3.0. (Example 3) A styrene-based resin composition was obtained in the same manner as in Example 1 except that the amount of the multi-branched macromonomer (a3-1) added in Example 1 was changed to 600 ppm. The polymerization average molecular weight Mw was 520,000 and the MFR was 1.8 g/10 minutes. Further, the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2 · 9. Comparative Example 1 Using the same reaction apparatus as in Example 1, 98 parts of styrene, 2 parts of butyl acrylate, 6 parts of ethylbenzene, and the multi-branched macromonomer U3-1) of Reference Example 1 were compared with styrene and 100 ppm of butyl acrylate in total, 100 ppm of polymerization initiator (2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane) relative to styrene and butyl acrylate The mixture of 100 parts of 100 pm was adjusted in 100 parts to carry out polymerization under the same conditions as in Example i. The mixed solution obtained by the polymerization was heated by a heat exchanger of 250 rpm. After the volatile component was removed under a reduced pressure of 5 kPa, the styrene-based resin composition was obtained by granulation. The obtained styrene resin composition had a weight average molecular weight Mw of 370,000, an MFR of 1.5 g/10 min, and a weight ratio of -40 to 201139470. The ratio of the average molecular weight to the number average molecular weight Μw/Mn was 3.2. Comparative Example 2 Using the same reaction apparatus as in Example 1, 98 parts of styrene, 2 parts of butyl acrylate, 7 parts of ethylbenzene, and the multi-branched macromonomer (a3-1) of Reference Example 1 were compared with respect to styrene. 100 ppm of the total amount of the butyl acrylate, and the polymerization initiator third-stage butyl peroxybenzoate is adjusted with respect to a mixture of 300 ppm of 100 parts of the total of styrene and butyl acrylate. The polymerization was continuously carried out under the following conditions using the apparatus shown in Fig. 1. Supply of mixed solution: 9 · 0 liter / hr in the reaction temperature of the stirred reactor: 1 3 Ot Reaction temperature in the circulating polymerization line (I): 1 30 ° C Reaction in the non-circulating polymerization line (II) Temperature: 130 to 145 t The mixed liquid obtained by the polymerization was heated at a heat exchanger of 260 ° C, and the volatile component was removed under a reduced pressure of 5 kPa, and then granulated to obtain a styrene resin composition. The weight average molecular weight Mw of the obtained styrene resin composition was 270,000, MFR was 3.5 g/10 minutes, and the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight was 2.2. Comparative Example 3 300 parts of styrene, 7 parts of ethylbenzene, and a multi-branched macromonomer (a3-1) of Reference Example 1 with respect to 300 ppm of a phenylethyl group, and a polymerization initiator (2, 2-Bis(4,4-di-tert-butylperoxycyclohexyl)propane) is adjusted in a mixture of 150 pPm relative to 100 parts of styrene -41 - 201139470, except for the acyclic polymerization line The reaction temperature of (II) was outside the range of 145 to 155 ° C, and polymerization was carried out under the same conditions as in Example 1. The mixture obtained by the polymerization was heated by a heat exchanger at 260 ° C, and the volatile component was removed under a reduced pressure of 5 kPa, and then granulated to obtain a styrene resin composition. The obtained styrene resin composition had a weight average molecular weight Mw of 280,000, an MFR of 2.7 g/10 min, and a ratio Mw/Mn of a weight average molecular weight to a number average molecular weight of 2.4. Comparative Example 4 A total of 100 parts of styrene, 87.5 parts of styrene, 12.5 parts of butyl acrylate, 7 parts of ethylbenzene, and the multi-branched macromonomer (a3-1) of Reference Example 1 with respect to 100 parts of styrene and butyl acrylate. 3 00 ppm, a polymerization initiator (2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane) is adjusted with respect to a mixture of 150 ppm of styrene in 1 part In addition to the reaction temperature in the acyclic polymerization line (II) is from 1 4 5 to 155. The polymerization was carried out under the same conditions as in Example 1 except for the range of (: the mixture obtained by the polymerization was heated by a heat exchanger at 260 ° C, and the volatile component was removed under a reduced pressure of 5 kPa. A styrene resin composition was obtained, and the obtained styrene resin composition had a weight average molecular weight Mw of 610,000, an MFR of 3.8 g/10 min, and a ratio of weight average molecular weight to number average molecular weight of Mw/Mn of 2.8. Comparative Example 5 85 parts of styrene, 15 parts of butyl acrylate, 7 parts of ethylbenzene, and the multi-branched macromonomer (a-3) of Reference Example 1 were compared with styrene and butyl acrylate-42-201139470 vinegar. a mixture of 300 ppm of a total amount of a polymerization initiator (2,2,4,4-di-tert-butylperoxycyclohexyl)propane) in terms of 15 parts by mass relative to the styrene portion. The liquid was adjusted to carry out polymerization under the same conditions as in Example 1 except that the reaction temperature of the ring polymerization line (Π) was in the range of 145 to 155 °C. The mixture obtained by the polymerization was heated by a heat exchanger at 260 ° C, and the volatile component was removed under reduced pressure of 5 kPa, and then granulated to obtain a styrene resin composition. The weight average molecular weight Mw of the obtained ethylene resin composition was 590,000, 3.2 g / 1 〇 minute, and the weight average molecular weight and the number average molecular weight Mw / Mn were 2.9. Double (100 non-circulated and combined benzene MFR ratio -43-201139470 [Table i] Example 1 Example 2 Example 3 Example 4 Giant monomer species a3-l a3-2 a3-3 a3 -4 Giant monomer addition amount 300 300 300 300 BuA usage 6.5 6.5 6.5 6.5 MFR (g/10 min) 4.0 3.9 4.0 4.0 Weight average molecular weight (χιό4) 38 35 39 36 Mw/Mn 2.8 2.8 2.8 2.8 Summer type punching strength (MPa) 2.4 2.4 2.4 2.4 Vicat softening temperature 90 90 90 90 Injection molding process, extrusion film forming processability, mold release property, practical heat resistance ◎ ◎ ◎ ◎ MD/TD MD/TD MD/TD MD/TD Extension ratio (times) 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 i Heating shrinkage stress MD/TD MD/TD MD/TD MD/TD Extension (MPa) 0.24/0.42 0.27 /0.40 0.27/0.42 0.27/0.42 image sharpness ◎ ◎ ◎ ◎ flexural strength 〇〇〇〇 optimum heating time 〇〇〇〇-44 - 201139470 [Table 2] Example 5 Example 6 Example 7 Example 8 Giant monomer species a3-5 a3-l a3-l a3-2 Giant monomer addition amount 300 100 500 100 BuA usage 6.5 6.5 6.5 6.5 MF R (g/10 min) 3.9 4.3 3.6 4.4 Weight average molecular weight 〇1〇4) 32 34 46 31 Mw/Mn 2.9 2.8 2.9 2.7 Summer type punching strength (MPa) 2.4 2.3 2.9 2.3 Vicat softening temperature 90 90 90 90 Injection Molding processability 〇 〇 压 Extrusion film forming processability 〇〇 〇 〇 release property 〇〇〇〇 practical heat resistance ◎ ◎ ◎ ◎ Axial extension stretching ratio (times) MD/TD 2.3/3.1 MD/TD 2.3/3.1 MD/TD 2.3/3.1 MD/TD 2.3/3.1 Heat shrinkage stress (MPa) MD/TD 0.25/0.39 MD/TD 0.27/0.39 MD/TD 0.27/0.43 MD/TD 0.24/0.38 Sheet image clarity ◎ ◎ ◎ ◎ Folding strength 〇〇〇〇 optimum heating time 〇〇〇〇-45- 201139470 [Table 3] Example 9 Example 10 Example 11 Example 12 Giant monomer species a3-2 a3-3 a3-3 a3-4 Giant monomer addition amount 500 100 500 100 BuA usage 6.5 6.5 6.5 6.5 MFR (g/10 min) 3.5 4.6 3.3 4.3 Weight average molecular weight (X104) 43 36 51 33 Mw/Mn 2.9 2.8 3.0 2.8 Summer type punching strength (MPa ) 2.7 2.3 2.7 2.4 Vicat softening temperature 90 90 90 90 Injection molding process 〇 ◎ 〇 ◎ Extrusion film forming plus 〇〇 〇〇 〇 release property 〇〇〇〇 practical heat resistance ◎ ◎ ◎ ◎ stretch ratio (times) MD / TD 2.3 / 3.1 MD / TD 2.3 / 3.1 MD / TD 2.3 / 3.1 MD / TD 2.3 / 3.1 heat shrinkage Stress MD/TD MD/TD MD/TD MD/TD Extension (MPa) 0.27/0.42 0.25/0.40 0.27/0.43 0.26/0.41 Image clarity ◎ ◎ ◎ ◎ Folding strength 〇〇 ◎ 〇 Optimum heating time 〇〇〇 〇-46- 201139470 [Table 4] Example 13 Example Η Example 15 Example 16 Giant monomer species a3-4 a3-5 a3-5 a3-l Giant monomer addition amount 500 100 500 300 BuA usage 6.5 6.5 6.5 4.5 MFR (g/10 min) 3.2 4.4 3.4 4.2 Weight average molecular weight (XI 〇 4) 44 31 40 33 Mw/Mn 2.9 2.8 3.3 2.9 Summer type punching strength (MPa) 2.7 2.3 2.5 2.4 Vicat softening temperature 90 90 90 94 Injection molding process 〇 〇〇 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 〇〇 〇〇 Practical heat resistance ◎ ◎ ◎ ◎ MD / TD MD / TD MD / TD MD / TD extension ratio (times 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 Axis heating shrinkage stress MD/TD MD/TD MD/TD MD/TD extension thin (MPa) 0.28/0.44 0.23/0.37 0.27/0.42 0.27/0.45 image sharpness ◎ ◎ ◎ ◎ flexural strength 〇〇〇〇 optimum heating time 〇〇〇〇-47- 201139470 [Table 5] Example 17 Example 18 Example 19 Example 20 Giant monomer species a3-l a3-2 a3-2 a3-3 Giant monomer addition amount. 300 300 300 300 BuA usage 12.5 4.5 12.5 4.5 MFR (g/10 min) 4.0 4.0 4.2 4.0 Weight average Molecular weight (χιό4) 44 32 43 36 Mw/Mn 2.8 2.7 2.8 2.8 Summer type punching strength (MPa) 2.7 2.3 2.7 2.3 Vicat softening temperature 80 94 80 94 Injection molding processability ◎ 〇 〇 〇 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜〇〇 release property 〇〇〇〇 practical heat resistance 〇 ◎ ◎ MD / TD MD / TD MD / TD MD / TD extension ratio (time) 2.3 / 3.1 2.3 / 3.1 2.3 / 3.1 2.3 / 3.1 shaft heating shrinkage stress MD /TD MD/TD MD/TD MD/TD Extension (MPa) 0.20/0.35 0.29/0.44 0.22/0.36 0.30/0.44 Image sharpness ◎ ◎ ◎ ◎ Folding strength 〇〇〇〇 Optimum heating time 〇〇〇〇- 48 - 201139470 [Table 6] Example 21 Example 22 Example 23 Example 24 Giant monomer species a3-3 a3-4 a3-4 a3-5 Giant monomer addition amount 300 300 300 300 BuA usage 12.5 4.5 12.5 4.5 MFR (g/10 min) 4.2 3.9 4.1 3.7 Weight average molecular weight (χιό4 47 33 44 31 Mw/Mn 2.9 2.7 2.8 2.9 Summer type punching strength (MPa) 2.6 2.5 2.7 2.3 Vicat softening temperature 80 94 80 94 Injection molding workability ◎ 〇 〇 〇 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜Moulding 〇〇〇〇 Practical heat resistance 〇 ◎ 〇 ◎ Extension ratio (times) MD/TD MD/TD MD/TD MD/TD 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 Axis heating shrinkage stress MD/TD MD /TD MD/TD MD/TD extension sheet (MPa) 0.22/0.37 0.30/0.46 0.23/0.37 0.27/0.42 Image clarity ◎ ◎ ◎ ◎ Folding strength ◎ 〇〇〇 Optimum heating time 〇〇〇〇-49- 201139470 [Table 7] Example 25 Example 26 Example 27 Example 28 Giant monomer species a3-5 a3-l a3-l a3-l Giant monomer addition amount 300 100 100 500 BuA usage 12.5 4.5 12.5 4.5 MFR( g/10 points) 4.6 3.8 4.4 3.5 Weight average molecular weight (χιό4) 46 31 40 40 Mw/Mn 3.6 2.7 2.8 2.8 Summer rush撃Strength (MPa) 2.8 2.3 2.8 2.7 Vicat softening temperature 80 94 80 94 Injection molding process ◎ 〇 〇 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 〇〇〇 〇〇〇 〇〇〇 〇〇〇 〇〇〇 〇〇〇 〇〇〇 MD MD /TD MD/TD MD/TD MD/TD Extension ratio (times) 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 Axis heating shrinkage stress MD/TD MD/TD MD/TD MD/TD extension (MPa) 0.20/ 0.35 0.29/0.45 0.20/0.35 0.30/0.45 Image sharpness ◎ 〇 ◎ ◎ Folding strength ◎ 〇〇〇 optimum heating time 〇〇〇〇-50- 201139470 [Table 8] Example 29 Example 30 Giant monomer A3-l a3-l Giant monomer addition amount 500 600 BuA usage 12.5 6.5 MFR (g/10 min) 4.1 1.8 Weight average molecular weight (X104) 58 52 Mw/Mn 3.0 2.9 Summer type punching strength (MPa) 3.1 2.8 Dimensions Card softening temperature 80 90 Injection molding workability ◎ Δ Extrusion film forming workability ◎ Δ Removability ◎ 〇 Practical heat resistance 〇 ◎ MD/TD MD/TD Extension ratio (times) 2.3/3.1 2.3/2.8 Axis heating shrinkage stress MD/TD MD/TD extension (MPa) 0.22/0.38 0.27/0.42 Sheet image clarity ◎ 〇 folding strength ◎ ◎ optimum heating time 〇〇-51- 201139470 [Table 9] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Giant monomer species a3-l a3-l a3 -l a3-l a3-l Giant monomer addition amount 100 100 300 300 300 BuA usage 2.0 2.0 12.5 15.0 MFR (g/10 min) 1.5 3.5 2.7 3.8 3.2 Weight average molecular weight (χΐ〇4) 37 27 28 61 59 Mw/Mn 3.2 2.2 2.4 2.8 2.9 Charging strength in summer (MPa) 2.8 2.3 2.2 2.9 3.1 Vicat softening temperature 97 98 103 78 75 Injection molding processability X Δ 0 Δ 〇 Extrusion film forming processability Δ X Δ Δ △ Modularity Δ XX 〇o Practical heat resistance ◎ ◎ ◎ o X Extension ratio (times) MD/TD MD/TD MD/TD MD/TD MD/TD 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 2.3/3.1 Axis Heat shrinkage stress MD/TD MD/TD MD/TD MD/TD MD/TD Extension sheet (MPa) 0.25/0.40 0.22/0.45 0.24/0.42 0.27/0.40 0.24/0.45 Image sharpness X Ο X oo Folding strength Ο ο X oo Optimum heating time 〇 〇 〇 [Industrial use possibility] $ 苯乙烯 Styrene resin composition obtained by the invention Ϋ conventional linear styrene-based resin composition having a broader molecular weight distribution, and therefore, even if -52-201139470 comprising ultrahigh molecular weight component has an excellent moldability. Further, when various molding methods using a mold are further applied, since the mold release property from the mold is good, it is not necessary to remove the film by using an additive or the like because the surface has no dirt, so the cost/time is good and the productivity is good. , can reduce the degree of production of defective products. Further, the obtained molded article has the same or similar mechanical strength as in the related art. Further, in the radiant heating type vacuum forming method, the sheet obtained by biaxially stretching the sheet is reproducible and a good molded article having no thickness unevenness can be obtained. When the secondary processing is carried out by the radiant heating type vacuum forming method, since the hot plate is not contacted, no hot plate dirt is generated, and the transparency of the styrene resin is not impaired, and the image clarity is excellent. Therefore, it can be applied to various outer casings or optical components which are further enlarged and thickened, various packaging materials which are mass-produced, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a step of an example of a continuous polymerization line in which a tubular reactor having a static mixing element is embedded. [Main component symbol description] 1 Piston pump 2 Stirred reactor 3 Gear pump 4 Tubular reactor with static mixing elements 5 Tubular reactor with static mixing elements 6 Tubular reactor with static mixing elements -53- 201139470 7 Gear pump 8 tubular reactor with static mixing elements 9 tubular reactor with static mixing elements 10 tubular reactor with static mixing elements 11 gear pump (I) circulating polymerization line (II) non-circulating polymerization line -54-