200927416 九、發明說明： 【發明所屬之技術領域】 本發明涉及適用作矽晶圓、磁碟片等之收藏輸送容器 用的材料之聚碳酸酯樹脂九粒的製造方法及其成形品。 【先前技術】 一般，用以收藏輸送矽晶圓、磁碟片等對於表面污染 敏感之薄板的容器’其能於輸送中經常保持矽晶圓表面正 Λ 常係極爲重要的。 Ο 最近’隨矽晶圓之大口徑化，對於晶圓表面來自容器 的污染之要求更加嚴苛，同時也需要有更高強度之材料。 不只晶圓’關於磁碟片收藏輸送容器等亦有同樣要求。聚 碳酸酯樹脂或以其爲主要成分的樹脂組成物已被嘗試用作 合乎該要求之成形材料。 例如，專利文獻1〜4記載，去除聚碳酸酯樹脂中之雜 質’或藉高溫加熱減少揮發氣體量，以防矽晶圓表面受污 © 染之方法。然而，矽晶圓、磁碟片用之收藏輸送容器因不 只使用一次’而係經水洗重複利用，專利文獻1〜4所述之 收藏輸送容器經水洗則有離子性雜質溶出，會有附著於容 器表面之離子性雜質污染矽晶圓等的表面之問題。 另有於熔融擠壓時注入水，去除聚碳酸酯樹脂中之雜 質的方法之提議。專利文獻5〜7提議，聚碳酸酯樹脂粉末 以附排氣口之擠壓機一邊注入少量的水一邊擠壓之方法。 然而’這些方法雖能某程度去除聚碳酸酯樹脂中之雜質、 氯化合物’但不足以作爲如上之晶圓等的收藏輸送容器之 200927416 材料。 專利文獻1 特開平 1 0-2 1 1 686號公報 專利文獻2 特開平 11-241012號公報 專利文獻3 國際公開第2000/043436號小冊 專利文獻4 特開2000-063505號公報 專利文獻5 特公平 05 -048 1 62號公報 專利文獻6 特公平 07-002364號公報 專利文獻7 特開平 09- 1 93230號公報 【發明內容】 本發明之目的在提供，氯原子含量低，溶出之氯離子 量少的聚碳酸酯樹脂之製造方法。本發明之目的亦在提供 適用作爲對於表面污染敏感之矽晶圓、磁碟片等薄板之表 面少有受污染之虞的收藏輸送容器材料之聚碳酸酯樹脂的 製造方法。本發明之目的並在提供，收藏物表面受污染之 疑慮少的收藏輸送容器等成形品。 本案發明人爲達成該目的，進行了精心探討結果發 現，使雙軸擠壓機之螺桿具特殊構造，提高水剛注入後之 混練性能’高效率混練聚碳酸醋樹脂，將水分散混合後排 氣而去揮發物，以提升去揮發物之效率，即可得氯化合物 含量低的聚碳酸酯樹脂九粒。並發現，以此九粒爲材料得 到之成形DCI經水洗亦少有氯離子產生，適用作砂晶圓、磁 碟片等之收藏輸送容器。本發明即係以這些見解爲基礎。 亦即依本發明可提供其特徵爲，聚碳酸酯樹脂粉粒體 以雙軸擠壓機溶融擠壓，製造九粒之方法中，雙軸擠壓機 200927416 係使用 (i)至少具有1個由注水部，注水部正下方之混練部，位 於混練部上游側、下游側或兩側之封環，及注水部下游側 的排氣部所構成之混練擠壓單元， • (ii)混練部之最上游螺桿元件爲正交捏揉盤（C)或順向捏 揉盤（f)，最下游螺桿元件爲逆向捏揉盤（r)， (iii)混練部各螺桿元件之長度（LO在0_25D~D之範圍，混 φ 練部的長度（L〇在D〜4D之範圍（D :料筒內徑）之雙軸擠壓 機， 連同自注水部（W)注水，調節排氣部（V)之真空度爲6.7kPa 以下的聚碳酸酯樹脂九粒之製造方法。 依本發明並可提供，由得自該製造方法之聚碳酸酯樹 脂九粒形成之成形品。 以下詳細說明本發明。 【實施方式】 ® 〈聚碳酸酯樹脂〉 用於本發明之聚碳酸酯樹脂係於溶劑存在下，使二元 酚與碳酸酯前驅物經界面聚合法反應而得之芳族聚碳酸酯 樹脂。於此所用之二元酚有例如氫醌 '雷瑣辛、4,4’-二羥 聯苯、雙（4-羥苯基）甲烷、1，1-雙（4-羥苯基）乙烷、2,2-雙（4-羥苯基）丙烷（俗稱雙酚A)、2,2-雙（3-甲基-4-羥苯基）丙烷、 1,1-雙（4·羥苯基）環己烷（俗稱雙酚Z)、2,2-雙（3-苯基-4-羥 苯基）丙烷、2,2-雙（3-異丙基-4-羥苯基）丙烷、2,2·雙（4-羥 苯基）丁烷、2,2-雙（3，5-二甲基-4-羥苯基）丙烷、4,4’-二羥聯 200927416 苯颯、4,4’-二羥聯苯亞颯、4,4’-二羥聯苯硫醚、3,3’-基- 4,4’-二羥聯苯硫醚、4,4’-二羥聯苯醚、9,9-雙（4-羥三 荞、9,9 -雙{(4·羥基-3 -甲基）苯基丨莽、1，1-雙（4-• 基>-3,3,5-三甲環己烷、α,α’-雙（4-羥苯基）間二異丙 ' 1,3-雙（4-羥苯基）-5,7-二甲金剛烷等。其中以雙酚a、 2、9,9-雙{(4-經'基-3-甲基）苯基}弗、1，1-雙（4-羥苯基）-3 三甲環己烷、〇：，〇:’-雙（4-羥苯基）間二異丙苯爲佳。這 Q 單獨使用，亦可倂用二種以上。 碳酸酯前驅物係羰鹵化物或鹵甲酸酯等，具體有 或二元酚的二鹵甲酸醋等。 丨， 該二元酚與碳酸酯前驅物以界面聚縮合法反應製 碳酸酯樹脂之際，必要時亦可使用末端停止劑、二元 抗氧化劑等。聚碳酸酯樹脂可爲將三官能以上之多官 芳族化合物共聚而得之分枝聚碳酸酯樹脂，亦可爲將 或脂族二官能性羧酸共聚而得之聚酯碳酸酯樹脂，並 ® 爲混合2種以上的得到之聚碳酸酯樹脂而成之混合物 界面聚縮合法之反應通常係二元酚與光氣之反應 於酸結合劑、觸媒及有機溶劑之存在下促使反應。 酸結合劑係可使用例如氫氧化鈉、氫氧化鉀等鹼 氫氧化物或吡啶等胺化合物。 有機溶劑係可使用例如二氯甲烷、氯仿、1，2-二 烷、1,1-二氯乙烷、溴乙烷、氯丁烷、氯丙烷及氯苯等 烴；使用二氯甲烷尤佳。這些溶劑可單獨或混合2種 使用。 二甲 蓉基） 羥苯 苯、 雙酚 ,3,5- 些可 光氣 造聚 酚之 能性 芳族 亦可 〇 ，係 金屬 氯乙 鹵化 以上 200927416 用以促進反應之胺系觸媒有例如三乙胺、溴化四正丁 銨、溴化四正丁鱗等三級胺、四級銨化合物，四級鱗化合 物等觸媒；尤佳者爲使用三乙胺。 . 界面聚縮合法之反應溫度通常係0~40°C，反應時間爲 ♦ 10分鐘〜5小時左右，反應中之pH以保持在9以上爲佳。 該聚合反應中，通常會使用末端停止劑。該末端停止 劑可爲單官能酚類。單官能酚類一般係用作末端停止劑以 φ 調節分子量，得到之聚碳酸酯樹脂因末端由衍生自單官能 酚類之基封鎖，熱安定性優於未經如此封鎖者。該單官能 酚類有例如酚、對三級丁酚、對異丙苯基酚及異辛酚。 這些末端停止劑宜以占得到之聚碳酸酯樹脂的所有末 端之至少5莫耳％導入，至少10莫耳％更佳；末端停止劑 可單獨或混合2種以上使用。 聚碳酸酯樹脂的分子量係以黏度平均分子量（M)lx 104 〜4xl04 爲佳，1.3xl04~3xl04 更佳，1.6xl04~2.4xl04 尤佳。 © 具該黏度平均分子量之聚碳酸酯樹脂強度充分，且成形時 熔融流動性良好，無成形應變而較佳。該黏度平均分子量 係在20°C溶解聚碳酸酯樹脂0.7g於二氯甲烷l〇〇ml，由該 溶液求出比黏度（7/ SP)，代入下式求出。 7? /c=U ] + 〇_45x[t? ]2c (其中 U ]係極限黏度） [η ] = 1.23χ1〇·4Μ0·83 c = 0.7 該反應得之聚碳酸酯樹脂的有機溶劑溶液，通常係以水 洗淨。此水洗步驟係以使用離子交換水等導電度l〇A S/cm -10- 200927416 以下之水爲佳，1# S/cm以下之水更佳；混合該有機溶劑溶 液與水，攪拌後靜置或以離心分離機等使有機溶劑溶液相 與水相分液，取出有機溶劑溶液，重複進行而去除水溶性 雜質。以水洗去除水溶性雜質，得到之聚碳酸酯樹脂的色 相即良好。 爲去除觸媒等雜質，該聚碳酸酯樹脂的有機溶劑溶液 並以經施行酸洗、鹼洗爲佳。 用於酸洗之酸係以磷酸、鹽酸、硫酸等之水溶液爲佳， 以濃度0.004〜40g/升（或pH 5以下）之水溶液爲佳。用於鹼 洗之鹼有氫氧化鈉、氫氧化鉀等鹼金屬化合物，氫氧化鈣、 氫氧化鋇、氫氧化鎂等鹼土金屬化合物，氫氧化鈉尤佳； 以濃度0.1~20g/升（或pH 11. 5以上）之水溶液爲佳。 用於鹼洗、酸洗之水溶液與有機溶劑溶液之比率若在 水溶液/有機溶劑溶液（容量比）爲0.2~ 1.5之範圍，則可高效 率洗淨而較佳。 其次，去除該經水洗之有機溶劑溶液的溶劑，得聚碳 酸酯樹脂粉粒體。 得聚碳酸酯樹脂粉粒體之方法（造粒步驟）因操作、後 處理簡便，較佳者係於存在有聚碳酸酯樹脂粉粒體及溫水 (40〜90°C左右）之造粒裝置中，攪拌狀態下連續供給聚碳酸 粒 造 〇 澧 漿。 造佳 製較 以爲 發機 蒸合 劑混 溶等 該機 將揉 , 捏 液、 溶槽 劑拌 溶攪 機用 有採 的以 脂係 樹置 酯裝 該漿體亦可於嗣後施以熱水處理。熱水處理步驟係供 給該漿體於饋入有9 0~ 100 °C之熱水的熱水處理容器，或供 200927416 給後藉吹入蒸氣等使水溫達90〜1 〇〇 °C ’以去除漿體所含之 有機溶劑。 於造粒步驟排出之漿體或該熱水處理後之漿體，較佳 者爲藉過濾、離心分離等將水及有機溶劑某程度去除，回 收聚碳酸酯樹脂的濕潤糊體。 其次將聚碳酸酯樹脂的濕潤糊體乾燥。乾燥機可係傳 導加熱方式或熱風加熱方式’聚碳酸酯樹脂可係靜置、經 φ 輸送經攪拌。其中以傳導加熱方式並作聚碳酸酯樹脂之攪 拌的溝形或圓筒乾燥機爲佳，溝形乾燥機尤佳。乾燥溫度 以1 3 0〜1 5 0 °C爲佳。 ·> 本發明中，供作混練擠壓處理之聚碳酸酯樹脂的形狀 可係粉末狀、微粒狀、片狀、九粒狀中任一，較佳者爲粉 末狀、微粒狀或片狀。 本發明中，供作混練擠壓處理之聚碳酸酯樹脂內的氯 原子含量係以5〜2,000ppm爲佳，5〜l,500ppm更佳。氯原子 ® 含量在該範圍則可有效達成本發明之目的。 <雙軸擠壓機 > 〜 雙軸擠壓機至少具有1個由注水部（1)、混練部（2)、封 環（3)及排氣部（4)構成之混練擠壓單元。雙軸擠壓機並以具 有輔助排氣部（5)、添加劑導入部（6)爲佳。第1圖係用於本 發明之雙軸擠壓機的構造之一例。 (注水部（1)) 注水部係將水注入之部位。注水部有6個以上則引起 樹脂劣化而不佳。 -12- 200927416 (混練部（2)) 混練部位在擠壓機之注水部正下方，係混練樹脂的部 位。本發明中，混練部之螺桿構造極爲重要。 混練部之最上游螺桿元件係正交捏揉盤（c)或順向捏揉 盤（f)，最下游螺桿元件係逆向捏揉盤（r)。 螺桿構造係以例如順向（f)·逆向（r)、同樣c-r、c-f-r、 f-c-r、c-c-r-r、f-f-r-r 之組合爲佳。 D 捏揉盤係以雙螺旋型爲佳。捏揉盤之較佳螺旋角爲 15〜90度，45~90度更佳。 各捏揉盤係由複數盤構成，盤數以2~7爲佳，3~6更佳。 ·> 混練部各螺桿元件之長度（L·)係0.25D-D，0.5D〜0.75D 更佳。D係料筒內徑。混練部之長度（1^)係D~4D，1.5D-3.5D 更佳。螺桿總長度（L3)係以28D-49D爲佳，31.5D~45.5D更 佳。 以如上之混練部螺桿，得到之聚碳酸酯樹脂丸粒中氯 w 化合物含量即降低。得到之九粒所形成之成形品藉由水的 氯離子溶出量少，適用作矽晶圓、磁碟片之收藏輸送容器。 (封環（3)) 封環係位於混練部上游側、下游側或兩側。 (排氣部（4)) 排氣部位在注水部下游側，係排除混練產生之氣體的 部位。 (輔助排氣部（5)) 雙軸擠壓機係以於混練擠壓單元上游側具有輔助排氣 -13- 200927416 部爲佳。因此，雙軸擠壓機之排氣部係以2個爲佳，2~6 個更佳’ 2~5個尤佳。僅有1個則得到之聚碳酸酯樹脂九粒 中的殘留氯離子量偏高；而排氣部過多則因擠壓機螺桿總 長度（L3)加大而易於造成樹脂燒焦、劣化等不良影響。 雙軸擠壓機之混練擠壓單元係以1~5個爲佳，1〜3個更 佳，1或2個尤佳。 (添加劑導入部（6)) 0 雙軸擠壓機可於混練擠壓單元下游側具有添加劑導入 部。雙軸擠壓機係以於添加劑導入部下游側具有輔助混練 部爲佳。爲提高添加劑之分散性，可於添加劑導入部下游 側設置輔助混練部。輔助混練部之螺桿構造若係能充分混 練添加劑者即可，無特殊限制。例如可以順向捏揉盤、正 交捏揉盤、逆向捏揉盤單獨或組合使用。 <混練條件> 混練係連同自注水部，之注水調節排氣部之真空度於 © 6.7kPa以下而進行。 自注水部添加之注水量太少則不得注水添加效果，得 到之聚碳酸酯樹脂九粒中氯原子含量無法降低，注水量太 多則排氣部之脫氣不足，會於聚碳酸酯樹脂引起水解等不 良影響。因此注水部之注水量係以聚碳酸酯樹脂每100重 量份爲0.1~5重量份爲佳’ 〇·2~4重量份更佳。 注入之水於25 °C測定之導電度宜係1μ S/cm以下，〇.5 μ S/cm以下更佳。使用該導電度S/cm以下之水，則聚 碳酸酯樹脂更不易起水解’樹脂分子量下降受到抑制而較 -14- 200927416 佳。 雙軸擠壓機各排氣部之真空度係6.7kPa以下，2.0 kPa 以下更佳。真空度在該範圍則注入添加之水於排氣部充分 去除，氯原子含量減少，同時不於芳族聚碳酸酯樹脂有水 解等不良影響而較佳。 添加劑之導入方法無特殊限制，可將添加劑單獨導 入’亦可先摻合複數之添加劑而導入。並亦可先將添加劑 Q 摻合於原料聚碳酸酯樹脂粉粒體成添加劑母料添加。添加 劑之熔點低者於添加劑導入部熔化會造成堵塞，故以將預 先摻合聚碳酸酯樹脂粉粒體與添加劑的添加劑母料導入雙 |> 軸擠壓機之方法爲佳。 添加劑之導入量取決於所要求之特性，導入添加劑母 料時’相對於得到之聚碳酸酯樹脂九粒（總擠壓量），添加 劑母料係以Ο·1~30重量％爲佳。0.2〜20重量％更佳，0.3〜10 重量％尤佳。以超過此範圍之量導入，則氯化合物之減少效 Ο W 果易有不足；以低於此範圍之量導入，則添加劑導入量變 異加大’有時無法賦予所要求之特性。 因此較佳者爲，將預先摻合聚碳酸酯樹脂粉粒體與添 加劑之添加劑母料，以相對於得到之九粒的〇. i ~30重量％， 由添加劑導入部導入雙軸擠壓機。 <各種添加劑> 爲於本發明之聚碳酸酯樹脂九粒及以該丸粒形成之成 形品’在無損於本發明目的之範圍賦予各種特性，可使用 各種添加劑。可配合之添加劑有脫模劑、熱安定劑、紫外 -15- 200927416 線吸收劑、上藍劑、抗靜電劑、阻燃劑、熱線遮蔽劑、螢 光染料（含螢光增白劑）、顏料、光擴散劑、強化塡料、其 它樹脂或彈性體等。 脫模劑係以其90重量％以上由醇與脂酸的酯類構成者 爲佳。醇與脂肪酸的酯類具體有一元醇與脂肪酸的酯類及/ 或多元醇與脂肪酸的部分酯類或全酯類。該一元醇與脂肪 酸的酯類係以碳原子數1〜20之一元醇與碳原子數10〜30之 φ 飽和脂肪酸的酯類爲佳。又，多元醇與脂肪酸的部分酯類 或全酯類係以碳原子數卜25之多元醇與碳原子數10〜30之 飽和脂肪酸的部分酯類或全酯類爲佳。 具體而言，一元醇與飽和脂肪酸之酯類有硬脂酸硬脂 酯、稼櫚酸棕櫚酯、硬脂酸丁酯、月桂酸甲酯、棕櫚酸異 丙酯等；硬脂酸硬脂酯爲較佳。 具體而言，多元醇與飽和脂肪酸之部分酯類或全酯類 有一硬脂酸甘油酯、二硬脂酸甘油酯、三硬脂酸甘油酯、 © 硬脂酸一山梨酯、一蘿酸甘油酯、新戊四醇一硬脂酸酯、 新戊四醇四硬脂酸酯、新戊四醇四壬酸酯、丙二醇一硬脂 酸酯、聯苯酸聯苯酯、山梨醇一硬脂酸酯、硬脂酸2·乙己 酯、二新戊四醇陸硬脂酸酯等二新戊四醇之全酯類或部分 酯類等。 這些酯類之中，以一硬脂酸甘油酯、三硬脂酸甘油酯、 新戊四醇四硬脂酸酯、三硬脂酸甘油酯與硬脂酸硬脂醋的 混合物爲較佳。 以脫模劑爲重量％時’脫模劑中該酯類之量係以 -16- 200927416 90重量％以上爲佳，95重量％以上更佳。 聚碳酸酯樹脂粉粒體中脫模劑之含量係以相對於聚碳 酸酯樹脂粉粒體100重量份在〇·〇〇5~2·0重量份之範圍爲 佳’ 0.01~0.6重量份更佳，〇.〇2~0.5重量份尤佳。 熱安定劑者有磷系熱安定劑、硫系熱安定劑及受阻酣 系熱安定劑。 磷系熱安定劑有亞磷酸、磷酸、亞磺酸 '磺酸及這些 φ 之酯類等；具體有亞磷酸三苯酯、亞磷酸參（壬苯）醋、亞 憐酸參（2,4 -二（三級丁）苯）醋、參（2,6 -二（三級丁）苯基）亞磷 酸酯、亞磷酸三癸酯、亞磷酸三辛酯、亞磷酸三（十八）酯、 亞磷酸二癸酯一苯酯、亞磷酸二辛酯一苯酯、亞磷酸二異 丙酯一苯酯、亞磷酸一丁酯二苯酯、亞磷酸一癸酯二苯酯、 亞磷酸一辛酯二苯酯、雙（2,6-二（三級丁）-4-甲苯）新戊四醇 二亞磷酸酯、2，2-亞甲雙（4,6-二（三級丁）苯）辛基亞磷酸 酯、雙（壬苯基）新戊四醇二亞磷酸酯、雙（2,4-二（三級丁） ® 苯）新戊四醇二亞磷酸酯、二硬脂基新戊四醇二亞磷酸酯、 磷酸三丁酯、磷酸三乙酯、磷酸三甲酯、磷酸三苯酯、磷 酸二苯酯一鄰二甲苯酯、磷酸二丁酯、磷酸二辛酯、磷酸 二異丙酯、苯膦酸二甲酯、苯膦酸二乙酯、苯膦酸二丙酯、 肆（2,4-二（三級丁）苯）-4,4’-聯苯二亞膦酸酯、肆（2,4-二（三 級丁）苯）-4,3’-聯苯二亞膦酸酯、肆（2,4-二（三級丁）苯）-3,3’-聯苯二亞膦酸酯、雙（2,4-二（三級丁）苯）-4-苯基苯基亞膦酸 酯及雙（2,4-二（三級丁）苯）-3-苯基苯基亞膦酸酯等。 其中可使用參（2,4-二（三級丁）苯基）亞磷酸酯、參（2,6- -17- 200927416 二（三級丁）苯基）亞磷酸酯、肆（2,4-二（三級丁）苯基）-4,4’-聯苯二亞膦酸酯、肆（2,4-二（三級丁）苯基）-4,3’·聯苯二亞滕 酸酯、肆（2,4-二（三級丁）苯基）-3,3’-聯苯二亞膦酸酯、雙 (2,4-二（三級丁）苯基）-4-苯基苯基亞膦酸酯及雙（2，4-二（三 級丁）苯基）-3-苯基苯基亞膦酸酯；使用肆（2,4-二（三級丁） 苯基）-4,4’-聯苯二亞膦酸酯尤佳。 聚碳酸酯樹脂粉粒體中磷系熱安定劑之含量係以相對 φ 於聚碳酸酯樹脂粉粒體100重量份〇.〇〇1~〇.2重量份爲佳。 硫系熱安定劑可舉出新戊四醇肆（3-月桂硫基丙酸 酯）、新戊四醇肆（3-肉豆蔻硫基丙酸酯）、新戊四醇肆（3-硬 脂硫基丙酸酯）、二月桂基-3，3’-硫二丙酸酯、二肉豆蔻基 -3,3’-硫二丙酸酯、二硬脂基-3,3’-硫二丙酸酯等，其中以 新戊四醇肆（3-月桂硫基丙酸酯）、新戊四醇肆（3 -肉豆蔻硫 基丙酸酯）、二月桂基- 3,3’-硫二丙酸酯、二肉豆蔻基- 3,3’-硫二丙酸酯爲佳。新戊四醇肆（3-月桂硫基丙酸酯）尤佳。該 〇 硫醚系化合物有市售之住友化學工業（股）的Sumilizer TP-D(商品名）及Sumilizer TPM(商品名）等可採用。 聚碳酸酯樹脂粉粒體中硫系熱安定劑之含量係以相對 於聚碳酸酯樹脂粉粒體1〇〇重量份爲〇.〇〇1~〇.2重量份爲 佳。 受阻酚系熱安定劑有三甘醇雙[3-(3-三級丁基-5-甲基 -4-羥苯基）丙酸酯]、1,6-己二醇雙[3-(3,5-二（三級丁）-4-羥 苯基）丙酸酯]、新戊四醇肆[3-(3,5-二（三級丁）-4-羥苯基）丙 酸酯]' 3-(3,5-二（三級丁）-4-羥苯基）丙酸十八酯、1，3,5-三 -18- 200927416 甲基·2,4,6-參（3,5-二（三級丁）-4-羥苯甲基）苯、N，N-六亞甲 雙（3,5-二（三級丁）-4-羥氫桂皮醯胺）、3,5-二（三級丁）·4-羥 苯甲基膦酸二乙酯、參（3,5-二（三級丁）-4-羥苯甲基）異三聚 氰酸酯及3,9-雙{1,1-二甲基- 2-[；S -(3-三級丁基-4-羥基- 5-甲苯基）丙醯氧]乙基}-2,4,8，10-四噚螺[5.5]十一烷等； 3-(3,5-二（三級丁）-4-羥苯基）丙酸十八酯尤佳。 聚碳酸酯樹脂粉粒體中受阻酚系熱安定劑之含量係以 0 相對於聚碳酸酯樹脂粉粒體100重量份爲0.001〜0.3重量份 爲佳。 紫外線吸收劑係以選自苯并三唑系紫外線吸收劑、二 苯基酮系紫外線吸收劑、三阱系紫外線吸收劑、環亞胺酯 系紫外線吸收劑及氰丙烯酸酯系之群的至少1種紫外線吸 收劑爲佳。 苯并三唑系紫外線吸收劑可舉出有2-(2-羥基-5-甲苯 基）苯并三唑、2-(2·羥基-5-三級辛苯基）苯并三唑、2-(2-羥 ® 基-3,5-二異丙苯基苯）苯并三唑、2-(2-羥基-3-三級丁基-5-甲苯基）-5-氯苯并三唑、2,2’-亞甲雙[4-(1,1,3,3-四甲基丁 基）-6-(2H-苯并三唑-2-基）酚]、2-(2-羥基-3,5-二（三級丁）苯 基）苯并三唑、2-(2-羥基-3,5-二（三級丁）苯基）-5-氯苯并三 唑、2-(2-羥基-3，5-二（三級戊）苯基）苯并三唑、2-(2-羥基- 5-三級辛苯基）苯并三唑、2-(2-羥基-5-三級丁苯基）苯并三 唑、2-(2-羥基-4-辛氧苯基）苯并三唑、2,2’-亞甲雙（4-異丙 苯基-6-苯并三唑苯基）、2,2’-對苯雙（1，3-苯并曙畊-4-酮）、 2-[2-羥基- 3-(3,4,5,6-四氫酞醯亞胺甲基）-5-甲苯基]苯并三 -19- 200927416 唑；這些可以單獨或2種以上的混合物使用。 較佳者爲2-(2 -羥基-5-甲苯基）苯并三唑、2-(2 -羥基- 5-三級辛苯基）苯并三唑、2-(2-羥基-3,5-二異丙苯基苯）苯并 三唑、2-(2-羥-3-三級丁基-5-甲苯基）-5-氯苯并三唑、2,2’-亞甲雙[4-(1，1，3,3-四甲丁基）-6-(2H-苯并三唑-2-基）酚]、 2-[2-羥-3-(3,4,5,6-四氫酞醯亞胺甲基）-5 -甲苯基]苯并三 唑；更佳者爲 2-(2-羥-5-三級辛苯基）苯并三唑、2,2’_亞甲 ❹ 雙[4-(1，1，3,3-四甲丁基）-6-(211-苯并三唑-2-基）酚]。 二苯基酮系紫外線吸收劑有2,4-二羥二苯基酮、2-羥 基-4-甲氧二苯基酮、2-羥基-4-辛氧二苯基酮、2-羥基-4-苯甲氧二苯基酮、2-羥基-4-甲氧基-5-硫羥基二苯基酮、2-羥基-4-甲氧基-5-硫羥基三氫化二苯基酮、2,2’-二羥基-4-甲氧二苯基酮、2,2’，4,4’-四羥二苯基酮、2,2’-二羥基-4,4’-二甲氧二苯基酮、2,2’-二羥基-4,4’-二甲氧基-5-鈉硫羥基二 苯基酮、雙（5-苯甲醯基-4-羥基-2-甲氧苯基）甲烷、2-羥基 〇 -4-正十二氧二苯基酮、2-羥基-4-甲氧基- 2’-羧二苯基酮等。 三阱系紫外線吸收劑可舉出有2-(4,6-二苯基-1，3,5-三 畊-2-基）-5-[(己基）氧基]酚、2-(4,6-雙（2,4-二甲苯基）-1，3,5-三阱-2-基）-5-[(辛基）氧基]酚等。 環亞胺酯系紫外線吸收劑可例示有2,2’-雙（3,1-苯并噚 畊-4-酮）、2,2’-對伸苯雙（3,1-苯并曙畊-4-酮）、2,2’-間苯雙 (3,1-苯并噚哄-4-酮）、2,2’-(4,4’-二伸苯）雙（3，1-苯并噚阱-4-酮）、2,2’-(2,6-萘）雙（3，1-苯并曙阱-4-酮）、2,2’-(1，5-萘）雙 (3，1-苯并噚阱-4-酮）、2,2’-(2-甲基-對伸苯）雙（3,1-苯并苯并 -20- 200927416 曙阱-4-酮）、2,2’-(2-硝基-對伸苯）雙（3,1-苯并苯并曙阱-4-酮）及2,2’-(2-氯對伸苯）雙（3，1-苯并苯并噚畊-4-酮）等。其 中以2,2’-對伸苯雙（3，1-苯并噚畊-4-酮）'2,2'-(4,4’-二伸苯） 雙（3,1-苯并聘阱-4-酮）及2,2’-(2,6-萘）雙（3,1-苯并噚阱-4-酮）較爲合適；2,2’-對伸苯雙（3,1-苯并噚阱-4-酮）尤合適。 該化合物有市售之竹本油脂（股）的CEi-P(商品名）可採用。 氰丙烯酸酯系紫外線吸收劑有例如1,3-雙[(2’·氰 ❹ -3’，3’-二苯丙烯醯）氧基]-2,2-雙[(2-氰- 3,3-二苯丙烯醯基） 氧基]甲基）丙烷，及1,3-雙[(2-氰-3,3-二苯丙烯醯基）氧基] 苯等。 紫外線吸收劑之配合量係以相對於聚碳酸酯樹脂粉粒 體100重量份爲0.01~3.0重量份爲佳，0.02〜1.0重量份更 佳，0.05~0.8重量份尤佳。在該配合量範圍則隨用途可賦 予聚碳酸酯樹脂成形品以充分之耐候性。 上藍劑有拜耳公司之 Macrolex Violet B、Macrolex Blue © RR 及 Clariant 公司之 POLYSINSLEN Blue RLS 等。上藍劑 可用以去除聚碳酸酯樹脂粉粒體之偏黃色調。尤以經賦予 耐候性之聚碳酸酯樹脂粉粒體者，因配合有一定量之紫外 線吸收劑，事實上由於「紫外線吸收劑之作用、著色」聚 碳酸酯樹脂成形品容易帶有偏黃色調，尤以爲賦予薄片、 鏡片自然之透明感，上藍劑之配合極爲有效。 上藍劑之配合量係以相對於聚碳酸酯樹脂粉粒體 0.05~1.5ppm 爲佳，0.1~1.2ppm 更佳。 又，聚碳酸酯樹脂於混練擠壓之際，樹脂溫度係依聚 -21- 200927416 碳酸酯樹脂分子量等適當設定，以27〇~35(TC左右ί <成形品> 依前述方法得之聚碳酸酯樹脂丸粒可藉擠壓成 出成形等一般方法成形。本發明包含由依前敘方法 碳酸酯樹脂九粒成形而得之成形品。 由該聚碳酸酯樹脂九粒成形而得之成形品，其 出之氯離子量顯著降低。 φ 成形品在水中於8(TC加熱處理24小時後，自該 溶出之氯離子量係以l〇ng/cm2以下爲佳，9ng/cm2 佳。下限無特殊限制，而要達到0.5ng/cm2以下則窄 該成形品適用作矽晶圓、磁碟片之收藏輸送容器。 實施例 以下舉實施例更具體說明本發明，但本發明不 些實施例。實施例中，除非特加聲明，份表重量份， 量％。評估係依下述方法爲之。 · ® (1)氯離子量： 聚碳酸酯樹脂九粒以射出成形得厚度1 mm之試 切取縱20mm，橫25mm之大小，置入萃取袋，加 15cm3，密閉下於80°C加熱24小時後，放冷至室溫 以離子層析定量水中之CT，求出成形品表面積每1 cr萃取量。所用之裝置及條件如表1。 I佳。 形、射 得之聚 以水溶 成形品 以下更 困難。 限於這 %表重 樣板， 超純水 ，其次 cm2之 -22- 200927416 表1 裝置 DIONEX 公司 DX-500 試樣注入量 0.5 cm3 讎液 NaOH 分離管柱 IonPac AS4A-SC 偵測器 導電率計 (2)氯原子含量 將聚碳酸酯樹脂九粒完全燃燒，生成之氯化氫（HC1)以 〇 銀離子（Ag + )作電位滴定，由此電位滴定所需之電量求出氯 原子含量。 (3 )色相（九粒之b値） 使用色相計（日本電色（股）製SE-2000)測定b値。b値 愈高愈偏黃’表示熔融擠壓時聚碳酸酯樹脂熱安定性差。 實施例1~11及比較例1~5 於第2〜7圖之具有三個排氣口（最靠近原料供給斗起爲 〇 ^1、乂2、73)，排氣口乂2、乂3的直接前方設有注水部（最 靠近原料供給斗起之注水處起爲Wl、W2)的螺桿徑3〇ιηιηφ 之雙軸擠壓機[日本製鋼所製TEX30α ，螺桿構造全體之 L3/D = 45.5] ’供給表2記載之原料樹脂及添加劑，以表2之 濟壓條件擠壓成條束狀，切斷製成九粒。 添加劑係先與下述樹脂原料C摻合製成目標添加量之 5〇倍濃度的母料，以相對於得到之聚碳酸酯樹脂九粒（樹脂 原料與母料的合計量）2重量％之比率，由添加劑導入部導 入該母料。添加劑之目標添加量如表3。得到之聚碳酸酯 -23- 200927416 樹脂九粒的評估結果如表4。 表2中原料樹脂、添加劑及注水部之螺桿記號如下。 樹脂原料A:使雙酚A與光氣於二氯甲烷中以一般方 法反應得之黏度平均分子量丨8,500的聚碳酸酯樹脂粉末 (氯原子含量50ppm)。 樹脂原料B:使雙酚A與光氣於二氯甲烷中以一般方 法反應得之黏度平均分子量18,5〇〇之聚碳酸酯樹脂粉末 (氯原子含量236ppm)。 樹脂原料C:使雙酚A與光氣於二氯甲烷中以一般方 法反應得之黏度平均分子量22,400之聚碳酸酯樹脂粉末 丨， (氯原子含量ggppm)。 添加劑： 紫外線吸收劑：2-(2-羥基-5-三級辛苯基）苯并三唑 脫模劑：新戊四醇四硬脂酸酯 磷系安定劑：參（2,4-二（三級丁）苯基）亞磷酸酯 受阻酚系熱安定劑：3-(3,5 -二（三級丁）-4 -羥苯基） 丙酸十八酯 上藍劑：拜耳公司製Macrolex Violet B 螺桿A(參照第2圖）： 螺桿形狀（混練部之螺桿元件的螺角係正交捏揉盤爲 90度，逆向捏揉盤45度，La係2.0D)爲注水部於擠壓機注 水部開口上游側1.0D處配置封環（長度〇.5d)，往環之下游 2組正交捏揉盤（長度0.5d;由長度〇.1D之5盤構成）、2 組逆向捏揉盤（長度0.5D;由長度0.1D之5盤構成）後，配 -24- 200927416 置有封環（長度0.5D)。 螺桿B (參照第3圖）： 螺桿形狀（混練部之螺桿元件的螺角係順向捏揉盤爲 45度，逆向捏揉盤45度，L2爲2.0D)爲注水部於擠壓機注 水部開口上游側1.0D處配置封環（長度0.5D)，往環之下游 起3組順向捏揉盤（長度0.5D ;由長度0.1D之5盤構成）、 1組逆向捏揉盤（長度0.5D;由長度0.1D之5盤構成）後， & 配置有封環（長度0.5D)。 螺桿C(參照第4圖）： 螺桿構造係擠壓機注水部開口上游側1.0D處配置之封 環（長度0.5D)更換爲通常之全螺紋盤。 螺桿D(參照第5圖）： 螺桿構造（輔助混練部之螺桿元件的螺角係順向捏揉 盤爲45度，L2係1.0D)係螺桿A中，擠壓機注水部（W2)下 游側之排氣口（V3)的下游側設有添加劑導入部，更於其下 ❹ 游側配置有2組順向捏揉盤（長度0.5D ;由長度0.1D之5 盤構成）。 螺桿E(參照第6圖）： 螺桿構造係螺桿B中，取代逆向捏揉盤，改用順向捏 揉盤。 螺桿F(參照第7圖）： 螺桿構造係螺桿D中，取代正交捏揉盤及逆向捏揉 盤，全部改用順向捏揉盤。 -25- 200927416 CSI嗽 排氣真空度 (kPa) 1—Η 1 1 Η cn 1 CO CO 1 1 1 1 » On cs r_ H cn cn r λ 1 1 1 1 1 1 οο CN 1 < R Γ·· < On V Η cn cn 1 t 〇〇 CS Η cn cn r—Η H 严H r" < CO » "< r-H 7.20 7.20 1.30 1—Η *—Η i 1 $ Γ~ "< οο CS » i « ^ 产 < "< CO ι—Η 1.30 1.29 1 4 « i 7.20 7.20 7.20 1.30 S s CS1 0.53 1 0.52 1 0.50 1 1 1 0.50 1 1 1 1 1 1 1 m - 1—^ 0.52 0.54 0.54 0.51 0.50 0.52 0.51 0.52 0.52 r—H IT) 1 i 0.52 0.55 0.50 0.54 0.51 螺桿轉數 (rpm) in CSl 1 < 1 < 1—Η 1 1 4 CS (Ν ϊ—H r'~'< 1 ' < cs t-H CO csi ON τ < 1 1 < 〇 擠壓量 (kg/hr) 沄 沄 沄 螺桿構造 1 1 1 < < PQ PQ <： < PQ u u Q Q PQ m Q P-J Ρη 添加劑 導入 摧 摧 摧 壊 m 摧 摧 摧 m 擗 擗 璀 摧 蚺 摧 蚺 樹脂原料 類型 < C < < m PQ < < U U < PQ U < U i 1 實施例 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 比較例1 比較例2 比較例3 比較例4 比較例5 -9CN1- 200927416 表3 添加劑 添加量 紫外線吸收劑 0.2 wt% 脫模劑 0.1 wt% 磷系安定劑 0.03 wt% 受阻酚系安定齊！I 0.05 wt% 上藍劑 0.5 ppm。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [Prior Art] In general, it is extremely important to collect a container for transporting a sheet sensitive to a surface contamination such as a wafer or a disk, which is capable of constantly maintaining the surface of the wafer. Ο Recently, the large diameter of the wafers has become more demanding on the surface of the wafer from the contamination of the container, and it also requires higher strength materials. There are also requirements for not only wafers, but also for magnetic disk storage containers. A polycarbonate resin or a resin composition containing the same as the main component has been tried as a molding material satisfying the requirements. For example, Patent Documents 1 to 4 disclose a method of removing impurities in a polycarbonate resin or reducing the amount of volatile gas by heating at a high temperature to prevent contamination of the surface of the wafer. However, the storage container for the wafer and the magnetic disk is reused by water washing not only once, and the storage container described in Patent Documents 1 to 4 is eluted with ionic impurities by water washing, and may be attached thereto. The ionic impurities on the surface of the container contaminate the surface of the wafer or the like. There is also a proposal for a method of injecting water during melt extrusion to remove impurities in the polycarbonate resin. Patent Documents 5 to 7 propose a method in which a polycarbonate resin powder is extruded while injecting a small amount of water into an extruder having an exhaust port. However, these methods can remove impurities and chlorine compounds in the polycarbonate resin to some extent, but are not sufficient as the 200927416 material for the collection container of the above wafer or the like. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. 2000-043436. Patent Publication No. 2000-043436 Japanese Patent Publication No. Hei 09-002364 (Patent Document) Japanese Patent Application Laid-Open No. Hei. A method of manufacturing a small polycarbonate resin. It is also an object of the present invention to provide a method for producing a polycarbonate resin which is suitable for a collecting container material which is less contaminated on the surface of a sheet such as a wafer or a disk which is sensitive to surface contamination. It is an object of the present invention to provide a molded article such as a collection transport container having a small degree of contamination of the surface of the collectible. In order to achieve this goal, the inventor of the present invention conducted a careful investigation and found that the screw of the twin-screw extruder has a special structure to improve the kneading performance after the water injection. The high-efficiency kneading polycarbonate resin disperses and mixes the water. By removing the volatile matter from the gas to increase the efficiency of the volatile matter, nine particles of the polycarbonate resin having a low chlorine compound content can be obtained. It has also been found that the formed DCI obtained by using the nine particles as a material is also produced by chlorine ions, and is suitable for use as a collection container for sand wafers, magnetic disks and the like. The present invention is based on these findings. That is, according to the present invention, a method in which a polycarbonate resin powder or granule is melt-extruded by a biaxial extruder to produce nine grains is used, and the biaxial extruder 200927416 is used (i) at least one The kneading unit directly under the water injection unit is located at the upstream side, the downstream side or both sides of the kneading unit, and the kneading unit composed of the exhaust unit on the downstream side of the water injection unit. • (ii) The kneading unit The most upstream screw element is an orthogonal kneading disk (C) or a forward kneading disk (f), the most downstream screw element is a reverse kneading disk (r), and (iii) the length of each screw element of the kneading section (LO is The range of 0_25D~D, the length of the mixing φ section (L〇 in the range of D~4D (D: inner diameter of the barrel) of the twin-screw extruder, together with the water injection (W) water injection, adjust the exhaust part ( V) A method for producing a polycarbonate resin having a vacuum degree of 6.7 kPa or less. According to the present invention, a molded article formed of nine particles of a polycarbonate resin obtained by the production method can be provided. [Embodiment] ® <Polycarbonate Resin> Used in the polycarbonate resin system of the present invention. An aromatic polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polymerization method in the presence of a solvent. The dihydric phenol used herein is, for example, hydroquinone 'Rezin, 4, 4'- Hydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2 , 2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (commonly known as bisphenol Z), 2,2-bis(3-phenyl 4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2·bis(4-hydroxyphenyl)butane, 2,2-dual ( 3,5-Dimethyl-4-hydroxyphenyl)propane, 4,4'-dihydroxyl 200927416 benzoquinone, 4,4'-dihydroxybiphenyl hydrazine, 4,4'-dihydroxybiphenyl sulphide Ether, 3,3'-yl- 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ether, 9,9-bis(4-hydroxytriazine, 9,9-double { (4. hydroxy-3-methyl)phenylhydrazine, 1,1-bis(4-•yl>-3,3,5-trimethylcyclohexane, α,α'-bis(4-hydroxybenzene) Di-isopropyl '1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, etc. Among them, bisphenol a, 2, 9, 9-double {(4-trans) -3-methyl) Phenyl}e, 1,1-bis(4-hydroxyphenyl)-3trimethylcyclohexane, hydrazine:, hydrazine: '-bis(4-hydroxyphenyl)-diisopropylbenzene is preferred. Two or more types may be used. The carbonate precursor is a carbonyl halide or a haloformate, and the like, or a dihaloformic acid vinegar of a dihydric phenol or the like. 丨, the dihydric phenol and the carbonate precursor are When the interfacial polycondensation method is used to produce a carbonate resin, a terminal stopper, a binary antioxidant, etc. may be used as necessary. The polycarbonate resin may be a branched polymer obtained by copolymerizing a trifunctional or higher polyaromatic compound. The carbonate resin may be a polyester carbonate resin obtained by copolymerizing an aliphatic difunctional carboxylic acid, and a mixture of two or more kinds of obtained polycarbonate resins may be subjected to an interfacial polycondensation reaction. It is usually the reaction of a dihydric phenol with phosgene in the presence of an acid binder, a catalyst and an organic solvent to promote the reaction. As the acid binder, for example, an alkali hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine can be used. As the organic solvent, for example, a hydrocarbon such as dichloromethane, chloroform, 1,2-dioxane, 1,1-dichloroethane, ethyl bromide, chlorobutane, chloropropane or chlorobenzene can be used; . These solvents may be used singly or in combination of two. Dimethyl phenyl benzene benzene, bisphenol, 3, 5 - some phosgene polyphenols can also be argon, which is a metal chloroethyl halide. 200927416 The amine catalyst used to promote the reaction is, for example. A tribasic amine such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butyl bromide; a quaternary ammonium compound; a catalyst such as a quaternary scaly compound; and particularly preferably triethylamine. The reaction temperature of the interfacial polycondensation method is usually 0 to 40 ° C, the reaction time is ♦ 10 minutes to 5 hours, and the pH in the reaction is preferably maintained at 9 or more. In the polymerization reaction, a terminal stopper is usually used. The terminal stop agent can be a monofunctional phenol. The monofunctional phenols are generally used as terminal stoppers to adjust the molecular weight by φ, and the polycarbonate resin obtained is blocked by a group derived from a monofunctional phenol, and the thermal stability is superior to those not sealed as such. The monofunctional phenols are, for example, phenol, p-terphenylbutanol, p-cumylphenol and isooctylphenol. These terminal stoppers are preferably introduced at least 5 mol% of all the terminals of the obtained polycarbonate resin, more preferably at least 10 mol%; and the terminal stoppers may be used singly or in combination of two or more. The molecular weight of the polycarbonate resin is preferably a viscosity average molecular weight (M) of lx 104 〜4xl04, more preferably 1.3xl04~3xl04, and particularly preferably 1.6xl04~2.4xl04. © Polycarbonate resin having such a viscosity average molecular weight is sufficient in strength, and melt flowability at the time of molding is good, and it is preferable that there is no form strain. The viscosity average molecular weight was 0.7 g of a polycarbonate resin dissolved in 10 ml of methylene chloride at 20 ° C, and the specific viscosity (7 / SP) was determined from the solution and substituted for the following formula. 7? /c=U ] + 〇_45x[t? ]2c (where U ] is the ultimate viscosity) [η ] = 1.23χ1〇·4Μ0·83 c = 0.7 The organic solvent solution of the polycarbonate resin obtained by the reaction It is usually washed with water. The water washing step is preferably using water having a conductivity of 10 〇 AS/cm -10- 200927416 or less, and water of 1 # S/cm or less is more preferable; mixing the organic solvent solution with water, stirring and allowing to stand Alternatively, the organic solvent solution phase and the aqueous phase are separated by a centrifugal separator or the like, and the organic solvent solution is taken out and repeated to remove water-soluble impurities. The water-soluble impurities were removed by washing with water to obtain a good color of the polycarbonate resin. In order to remove impurities such as a catalyst, the organic solvent solution of the polycarbonate resin is preferably subjected to pickling or alkali washing. The acid used for pickling is preferably an aqueous solution of phosphoric acid, hydrochloric acid, sulfuric acid or the like, preferably an aqueous solution having a concentration of 0.004 to 40 g/liter (or pH 5 or less). The alkali used for alkali washing includes an alkali metal compound such as sodium hydroxide or potassium hydroxide, an alkaline earth metal compound such as calcium hydroxide, barium hydroxide or magnesium hydroxide, and sodium hydroxide is particularly preferable; and the concentration is 0.1 to 20 g/liter (or An aqueous solution of pH 11. 5 or more is preferred. The ratio of the aqueous solution to the alkaline washing and the pickling to the organic solvent solution can be efficiently washed as long as the aqueous solution/organic solvent solution (capacity ratio) is in the range of 0.2 to 1.5. Next, the solvent of the water-washed organic solvent solution is removed to obtain a polycarbonate resin powder. The method for obtaining polycarbonate resin granules (granulation step) is simple in operation and post-treatment, and is preferably granulated in the presence of polycarbonate resin granules and warm water (about 40 to 90 ° C). In the apparatus, the polycarbonate granules are continuously supplied under stirring. It is better to think that the machine is more suitable for mixing with the steaming agent, and the kneading liquid and the solvent-dissolving agent are used to prepare the slurry with the fat tree. . The hot water treatment step is to supply the slurry to a hot water treatment container that feeds hot water of 90 to 100 ° C, or for 200927416, by blowing steam into the water to make the water temperature reach 90~1 〇〇 °C ' To remove the organic solvent contained in the slurry. The slurry discharged in the granulation step or the slurry after the hot water treatment is preferably such that the water and the organic solvent are removed to some extent by filtration, centrifugation or the like to recover the wet paste of the polycarbonate resin. Next, the wet paste of the polycarbonate resin was dried. The dryer can be a heating method or a hot air heating method. The polycarbonate resin can be allowed to stand still and conveyed by φ. Among them, a groove-shaped or cylindrical dryer in which conduction heating is used as a stirring of a polycarbonate resin is preferable, and a groove-shaped dryer is particularly preferable. The drying temperature is preferably from 1 3 0 to 1 50 °C. In the present invention, the shape of the polycarbonate resin to be subjected to the kneading extrusion treatment may be any of powder, fine particles, flakes, and nine-grain, preferably in the form of powder, fine particles or flakes. . In the present invention, the content of chlorine atoms in the polycarbonate resin to be subjected to kneading extrusion treatment is preferably 5 to 2,000 ppm, more preferably 5 to 1,500 ppm. The chlorine atom ® content is within this range to effectively achieve the object of the present invention. <Biaxial extruder> ~ The twin-screw extruder has at least one kneading extrusion unit composed of the water injection portion (1), the kneading portion (2), the seal ring (3), and the exhaust portion (4) . The twin-screw extruder preferably has an auxiliary exhaust portion (5) and an additive introduction portion (6). Fig. 1 is an example of the structure of a twin-screw extruder used in the present invention. (Water injection part (1)) The water injection part is a part where water is injected. If there are six or more water injection parts, the deterioration of the resin is not preferable. -12- 200927416 (Mixed part (2)) The kneading part is directly below the water injection part of the extruder, and is the part where the resin is mixed. In the present invention, the screw structure of the kneading section is extremely important. The most upstream screw element of the kneading section is an orthogonal kneading disk (c) or a forward kneading disk (f), and the most downstream screw element is a reverse kneading disk (r). The screw structure is preferably, for example, a combination of forward (f) and reverse (r), the same c-r, c-f-r, f-c-r, c-c-r-r, and f-f-r-r. D The pinch plate is preferably a double helix type. The preferred helix angle of the pinch pan is 15 to 90 degrees, and 45 to 90 degrees is better. Each of the kneading discs is composed of a plurality of discs, and the number of discs is preferably 2 to 7, and more preferably 3 to 6. · The length (L·) of each screw element in the kneading section is 0.25D-D, and 0.5D to 0.75D is more preferable. D is the inner diameter of the barrel. The length of the kneading section (1^) is D~4D, and 1.5D-3.5D is better. The total length of the screw (L3) is preferably 28D-49D, and 31.5D~45.5D is better. The content of the chlorine compound in the polycarbonate resin pellet obtained by the above-mentioned kneading section screw was lowered. The molded article formed of the obtained nine particles has a small amount of chlorine ion eluted from water, and is suitable as a storage container for a wafer or a magnetic disk. (Sealing ring (3)) The sealing ring is located on the upstream side, the downstream side or both sides of the kneading section. (Exhaust part (4)) The exhaust part is on the downstream side of the water injection part, and is a part where the gas generated by the kneading is excluded. (Auxiliary exhaust section (5)) The twin-shaft extruder is preferably provided with an auxiliary exhaust gas on the upstream side of the kneading extrusion unit -13-200927416. Therefore, the exhaust part of the twin-screw extruder is preferably 2, and 2 to 6 is better, preferably 2 to 5. Only one of the obtained polycarbonate resins has a high amount of residual chlorine ions in the nine particles. When the number of exhausted portions is too large, the total length of the extruder screw (L3) is increased, which tends to cause burnt and deterioration of the resin. influences. The mixing and extrusion unit of the twin-screw extruder is preferably 1 to 5, preferably 1 to 3, and preferably 1 or 2. (Additive introduction portion (6)) 0 The twin-screw extruder has an additive introduction portion on the downstream side of the kneading extrusion unit. The twin-screw extruder preferably has an auxiliary kneading portion on the downstream side of the additive introduction portion. In order to improve the dispersibility of the additive, an auxiliary kneading portion may be provided on the downstream side of the additive introduction portion. The screw structure of the auxiliary mixing section can be sufficiently mixed with the additive without any particular limitation. For example, the kneading disk, the positive kneading disk, and the reverse kneading disk can be used separately or in combination. <Kneading condition> The kneading system and the self-injection unit are used to adjust the degree of vacuum of the water discharge regulating portion to be 6.7 kPa or less. If the water injection amount added to the water injection part is too small, the water addition effect is not allowed, and the chlorine atom content of the obtained polycarbonate resin can not be reduced. If the water injection amount is too large, the degassing of the exhaust portion is insufficient, which may be caused by the polycarbonate resin. Adverse effects such as hydrolysis. Therefore, the water injection amount of the water injection portion is preferably 0.1 to 5 parts by weight per 100 parts by weight of the polycarbonate resin, more preferably 2 to 4 parts by weight. The conductivity of the injected water at 25 ° C is preferably 1 μ S / cm or less, more preferably 5 5 μ S / cm or less. When the water having a conductivity of S/cm or less is used, the polycarbonate resin is less likely to be hydrolyzed. The decrease in the molecular weight of the resin is suppressed, which is better than that of -14-200927416. The vacuum degree of each exhaust portion of the twin-screw extruder is 6.7 kPa or less, and more preferably 2.0 kPa or less. When the degree of vacuum is within this range, the water to be injected is sufficiently removed in the exhaust portion, and the chlorine atom content is reduced, and it is preferable that the aromatic polycarbonate resin is not adversely affected by hydrolysis or the like. The method of introducing the additive is not particularly limited, and the additive may be introduced alone or may be introduced by first incorporating a plurality of additives. It is also possible to first add the additive Q to the raw material polycarbonate resin granules to form an additive masterbatch. When the melting point of the additive is low, the melting of the additive introduction portion causes clogging, so that it is preferable to introduce the additive masterbatch which is previously blended with the polycarbonate resin powder and the additive into the double |> The amount of the additive to be introduced depends on the desired characteristics, and when the additive master batch is introduced, it is preferably from 1 to 30% by weight based on the obtained polycarbonate resin (total extrusion amount). 0.2 to 20% by weight is more preferable, and 0.3 to 10% by weight is particularly preferable. When it is introduced in an amount exceeding this range, the effect of reducing the chlorine compound is likely to be insufficient; if it is introduced in an amount less than this range, the amount of introduction of the additive is increased, and the desired characteristics may not be imparted. Therefore, it is preferred that the additive masterbatch of the polycarbonate resin granules and the additive is previously blended, and is introduced into the biaxial extruder from the additive introduction portion with respect to the obtained y. . <Various Additives> Various additives can be used to impart various characteristics to the nine-particulate polycarbonate resin of the present invention and the molded article formed from the pellets without departing from the object of the present invention. Additives can be compounded with release agent, thermal stabilizer, UV-15-200927416 line absorber, bluing agent, antistatic agent, flame retardant, hot wire masking agent, fluorescent dye (including fluorescent whitening agent), Pigments, light diffusing agents, reinforcing coatings, other resins or elastomers, etc. The release agent is preferably composed of an ester of an alcohol and a fatty acid in an amount of 90% by weight or more. Esters of alcohols and fatty acids are specific esters of monohydric alcohols and fatty acids and/or partial esters or full esters of polyhydric alcohols and fatty acids. The ester of the monohydric alcohol and the fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a φ saturated fatty acid having 10 to 30 carbon atoms. Further, a partial ester or a full ester of a polyhydric alcohol and a fatty acid is preferably a partial ester or a full ester of a saturated fatty acid having a carbon number of 25 and a saturated fatty acid having 10 to 30 carbon atoms. Specifically, esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmitate palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc.; stearyl stearate; It is better. Specifically, a partial ester or a full ester of a polyhydric alcohol and a saturated fatty acid has glyceryl stearate, glyceryl distearate, glyceryl tristearate, glyceryl monostearate, glycerol monodextrose Ester, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetradecanoate, propylene glycol monostearate, biphenyl biphenylate, sorbitol monostearyl a full ester or a partial ester of dipentaerythritol such as an acid ester, 2, ethylhexyl stearate or dipentaerythritol tartoic acid ester. Among these esters, a mixture of glyceryl monostearate, glyceryl tristearate, pentaerythritol tetrastearate, glyceryl tristearate and stearic acid stearyl sulphate is preferred. When the release agent is used as the weight %, the amount of the ester in the release agent is preferably from -16 to 200927416 by 90% by weight or more, more preferably 95% by weight or more. The content of the release agent in the polycarbonate resin granules is preferably from 0.01 to 0.6 parts by weight based on 100 parts by weight of the polycarbonate resin granules in terms of 〇·〇〇 5 to 2.0 parts by weight. Good, 〇. 〇 2~0.5 parts by weight is especially good. The heat stabilizers are phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and blocked heat-stable stabilizers. Phosphorus thermal stabilizers include phosphorous acid, phosphoric acid, sulfinic acid 'sulfonic acid and esters of these φ; specifically, triphenyl phosphite, phosphinic acid ginseng, bismuth acid (2, 4) -2 (tertiary butyl) benzene) vinegar, ginseng (2,6-di(tris-butyl)phenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tris (octadecyl) phosphite , diphenyl phthalate monophenyl ester, dioctyl phenyl phosphite monophenyl ester, diisopropyl phosphite monophenyl ester, monobutyl phthalate diphenyl ester, monodecyl phosphite diphenyl ester, phosphorous acid Octyl diphenyl ester, bis(2,6-di(tri-butyl)-4-toluene) pentaerythritol diphosphite, 2,2-methylenebis(4,6-di(tri-butyl) Benzene octyl phosphite, bis(indolyl) pentaerythritol diphosphite, bis(2,4-di(tributyl)) benzene) pentaerythritol diphosphite, distearyl Neopentyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl phosphate mono-o-xyl ester, dibutyl phosphate, dioctyl phosphate, Diisopropyl phosphate, dimethyl phenylphosphonate, benzene Diethyl acid, dipropyl phenylphosphonate, bismuth (2,4-di(tert-butyl)benzene)-4,4'-biphenyldiphosphinate, bismuth (2,4-di (three-stage) Butyl) phenyl)-4,3'-biphenyldiphosphinate, bismuth (2,4-di(tert-butyl)benzene)-3,3'-biphenyldiphosphinate, bis (2, 4-di(tertiary butyl)benzene)-4-phenylphenylphosphinate and bis(2,4-di(tert-butyl)benzene)-3-phenylphenylphosphinate. Among them, ginseng (2,4-di(tert-butyl)phenyl) phosphite, ginseng (2,6--17-200927416 bis(tri-butyl)phenyl)phosphite, ruthenium (2,4) can be used. -Bis(tri-butyl)phenyl)-4,4'-biphenyldiphosphinate, bismuth (2,4-di(tert-butyl)phenyl)-4,3'·biphenyldioxide Acid ester, hydrazine (2,4-di(tert-butyl)phenyl)-3,3'-biphenyldiphosphinate, bis(2,4-di(tert-butyl)phenyl)-4- Phenylphenylphosphonite and bis(2,4-di(tert-butyl)phenyl)-3-phenylphenylphosphinate; using bismuth (2,4-di(tertiary) benzene) The base 4,4'-biphenyldiphosphinate is especially preferred. The content of the phosphorus-based thermal stabilizer in the polycarbonate resin granules is preferably φ. 〇〇1 to 2. 2 parts by weight based on 100 parts by weight of the polycarbonate resin granules. Examples of the sulfur-based heat stabilizers include neopentyl quinone oxime (3-lauryl thiopropionate), neopentyl sterol oxime (3-myristyl thiopropionate), and neopentyl quinone oxime (3-hard). Lipidyl propionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-sulfur Dipropionate, etc., of which is neopentyl lanthanum strontium (3-lauryl thiopropionate), neopentyl sterol oxime (3 - myristyl thiopropionate), dilauryl-3, 3'- Thiopropionate and dimyristyl-3,3'-thiodipropionate are preferred. Pentaerythritol bismuth (3-lauroyl thiopropionate) is preferred. The thioether compound is commercially available as Sumilizer TP-D (trade name) and Sumilizer TPM (trade name) of Sumitomo Chemical Industries Co., Ltd., and the like. The content of the sulfur-based heat stabilizer in the polycarbonate resin granules is preferably from 〇〇1 to 〇.2 parts by weight based on 1 part by weight of the polycarbonate resin granules. Hindered phenolic thermal stabilizers are triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis [3-(3) , 5-di(tri-butyl)-4-hydroxyphenyl)propionate], neopentyl quinone [3-(3,5-di(tri-butyl)-4-hydroxyphenyl)propionate ]' 3-(3,5-di(tris-butyl)-4-hydroxyphenyl)propanoic acid octadecyl, 1,3,5-tri-18- 200927416 methyl·2,4,6-para ( 3,5-di(tri-butyl)-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di(tri-butyl)-4-hydroxyhydrocinnamate), 3 , 5-di(tertiary), diethyl 4-hydroxybenzylphosphonate, ginseng (3,5-di(tert-butyl)-4-hydroxybenzyl)isomeric cyanate and 3 ,9-bis{1,1-dimethyl-2-(;S-(3-tert-butyl-4-hydroxy-5-tolyl)propanyloxy]ethyl}-2,4,8, 10-tetraspiro[5.5]undecane, etc.; 3-(3,5-di(tris-butyl)-4-hydroxyphenyl)propanoic acid octadecyl ester is particularly preferred. The content of the hindered phenol-based thermal stabilizer in the polycarbonate resin granules is preferably 0.001 to 0.3 parts by weight based on 100 parts by weight of the polycarbonate resin granules. The ultraviolet absorber is at least 1 selected from the group consisting of a benzotriazole-based ultraviolet absorber, a diphenylketone-based ultraviolet absorber, a triple-trap ultraviolet absorber, a cyclic imide-based ultraviolet absorber, and a cyanoacrylate system. A kind of ultraviolet absorber is preferred. Examples of the benzotriazole-based ultraviolet absorber include 2-(2-hydroxy-5-tolyl)benzotriazole, 2-(2·hydroxy-5-trioctylphenyl)benzotriazole, and 2 -(2-hydroxy-based-3,5-diisopropylphenylbenzene)benzotriazole, 2-(2-hydroxy-3-tri-butyl-5-tolyl)-5-chlorobenzotriene Azole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2 -hydroxy-3,5-di(tert-butyl)phenyl)benzotriazole, 2-(2-hydroxy-3,5-di(tert-butyl)phenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di(tris-pentyl)phenyl)benzotriazole, 2-(2-hydroxy-5-trioctylphenyl)benzotriazole, 2-(2- Hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-isopropylphenyl- 6-benzotriazole phenyl), 2,2'-p-benzoic acid (1,3-benzoxanthene-4-one), 2-[2-hydroxy-3-(3,4,5,6) -tetrahydrofurfurimide methyl)-5-methylphenyl]benzotris-19- 200927416; these may be used singly or in combination of two or more. Preferred are 2-(2-hydroxy-5-tolyl)benzotriazole, 2-(2-hydroxy-5-tri-octylphenyl)benzotriazole, 2-(2-hydroxy-3, 5-diisopropylphenylbenzene)benzotriazole, 2-(2-hydroxy-3-tributyl-5-tolyl)-5-chlorobenzotriazole, 2,2'-methylene double [4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-[2-hydroxy-3-(3,4,5 , 6-tetrahydroindenine methyl)-5-tolyl]benzotriazole; more preferably 2-(2-hydroxy-5-trioctylphenyl)benzotriazole, 2,2 '_Methylene bismuth [4-(1,1,3,3-tetramethylbutyl)-6-(211-benzotriazol-2-yl)phenol]. The diphenyl ketone ultraviolet absorbers are 2,4-dihydroxydiphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-octyloxydiphenyl ketone, 2-hydroxy- 4-Benzyloxydiphenyl ketone, 2-hydroxy-4-methoxy-5-thiohydroxydiphenyl ketone, 2-hydroxy-4-methoxy-5-thiohydroxytrihydrodiphenyl ketone, 2,2'-dihydroxy-4-methoxydiphenyl ketone, 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,2'-dihydroxy-4,4'-dimethoxy Diphenyl ketone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium thiohydroxydiphenyl ketone, bis(5-benzylidene-4-hydroxy-2-methoxy Phenyl)methane, 2-hydroxyindole-4-n-dodecyldiphenyl ketone, 2-hydroxy-4-methoxy-2'-carboxydiphenyl ketone, and the like. The tritrap-based ultraviolet absorber may be exemplified by 2-(4,6-diphenyl-1,3,5-trin-2-yl)-5-[(hexyl)oxy]phenol, 2-(4) , 6-bis(2,4-dimethylphenyl)-1,3,5-trit-2-yl)-5-[(octyl)oxy]phenol or the like. The cycloimidate-based ultraviolet absorber can be exemplified by 2,2'-bis(3,1-benzoindole-4-one), 2,2'-p-benzoquinone (3,1-benzopyrene). -4-keto), 2,2'-m-benzobis(3,1-benzoindole-4-one), 2,2'-(4,4'-di-extended benzene) bis (3,1- Benzoindole-4-one), 2,2'-(2,6-naphthalene)bis(3,1-benzoxanthene-4-one), 2,2'-(1,5-naphthalene) Bis(3,1-benzoindole-4-one), 2,2'-(2-methyl-p-benzophenone) bis(3,1-benzobenzo-20- 200927416 曙 well-4- Ketone), 2,2'-(2-nitro-p-phenylene) bis(3,1-benzobenzoindole-4-one) and 2,2'-(2-chloro-p-phenylene) double (3,1-benzobenzoindole-4-one) and the like. Among them, 2,2'-p-benzoic bis(3,1-benzopyrene-4-one) '2,2'-(4,4'-di-extended benzene) bis (3,1-benzene) Trap-4-one) and 2,2'-(2,6-naphthalene)bis(3,1-benzoxanthene-4-one) are suitable; 2,2'-p-benzoquinone (3, 1-benzoxanthene-4-one) is particularly suitable. This compound can be used as CEi-P (trade name) of a commercially available bamboo oil (stock). The cyanoacrylate-based ultraviolet absorber is, for example, 1,3-bis[(2'-cyanoindole-3',3'-diphenylpropenyl)oxy]-2,2-bis[(2-cyanyl-3). 3-diphenylacrylinyl)oxy]methyl)propane, and 1,3-bis[(2-cyano-3,3-diphenylpropenyl)oxy]benzene. The amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 part by weight, more preferably 0.05 to 0.8 part by weight, per 100 parts by weight of the polycarbonate resin powder. In the blending amount range, the polycarbonate resin molded article can be imparted with sufficient weather resistance depending on the use. The blue agent is Macrolex Violet B from Bayer, Macrolex Blue © RR and POLYSINSLEN Blue RLS from Clariant. The bluing agent can be used to remove the yellowish tint of the polycarbonate resin powder. In particular, a polycarbonate resin granule which is imparted with weather resistance is provided with a certain amount of ultraviolet ray absorbing agent, and in fact, a polycarbonate resin molded article which is "effect of the ultraviolet absorbing agent and colored" is likely to have a yellowish color tone. In particular, it is considered to give the sheet and the lens a natural transparency, and the combination of the bluing agent is extremely effective. The blending amount of the bluing agent is preferably 0.05 to 1.5 ppm with respect to the polycarbonate resin powder, and more preferably 0.1 to 1.2 ppm. In addition, when the polycarbonate resin is kneaded and squeezed, the resin temperature is appropriately set according to the molecular weight of the polycarbonate resin, such as the molecular weight of 27-200927416, and is 27 〇 to 35 (about TC). <Molded article> The polycarbonate resin pellet obtained by the above method can be formed by a general method such as extrusion molding. The present invention comprises a molded article obtained by molding nine pieces of a carbonate resin according to the foregoing method. The molded article obtained by molding the polycarbonate resin in nine particles has a markedly reduced amount of chlorine ions. φ The molded article is in water at 8 (after heating for 24 hours, the amount of chloride ion eluted from the TC is preferably 1 ng/cm 2 or less, preferably 9 ng/cm 2 . The lower limit is not particularly limited, but is 0.5 ng/cm 2 . Hereinafter, the molded article is narrowly used as a storage container for a wafer or a magnetic disk. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to the examples. The weight of the table is determined by the following method: · (1) Chloride ion amount: The polycarbonate resin is nine pieces which are injection-molded to a thickness of 1 mm and cut to a length of 20 mm and a width of 25 mm. Into the extraction bag, add 15cm3, heat at 80 ° C for 24 hours in a sealed state, then cool to room temperature and quantify the CT in water by ion chromatography to determine the surface area per 1 cr of the molded product. The equipment and conditions used are as follows 1. I. It is more difficult to form and shoot the water-soluble molded product. It is limited to this % table weight model, ultra-pure water, followed by cm2-22-200927416 Table 1 Device DIONEX DX-500 sample injection amount 0.5 Cm3 mash NaOH separation column IonPac AS4A-SC detector Conductivity meter (2) Chlorine atom content Completely burns nine pieces of polycarbonate resin, and the generated hydrogen chloride (HC1) is titrated with barium silver ion (Ag + ), thereby determining the chlorine atom content by the amount of electricity required for potentiometric titration. (3) Hue (b 九 九 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯 聚碳酸酯Examples 1 to 11 and Comparative Examples 1 to 5 have three exhaust ports in the second to seventh figures (the closest to the raw material supply bucket are 〇^1, 乂2, 73), and the exhaust port 乂2. A twin-screw extruder with a screw diameter of 3〇ιηιηφ (the closest to the water injection from the raw material supply bucket, Wl, W2) is directly provided in front of the 乂3. TEX30α manufactured by Nippon Steel Co., Ltd., L3/ of the entire screw structure. D = 45.5] 'The raw material resin and the additive described in Table 2 were extruded into a bundle shape under the pressure conditions of Table 2, and cut into nine pieces. The additive was first blended with the following resin material C to make a target. Adding 5 times the concentration of the masterbatch to the total of the obtained polycarbonate resin (the combination of the resin raw material and the master batch) The ratio of 2% by weight was introduced into the master batch by the additive introduction portion. The target addition amount of the additive is shown in Table 3. The evaluation results of the obtained polycarbonate 23-200927416 resin were as shown in Table 4. The raw material resin in Table 2 The screw marks of the additive and the water injection unit are as follows. Resin material A: A polycarbonate resin powder (having a chlorine atom content of 50 ppm) having a viscosity average molecular weight of ,8,500 obtained by reacting bisphenol A and phosgene in methylene chloride in a usual manner. Resin material B: A polycarbonate resin powder (chlorine atom content: 236 ppm) having a viscosity average molecular weight of 18,5 Å obtained by reacting bisphenol A and phosgene in dichloromethane in a usual manner. Resin raw material C: polycarbonate resin powder ( (chlorine atom content ggppm) having a viscosity average molecular weight of 22,400 obtained by reacting bisphenol A with phosgene in dichloromethane in a usual manner. Additives: UV absorber: 2-(2-hydroxy-5-tertiary octylphenyl) benzotriazole release agent: pentaerythritol tetrastearate phosphorus system stabilizer: ginseng (2,4-two (tertiary butyl) phenyl) phosphite hindered phenolic thermal stabilizer: 3-(3,5-di(tris-butyl)-4-hydroxyphenyl) octadecyl propionate on blue: Bayer Macrolex Violet B Screw A (refer to Figure 2): The shape of the screw (the screw angle of the screw element in the kneading section is 90 degrees in the orthogonal kneading disk, the reverse kneading disk is 45 degrees, the La series 2.0D) is the water injection part. The sealing ring (length 〇.5d) is arranged at 1.0D on the upstream side of the opening of the nozzle of the press, and 2 sets of orthogonal kneading discs (length 0.5d; 5 disks of length 1.1D) downstream of the ring, 2 groups of reverse After pinching the tray (length 0.5D; consisting of 5 discs with a length of 0.1D), the fitting -24-200927416 is provided with a sealing ring (length 0.5D). Screw B (Refer to Fig. 3): Screw shape (the screw angle of the screw part of the kneading part is 45 degrees in the forward kneading plate, 45 degrees in the reverse kneading plate, and 2.0D in the L2). The water injection part is injected into the extruder. A sealing ring (length 0.5D) is arranged at 1.0D on the upstream side of the opening, and three sets of forward kneading discs (length 0.5D; 5 disks of length 0.1D) and 1 set of reverse kneading disks are arranged downstream of the ring ( After a length of 0.5D; consisting of 5 discs of length 0.1D), & is equipped with a seal ring (length 0.5D). Screw C (Refer to Fig. 4): The screw structure (length 0.5D) disposed at 1.0D on the upstream side of the opening of the injection unit of the extruder is replaced with a normal full-thread disk. Screw D (refer to Figure 5): The screw structure (the screw angle of the screw element in the auxiliary kneading section is 45 degrees in the forward kneading disk, and the L2 system is 1.0D). In the screw A, the downstream part of the extruder water injection part (W2) On the downstream side of the exhaust port (V3), an additive introduction portion is provided, and two sets of forward kneading disks (length 0.5D; 5 disks having a length of 0.1D) are disposed on the lower side. Screw E (refer to Fig. 6): In the screw structure of the screw B, instead of the reverse kneading disc, the forward kneading disc is used instead. Screw F (refer to Fig. 7): In the screw structure of the screw D, instead of the orthogonal kneading disc and the reverse kneading disc, all of them are replaced with a forward kneading disc. -25- 200927416 CSI嗽 Exhaust vacuum (kPa) 1—Η 1 1 Η cn 1 CO CO 1 1 1 1 » On cs r_ H cn cn r λ 1 1 1 1 1 1 οο CN 1 < R Γ·· < On V Η cn cn 1 t 〇〇 CS Η cn cn r—Η H 严H r"< CO » "< r-H 7.20 7.20 1.30 1—Η *—Η i 1 $ Γ~ "< οο CS » i « ^ Production <"< CO ι—Η 1.30 1.29 1 4 « i 7.20 7.20 7.20 1.30 S s CS1 0.53 1 0.52 1 0.50 1 1 1 0.50 1 1 1 1 1 1 1 m - 1—^ 0.52 0.54 0.54 0.51 0.50 0.52 0.51 0.52 0.52 r —H IT) 1 i 0.52 0.55 0.50 0.54 0.51 Screw revolutions (rpm) in CSl 1 < 1 < 1—Η 1 1 4 CS (Ν ϊ—H r'~' < 1 ' < cs t-H CO csi ON τ < 1 1 < 挤压 Extrusion (kg/hr) 沄 沄 螺杆 Screw construction 1 1 1 << PQ PQ <: < PQ u u Q Q PQ m Q P-J Ρη Additives Destroy Destroy 壊 m Destroy Destroy m 擗 擗 摧 Destroy 蚺 Destroy 树脂 Resin raw material Type < C << m PQ << U U < PQ U < U i 1 EXAMPLES Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparison Example 1 Comparative Example 3 Comparison Example 3 Comparison Example 4 Comparative Example 5 -9CN1- 200927416 Table 3 Additive Additives UV Absorber 0.2 wt% Release Agent 0.1 wt% Phosphate Stabilizer 0.03 wt% Hindered Phenol Stabilizer! I 0.05 wt% bluing agent 0.5 ppm
表4 實施例 溶出之氯離子量 (ng/cm2) 九粒中之氯原子含量 (ppm) 九粒之b値 實施例1 4 1 -0.2 實施例2 7 1 0.0 實施例3 6 1 -0.1 實施例4 9 1 0.1 實施例5 4 1 -0.2 實施例6 8 1 0.0 實施例7 9 1 0.1 實施例8 4 1 0.0 實施例9 8 1 0.0 實施例10 6 1 -2.3 實施例11 9 1 -2.5 比較例1 11 2 0.3 比較例2 11 2 0.4 比較例3 12 3 -2.5 比較例4 13 3 0.1 比較例5 14 3 -2.5 -27- 200927416 實施例12及比較例6 使用實施例1及比較例1中得之九粒，成形爲矽晶圓 用收藏輸送容器。浸泡此矽晶圓用收藏輸送容器於8〇〇C2 溫水中24小時。然後’將容器乾燥，於此容器插入特定片 數之矽晶圓，密閉後在容器內保持於常溫1週後，取出矽 晶圓’測定表面5處的水與晶圓表面之接觸角。測得之接 觸角平均値如表5。水與晶圓表面之接觸角係表示晶圓表 φ 面的污染程度之指標’接觸角大則晶圓表面之疏水性高， 表示污染程度高。接觸角係以10度以下爲佳。 表5 m 1角 插入前 保持後 實施例12 3.5 3.8 比較例6 3.5 12.5 發明效果Table 4 The amount of chloride ion eluted in the examples (ng/cm2) The content of chlorine atoms in the nine grains (ppm) 9 grains b値 Example 1 4 1 -0.2 Example 2 7 1 0.0 Example 3 6 1 -0.1 Implementation Example 4 9 1 0.1 Example 5 4 1 -0.2 Example 6 8 1 0.0 Example 7 9 1 0.1 Example 8 4 1 0.0 Example 9 8 1 0.0 Example 10 6 1 -2.3 Example 11 9 1 -2.5 Comparative Example 1 11 2 0.3 Comparative Example 2 11 2 0.4 Comparative Example 3 12 3 - 2.5 Comparative Example 4 13 3 0.1 Comparative Example 5 14 3 - 2.5 -27 - 200927416 Example 12 and Comparative Example 6 Using Example 1 and Comparative Example Nine of the first ones were formed into a collection container for the wafer. The wafer was immersed in a collection container for 8 hours in 8 ° C 2 warm water. Then, the container was dried, and the container was inserted into a specific number of wafers. After being sealed and kept at room temperature for one week, the wafer was taken out to measure the contact angle between the water at the surface 5 and the surface of the wafer. The measured contact angles are shown in Table 5. The contact angle between water and the surface of the wafer indicates the degree of contamination of the surface of the wafer φ. When the contact angle is large, the hydrophobicity of the surface of the wafer is high, indicating a high degree of contamination. The contact angle is preferably 10 degrees or less. Table 5 m 1 angle Before insertion After holding Example 12 3.5 3.8 Comparative Example 6 3.5 12.5 Effect of the invention
依本發明，使用注水部之混練部具備水分散效果優良 之螺桿而具有材料密封的附排氣口之雙軸擠壓機，可得氯 原子含量低，溶出之氯離子量少的聚碳酸酯樹脂。依本發 明可得適用作爲收藏物表面受污染之疑慮少的收藏輸送容 器之材料的聚碳酸酯樹脂。依本發明可得適用作爲矽晶 圓、磁碟片等之收藏輸送容器的材料之聚碳酸酯樹脂。依 本發明可得收藏物表面受污染之疑慮少的收藏輸送容器。 產業上之利用可能性 由本發明之製造方法得之聚碳酸酯樹脂適用作爲形成 -28 - 200927416 對於表面污染敏感之矽晶圓、磁碟片等的收藏輸送容器之 材料。 【圖式簡單說明】 第1圖用於本發明之雙軸擠壓機的構造之一例。 第2圖用於實施例之雙軸擠壓機的構造圖（螺桿A)。 第3圖用於實施例之雙軸擠壓機的構造圖（螺桿B)。 第4圖用於實施例之雙軸擠壓機的構造圖（螺桿C)。 第5圖用於實施例之雙軸擠壓機的構造圖（螺桿D)。 第6圖用於實施例之雙軸擠壓機的構造圖（螺桿E)。 第7圖用於實施例之雙軸擠壓機的構造圖（螺桿F)。 【主要元件符號說明】 1 1 注水部 2 混練部 3 封環 4 排氣部According to the present invention, a biaxial extruder having a gas-sealing portion having a water-dispersing effect and having a material-sealed venting port is used, and a polycarbonate having a low chlorine atom content and a small amount of eluted chlorine ions can be obtained. Resin. According to the present invention, a polycarbonate resin which is suitable as a material for a collecting and transporting container having less contamination of the surface of the collecting object can be obtained. According to the present invention, a polycarbonate resin which is suitable as a material for a collection container of a twin crystal, a magnetic disk or the like can be obtained. According to the present invention, it is possible to obtain a collecting and transporting container having less contamination of the surface of the collecting object. INDUSTRIAL APPLICABILITY The polycarbonate resin obtained by the production method of the present invention is suitably used as a material for forming a storage container of a wafer, a magnetic disk, or the like which is sensitive to surface contamination, -28 - 200927416. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of the structure of a twin-screw extruder of the present invention. Fig. 2 is a structural view (screw A) of the twin-screw extruder of the embodiment. Fig. 3 is a structural view (screw B) of the twin-screw extruder of the embodiment. Fig. 4 is a structural view (screw C) of the twin-screw extruder of the embodiment. Fig. 5 is a configuration diagram (screw D) of the twin-screw extruder of the embodiment. Figure 6 is a configuration diagram (screw E) of the twin-screw extruder of the embodiment. Fig. 7 is a configuration diagram (screw F) of the twin-screw extruder of the embodiment. [Description of main component symbols] 1 1 Water injection part 2 Kneading part 3 Sealing ring 4 Exhaust part
5 輔助排氣部 6 添加劑導入部 -29-5 Auxiliary exhaust unit 6 Additive introduction section -29-