200909472 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種熱塑性聚合物組成物，特別是指 一種备被應用來製成瓶子時，在吹瓶前瓶胚可被快速升溫 (heat up)且所製成的瓶子近乎無色的熱塑性聚合物組成物， 以及用於製備該組成物的方法。 【先前技術】 熱塑性聚合物，特別是聚對苯二甲酸乙二醋 (polyethylene terephthalate，簡稱 pET)或其共聚酯被應用 在膠片、瓶子或者其他供食物或飲料用容器的製造上是很 普遍的。一般而言，瓶子的製造過程分成兩階段，以下以 PET瓶子的製造為例來說明，第一階段為將pET注射到模 組中形成瓶胚（bottle preform)，第二階段為將壓縮的空氣注 入模組中並將瓶胚吹成瓶子，在第二階段時瓶胚的溫度要 被加熱到1〇〇 C左右以便進行吹瓶，因此再加熱（reheat)的 速率變成為第二階段的速率決定步驟，一般商業上再加熱 步驟中使用的加熱器都是石英燈管，其會放射出集中在波 長500nm〜2000nm間的電磁波。 然而’ PET對上述波長區間的電磁波的吸收率低，通 常會吸收疋因為裡面所含的不純物或添加物，例如殘留的 觸媒或其他雜質’因為電磁波被此等物質散色或這些物質 吸收電磁波而使得瓶胚能吸收電磁波，因此PET組成物的 再加熱時間就和組成物本身的透明度有很大的關係，當 PET組成物中所含不純物或添加物越多，愈可促進再加熱 200909472 的速率，但同時卻也造成航胚的霧化。再纟，所添加物質 的顏色越深，吸收電磁波能力越好，瓶胚加熱的時間也就 越短，但瓶子因此無法保持透明無色的狀態，此將無法滿 足目前商業上對於無色之瓶子或其他型態容器的大量需求 ’特別是對於亞洲市場而言。 已有不少專利揭露，藉由將添加劑添加到熱塑性聚合 物中，以提升吸收電磁輕射的效能並減少再加熱的時間， 如下述地：u.s.Pat.4408004利用碳黑來達到減少再加熱時 間的目的；有些鐵的氧化物也可以達到此目的，例如 U.S.Pat.4420581 #示三氧化二鐵可以減少再加熱時間； U.S.Pat.4408004 A 5419936則利用還原録聚合觸媒來提升 加熱速率’· 1^加4481314㈣某些g酉昆（anthraquin嶋） 類型的染料也可達此目的。u.s，Pat侧792則使用不參與 反應的鐵化合物’譬如FeP、FeSi或其組合物來減少再加熱 時間；U_S.Pat.7189777 %揭示添加活性碳來提升加熱速率 。以上所有添加劑都是黑體或灰體吸收，會吸收全光譜的 光’因此對於製成的瓶子或其他型態容器的顏色跟霧度都 會造成無法接受的影響，影響的多寡則和添加的量呈正比 ’在某些程度上可以利用改變添加劑的顆粒大小來減少這 些影響，但無法全部消除。 另，u.s.Pat.5529744揭露一由含有金屬粒子（譬如讥、200909472 IX. Description of the Invention: [Technical Field] The present invention relates to a thermoplastic polymer composition, and more particularly to a preform which can be rapidly heated when it is used to make a bottle. Up) and the resulting bottle is a near colorless thermoplastic polymer composition, and a method for preparing the composition. [Prior Art] Thermoplastic polymers, especially polyethylene terephthalate (pET) or its copolyesters, are commonly used in the manufacture of film, bottles or other containers for food or beverages. of. In general, the manufacturing process of the bottle is divided into two stages. The following is an example of the manufacture of a PET bottle. The first stage is to inject pET into the module to form a bottle preform, and the second stage is to compress the air. Injecting into the module and blowing the preform into a bottle. In the second stage, the temperature of the preform is heated to about 1 〇〇C for blowing, so the rate of reheating becomes the rate of the second stage. In the decision step, the heaters used in the general commercial reheating step are all quartz lamps which emit electromagnetic waves concentrated between wavelengths of 500 nm and 2000 nm. However, PET has a low absorption rate of electromagnetic waves in the above wavelength range, and usually absorbs impurities due to impurities or additives contained therein, such as residual catalyst or other impurities. Because electromagnetic waves are scattered by such substances or electromagnetic waves are absorbed by these substances. Therefore, the preform can absorb electromagnetic waves, so the reheating time of the PET composition has a great relationship with the transparency of the composition itself. The more impurities or additives contained in the PET composition, the more the reheating of 200,909,472 is promoted. The rate, but at the same time, also causes the atomization of the embryo. Furthermore, the deeper the color of the added substance, the better the ability to absorb electromagnetic waves, and the shorter the heating time of the preform, but the bottle cannot maintain a transparent and colorless state, which will not satisfy the current commercial colorless bottle or other. The large demand for type containers is especially for the Asian market. There have been many patents disclosed to increase the efficiency of absorbing electromagnetic light and reduce the time of reheating by adding additives to the thermoplastic polymer, as follows: usPat.4408004 uses carbon black to reduce the reheating time. The purpose of this; some iron oxides can also achieve this purpose, such as USPat.4420581 # shows that ferric oxide can reduce the reheating time; USPat.4408004 A 5419936 uses the reduction recording polymerization catalyst to increase the heating rate'· 1 ^ plus 4481314 (d) Some gypsum (anthraquin) type of dye can also achieve this purpose. U.s, Pat side 792 uses an iron compound that does not participate in the reaction, such as FeP, FeSi, or a combination thereof to reduce the reheating time; U_S. Pat. 7189777% reveals the addition of activated carbon to increase the heating rate. All of the above additives are absorbed by black or gray body and will absorb the light of the full spectrum'. Therefore, the color and haze of the bottle or other type of container will have an unacceptable impact, and the amount of influence and the amount added will be positive. These effects can be reduced to some extent by varying the particle size of the additive, but not all. In addition, u.s. Pat. 5529744 discloses a metal particle (such as ruthenium,
Sn、Ag、Au、Cu、As、Cd、Hg、pt 及/或 pd)的熱塑性聚 合物製成的瓶子’其主要利用聚合過程中添加還原劑及前 述該等金屬的化合物並使該等金属化合物還原成金屬粒子 200909472 ，ι特別是Sb，來增加聚醋再熱 製得的瓶子的黃度絕對值偏大 的速率，不過此專利所揭示 ’因此無法得到無色的瓶子 升製程=7減少瓶“熱時間，但節能並提 子因無法製得商f上大量需求的無色瓶 色㈣=對於可快速升溫域製成的瓶子近乎無 色的‘、·、』性聚合物組成物之亟大的需求。 【發明内容】 〇等&案所揭不n提升再熱速率的特定種類的碳系 、貝金屬化合物或金屬’在添加到熱塑性聚合物後都無 法呈現無色’因此無法滿足市場上對無色瓶子或其他型態 的容器的大量需求。 —本案申請人思及，熱塑性聚合物組成物要能在石英燈 管照射下快速升溫’除了如前述藉由增加能吸收該波長區 門電磁波的物I外，S能藉由在聚合物中添加適量的熱傳 導物質，應可使整體組成物具有更佳的熱傳導性質並因 此提高預製品（如瓶胚）加工前的升溫速率，因此申請人嘗試 由各式金屬粉末中來挑選出具有良好導熱特性且能使最終 瓶子呈現無色者，然而，如熟悉高分子技術人士所知的， 金屬粒子摻於聚合物後的最後顯色是由一極為複雜的機制 所控制’因此很難由微粒子單獨的顏色來推估於其被摻於 聚合物後會呈現的最终顏色’申請人經多方研究，最後發 現’銘、鎮、辞、鎢與鈣是在兼顧熱傳導與無色上絕佳的 選擇’只要控制該等特定種類金屬的粉末於熱塑性聚合物 7 200909472 中的添加量在一定的範圍，並使其分散在熱塑性聚合物中 ，即可達瓶胚快速升溫及瓶子近乎無色的雙重目的，而至 聚合物製備過程之何時添加或如何添加，則無特殊 因此，本發明之第-目的，即在提供一種快速升溫的 熱塑性聚合物組成物，包含-熱塑性聚合物及多數個金屬 粒子’其中該熱塑性聚合物具有—介於哉_之間 的數目平均分子量，而該等金屬粒子是鋁、鎂、辞、鎢、 药粒子，或此等之組合。本發明之該熱塑性聚合物組成物 可視需要而被製成一熔融物(melt)、醋粒(peiie〇、片材 ㈣⑽)或容器（eQntainer)，特別地適合用於製成瓶胚與瓶子 〇 本發月之第一目的，即在提供一種用於製備該快速升 溫的熱塑性聚合物組成物的方法，包含之步驟為：在該熱 塑性聚合物的-選自於下面群組中的階段添加該等金屬^ 子·聚口月9進料階段、液態聚合階段、固態聚合階段，以 及加工成型階段。 本發明之該快速升溫的熱塑性聚合物組成物，因為含 有可傳導熱的金屬粒子，因此可有效地提高升溫速率，因 此減少加工(譬如吹瓶)前再加熱的時間，大幅地降低製程成 本’再者’該等金屬粒子在選擇上是已先顧及其分散於聚 °物中最後的顯色與透明度，因此只要適當控制該等金屬 粒子的添加量與粒子大小，即能使該熱塑性聚合物組成物 的加工成品’譬如瓶子，呈現近乎無色的狀態，所以能符 200909472 這是前述所有前案 合市場，特別是亞洲市場廣大的需求 所無法達到的。 【實施方式】 較佳地，本發明組成物中的該等金屬粒子是銘粒子。 較佳地，在本發明之熱塑性聚合物組成物中基於該 熱塑性聚合物的總重計，該等金屬粒子的含量是介於二 至200PPM之間，更佳地，係介於lppM至ι〇〇ρρΜ之間， ，又更佳地，是介於20PPM至100PPM間，最佳地，是介 於 25PPM 至 100PPM 間。 較佳地，適用於本發明的該等金屬粒子具有—介於 至ΙΟΟμιη間的d5〇粒徑，更佳地，是具有一介於〇工至 50μπι間的dso粒徑，進一步更佳地，是具有一介於〇」至 ΙΟμηι間的粒徑，最佳地，是具有一介於〇1至叫瓜間 的d5〇粒徑。 較佳地，適用於本發明的熱塑性聚合物是由至少一衍 生自一二酸組份的重複單元A與至少一衍生自一二醇組份 的重複單元B構成的聚酯。較佳地’該二酸組份包含 C2〜Ci6 之脂族一缓酸（aliphatic dicarboxylic acid)、C8~C16 之 芳族二羧酸（aromatic dicarboxylic acid)，或此等之—組合。 選擇性地，該二酸組份包含至少一 C8~Cl6之芳族二羧 酸’且較佳地，該Cs-C!6之芳族二羧酸係為對苯二甲酸。 更佳地，該熱塑性聚合物是聚對苯二甲酸乙二酯或聚對苯 —曱酸乙二酯之共聚酯，且較佳地，以該二酸組份的總莫 爾數計’對苯二甲酸是佔該二酸組份的至少60mol%，而以 200909472 該二醇組份的總莫爾數計’乙二醇是佔該二醇組份的至少 60mol%。 選擇性地，該二酸組份包含二CrCi6之芳族二缓酸。 在本發明之一具體例中’該二CpC〗6之芳族二羧酸分別為 對苯二甲酸以及間苯二甲酸。更佳地，該二酸組份包含96_ 99mol%的對苯二甲酸及4-1 mol%的間苯二甲酸。 選擇性地，該二醇組份包含至少一 C2~C10之二醇，更 佳地’該二醇組份包含至少一 C2〜C5之二醇。在本發明之— 具體例中’該二醇組份包含乙二醇，且因聚合過程中，部 分乙二醇會脫水形成二乙二醇（diethylene glyC〇i，簡稱 DEG) ’因此聚合產物之共聚酯中會存在衍生自二乙二醇的 重複單元B。較佳地’在該聚酯中，以重複單元b的總莫 爾數計，衍生自乙二醇的重複單元B是佔95-99mol%，且 衍生自二乙二醇的重複單元B是佔5-lmol%。 由於金屬粒子可於熱塑性聚合物聚合的各個階段添加 ，因此本發明組成物中的熱塑性聚合物的分子量是涵蓋熱 塑性聚合物在液態聚合（一般聚合度約為】丨〇〇)與固態聚 合階段（一般聚合度約為100〜400)的分子量範圍，即具有 1，000〜60,000之間的數目平均分子量。選擇性地，該熱塑性 聚合物是具有1，000〜45,〇〇〇之間的數目平均分子量，更進 一步可選擇地，該熱塑性聚合物是具有1〇〇〇~35〇〇〇之間 的數目平均分子量，而在本發明的各具體例中，於聚合的 各階段所製得的組成物中的熱塑性聚合物分収具有u5〇 、19,000與31，000的數目平均分子量。 10 200909472 本發明之組成物可被用於製成一溶融物、醋粒、片材 或容器，且特別適用於製成瓶胚與瓶子。 因此，本發明還提供一種由本發明熱塑性聚合物組成 物製得的瓶胚，且該雜較佳地是具有—條抓至腑。 的L*亮度（brightness)，以及一介於如的霧度更佳地， 具有-介於80%至鹏的L*亮度，以及一介於2—3 5的霧 度。且較佳地，該瓶胚具有一介於_3至+3間的a*，更佳地 具有一介於-2至+2間的a*，更佳地，該a*是呈一約_2至〇 間的值。較佳地，該瓶胚具有—介於_5至+7間的b*，更佳 地是具有一介於·5至+5間的b*，最佳地，該b*是呈一約❶ 至5間的值。在本發明的各個具體例中，所製得的瓶胚的 霧度疋介於3_5至8.1之間，a*是介於」36至_142間且… 是介於4.73至4.98間 本發明也提供一種由本發明熱塑性聚合物組成物製得 的瓶子’且該瓶子較佳地是具有一介於88%至励％的L*， 以及一介於1-4的霧度。且較佳地，該瓶子具有一介於丨至 + 1間的a*，更佳地是具有一介於·〇·5至+〇 5間的，更佳 地’該a*疋呈-約_〇·5 〇間的值。較佳地，該瓶子具有 一介於-3至+5間的b*，更佳地是具有一介於_丨至科間的 b*，更佳地，該b*是呈一約〇至3間的值。在本發明的各 個具體例中’所製得的瓶子的霧度是介於2丨至4之間，# 疋”於-0.36至-0.47間且b*是介於2.41至2.59間（近乎無 色）0 當被用於本文時，L* ' #與b*數值是依據一使用1976 11 200909472 3 b的表色方式的Macbeth color eye 2145光譜儀所 測得，其中操作時使用的觀測角S 2。，發光源是D65。當 J式樣印疋瓶胚時，樣品厚度定為;當測試樣品是瓶 子，樣。。厚度定為〇 35mm。其中，L*值愈大，代表亮度 愈同，a*>〇代表顏色偏紅，a*<〇代表顏色偏綠；b*>〇代表 顏色偏頁，b*<G代表顏色偏藍。至於霧度，則是使用 HAZESUGA儀器並依據ASTM D1〇〇3方法來測得。 本發月之用於製備該快速升溫的熱塑性聚合物組成物 的方法匕3以下步驟：在該熱塑性聚合物的一選自於下 面群組中的階段添加該等金屬粒子：聚合前進料階段、液 態聚合階段、固態聚合階段，以及加工成型階段。在本發 明之具體例中，該等金屬粒子是在熱塑性聚合物的液態^ 。又時被a加。再者’添加時可以—次添加或分段添加 方式進行。同時，可視製程的需求而先將金屬粒子分散於 -液態介質中，之後再加入上述聚合物聚合或加工的各個 階段，較佳地，該液態介質為乙二醇。 再者，如果該等金屬粒子是於加工階段，譬如射出瓶 胚時才被添加，較佳時先被施予一乾燥處理。另外，若為 降低對生產線的污染並使粒子分散更為均勾，可先將金屬 粒子與部分的聚合物s旨粒先混合並先製得含金屬粒子的母 粒，之後再大量用於生產線。 【實施例】 以下以實施例進-步說明本發明，並搭配比較例暨功 效測試以彰顯本發明之優點’惟該等實施例僅為例示說明 12 200909472 之用，而非用以限制本發明β <測試方法> 除非另有指明’各次測試皆是在常溫常壓下，以下述 方式進行。 有黏度H $ 〇· 1 g之待測樣品並使其溶解於 25cc 之 溶劑（體積比為3:2之紛/四氯f院溶液）中，繼而於观 下以烏氏（Ubbelohde)黏度計進行測試。 2. L*、a*與b* :是依據一使用1976 CIE L* a* b*的表色方 式的Macbeth color eye 2145光譜儀所測得，有關操作之 參數與L*、a% b*數值大小的意義，係如前面實施方式 所述。 3. 霧度：使用haze SUGA儀器並依據ASTM_m〇〇3方法 來測得。 <實施例1> 液態聚合階埒 將38Kg之對苯二曱酸（TPA)、〇 9Kg之間苯二曱酸 (IPA)’以及l8.16Kg的混有1.125g鋁粉（購自鑫陶應用材 料公司’品名為鋁粉且型號為A1_H〇3_p〇2，粒徑（(15〇)是2± 1 μ m)的乙一醇（EG)喂入撥拌槽中擾拌成糊狀物，繼而將該 糊狀物倒入酯化槽中升溫（末溫為250。〇並同時使進行酯化 歷時6.5小時，當酯化率大於95%時可得一聚合產物（醋化 物’聚合度約為7，數目平均分子量約為1350)，將聚合產 物移行至聚合槽，添加1260g之觸媒（三氧化二銻，Sb2〇3) 、35PPM之抗氧化劑（填酸，H3P〇4)，接而升溫抽真空使聚 13 200909472 合至使固有黏度約為0.6dL/g左右（數目平均分子量約 19000)，之後進行切粒而製得摻有鋁粒子的PET共聚酯液 態聚合酯粒（其中基於PET重量，鋁粉的添加量是25PPM) 〇 固態聚合階段 將液態聚合酯粒倒入固聚反應器内，繼而升溫並抽真 空，之中先升溫至85°C使乾燥2.5小時，接著升溫至105 °C乾燥3小時，繼而升溫至150°C進行預結晶歷時2小時 ，接著再升溫至235°C，使聚合至固有黏度約為0.85dL/g 左右（數目平均分子量31,000)為止，之後進行切粒而製得 摻有鋁粒子的PET共聚酯固態聚合酯粒。 有關固態聚合後製得的PET共聚酯中的重複單元組成 ，因為聚合時EG是添加過量的，且聚合過程中部分乙二 醇間會脫水形成二乙二醇（DEG)，因此透過計算所添加的 TPA與IPA原料的量（會完全反應），並利用 GC(Perkin Elmer auto system)來測定共聚醋中DEG的量，而可確認在 PET共聚酯中，以結構單元A的總莫爾數計，衍生自TPA 與IPA的結構單元A分別佔97.7mol%及2.3mol%，而以結 構單元B的總莫爾數計，衍生自EG及DEG的結構單元B 分別佔 97.6mol%及 2.4mol%。 射胚階段 將固態聚合酯粒以160°C/5小時的條件乾燥後倒入射 出機（瑋綜機械公司製射出機），以275°C~280°C的條件射出 瓶胚。 14 200909472 吹瓶階段 將射出的瓶胚放入嘉明機械公司製的吹瓶機中，以石 英燈管在105°C的溫度加熱50秒鐘，再以紅外線測溫器測 量瓶胚的表面溫度（測出結果如表1所示），接著將加熱軟化 好的瓶胚放入吹瓶模槽内利用氮氣壓力（18~32Kg/cm3)吹成 瓶子。測得的瓶胚及瓶子的物性如表1與表2所示。 <實施例2> 除於液態聚合階段中混入的銘粉的量為50PPM外，以 和 <實施例1>相同的條件製作，且在固態聚合後獲得與實 施例1相同的PET共聚酯重複單元組成，所測得的瓶胚及 瓶子的物性如表1與表2所示。 <實施例3> 除於液態聚合階段中混入的銘粉的量為100ΡΡΜ外， 以和 <實施例1>相同的條件製作，且在固態聚合後獲得與 實施例1相同的PET共聚酯重複單元組成，所測得的瓶胚 及瓶子的物性如表1與表2所示。 <比較例> 除於液態聚合階段中未添加任何鋁粉外，以和 <實施例 1>相同的條件製作，且在固態聚合後獲得與實施例i相同 的PET共聚酯重複單元組成，所測得的瓶胚及瓶子的物性 如表1與表2所示。 表1 瓶胚 鋁粉添加 量（PPM) 瓶胚表面 ，、田由。广 ^皿度C L* a* b* 霧度 比較例 0 113 82. 43 -1. 36 4. 85 2. 2 ~ 實施例1 25 118 一 81. 5 -1. 37 4. 9 3. 5 15 200909472 實施例2 50 122 79. 94 -1. 41 4.98 5.6 實施例3 100 129 78. 31 -1. 42 4. 73 8. 1 表2 瓶子 在呂粉添加 量（PPM) L* a木 b* 霧度 比較例 0 89. 81 -0. 36 2. 9 1 實施例1 25 90. 94 -0. 47 2. 41 2. 1 實施例2 50 90. 5 -0· 46 2. 41 3 6 實施例3 100 89. 71 -0. 46 2. 59 4 結果與討論： 由上述表1與表2可知，雖然實施例2與3所製得瓶 胚的霧度稍咼，但在吹瓶成瓶子後，比較例1與實施例工 至3皆有達到一般業界可接受的瓶子亮度（L、9〇)範圍及霧 度（HaZeg4)範圍，再由瓶胚表面溫度的比較可知，添加有 鋁粉的實施例的確實可在保持最終產品瓶子近乎無色及透 明的條件下，有效的縮短瓶胚加熱時間，因此在相同的加 熱時間下，實施例的瓶胚可達到較高的表面溫度。 综上所述，本發明藉由在熱塑性聚合物製備的各個階 段中添力具有高熱導特性的金屬纟子而製得的熱塑性聚合 物組成物，不僅可在加工再熱階段（制是航料熱）快速地 升溫，同時還可獲得近乎無色及透明的最終加卫產品（特別 是瓶子），而能符合市場對於無色容器之廣大需求，此實為 添加黑體或灰體吸收粒子至熱塑性聚合物而具有高再埶功 效但卻損失顏色與透明度的該等先前技術，所遠遠不及的 〇 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請：利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 16 200909472 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 無 【主要元件符號說明】 無 17a bottle made of a thermoplastic polymer of Sn, Ag, Au, Cu, As, Cd, Hg, pt and/or pd) which mainly utilizes a reducing agent and a compound of the aforementioned metal during the polymerization and makes the metal The compound is reduced to metal particles 200209472, ι, especially Sb, to increase the absolute value of the absolute value of the yellowness of the bottle prepared by reheating the vinegar, but the patent discloses that it is therefore impossible to obtain a colorless bottle liter process = 7 reduction bottle "Hot time, but the energy-saving and temperament can not produce the colorless bottle color of the large demand on the commerce (4) = the color of the nearly colorless ', ·," polymer composition of the bottle which can be quickly heated [Description of the Invention] The specific types of carbon-based, shell-metal compounds or metals that do not increase the rate of reheating are not colorless after being added to the thermoplastic polymer, and thus cannot satisfy the market. A large demand for colorless bottles or other types of containers. - The applicant of this case contemplates that the thermoplastic polymer composition should be able to rapidly heat up under the illumination of a quartz lamp tube, except by increasing the energy absorption as described above. In addition to the object I of the electromagnetic wave in the wavelength region, S can increase the heat transfer property of the whole composition by adding an appropriate amount of heat conductive material to the polymer and thus increase the temperature rise of the preform (such as preform) before processing. Rate, so the applicant tried to select from the various metal powders to have good thermal conductivity and make the final bottle colorless. However, as is known to those skilled in the art of polymer technology, the metal particles are finally mixed with the polymer. Color is controlled by an extremely complicated mechanism 'so it is difficult to estimate the final color that will be presented by the individual color of the microparticles after it is incorporated into the polymer'. The applicant has studied it in many ways and finally found 'Ming, Zhen, and Ci Tungsten and calcium are excellent choices for both heat conduction and colorlessness. 'As long as the amount of the powder of the specific kind of metal is controlled in the thermoplastic polymer 7 200909472, and it is dispersed in the thermoplastic polymer, It can achieve the dual purpose of rapid heating of the preform and almost colorless bottle, and when the polymer preparation process is added or how to add it, there is no special Accordingly, it is a first object of the present invention to provide a rapidly temperature-increasing thermoplastic polymer composition comprising a thermoplastic polymer and a plurality of metal particles wherein the thermoplastic polymer has an average number between 哉Molecular weight, and the metal particles are aluminum, magnesium, rhenium, tungsten, drug particles, or a combination thereof. The thermoplastic polymer composition of the present invention can be made into a melt or vinegar as needed ( Peiie 〇, sheet (4) (10)) or container (eQntainer), particularly suitable for the first purpose of making preforms and bottles, ie, providing a thermoplastic polymer composition for preparing the rapid heating The method comprises the steps of: adding the metal, the liquid phase, the solid state polymerization stage, and the processing and forming stage in the stage of the thermoplastic polymer selected from the group consisting of . The rapidly warming thermoplastic polymer composition of the present invention can effectively increase the heating rate because it contains metal particles capable of conducting heat, thereby reducing the time for reheating before processing (such as blowing), and greatly reducing the process cost. Furthermore, 'the metal particles are selected and their final color development and transparency are dispersed in the poly-particles. Therefore, the thermoplastic polymer can be obtained by appropriately controlling the addition amount and particle size of the metal particles. The finished product of the composition, such as a bottle, is in a state of near-colorlessness, so it can be used in the above-mentioned market, especially in the Asian market. [Embodiment] Preferably, the metal particles in the composition of the present invention are Ming particles. Preferably, in the thermoplastic polymer composition of the present invention, the content of the metal particles is between 2 and 200 PPM, and more preferably between 1 and 200 PPM, based on the total weight of the thermoplastic polymer. Between ρρΜ, and, more preferably, between 20 PPM and 100 PPM, optimally between 25 PPM and 100 PPM. Preferably, the metal particles suitable for use in the present invention have a d5 〇 particle size between ΙΟΟμιη, more preferably a dso particle size between 〇 and 50 μπι, and even more preferably, There is a particle size between 〇" and ΙΟμηι, optimally, having a particle size of d5 from 〇1 to 瓜. Preferably, the thermoplastic polymer suitable for use in the present invention is a polyester composed of at least one repeating unit A derived from a diacid component and at least one repeating unit B derived from a diol component. Preferably, the diacid component comprises an aliphatic dicarboxylic acid of C2 to Ci6, an aromatic dicarboxylic acid of C8 to C16, or a combination thereof. Optionally, the diacid component comprises at least one C8 to Cl6 aromatic dicarboxylic acid' and preferably, the Cs-C!6 aromatic dicarboxylic acid is terephthalic acid. More preferably, the thermoplastic polymer is a copolyester of polyethylene terephthalate or polyethylene terephthalate, and preferably, based on the total number of moles of the diacid component' Terephthalic acid is at least 60 mole percent of the diacid component, and ethylene glycol is at least 60 mole percent of the glycol component based on the total moles of the polymer component of 200,909,472. Optionally, the diacid component comprises an aromatic bis-acid of diCrCi6. In a specific example of the present invention, the aromatic dicarboxylic acid of the two CpC 6 is terephthalic acid and isophthalic acid, respectively. More preferably, the diacid component comprises 96-99 mol% of terephthalic acid and 4-1 mol% of isophthalic acid. Optionally, the diol component comprises at least one C2 to C10 diol, more preferably the diol component comprises at least one C2 to C5 diol. In the specific embodiment of the present invention, the diol component comprises ethylene glycol, and part of the ethylene glycol is dehydrated during the polymerization to form diethylene gly C〇i (DEG). Repeating unit B derived from diethylene glycol will be present in the copolyester. Preferably, in the polyester, the repeating unit B derived from ethylene glycol is 95 to 99 mol%, based on the total number of moles of the repeating unit b, and the repeating unit B derived from diethylene glycol is 5-lmol%. Since the metal particles can be added at various stages of polymerization of the thermoplastic polymer, the molecular weight of the thermoplastic polymer in the composition of the present invention encompasses the polymerization of the thermoplastic polymer in a liquid state (generally about a degree of polymerization) and a solid state polymerization stage ( The molecular weight range generally has a degree of polymerization of from about 100 to about 400, i.e., has a number average molecular weight of between 1,000 and 60,000. Optionally, the thermoplastic polymer has a number average molecular weight of between 1,000 and 45, 〇〇〇, and still further, the thermoplastic polymer has between 1 and 35 Å. The number average molecular weight, and in each of the specific examples of the present invention, the thermoplastic polymer in the composition obtained at each stage of the polymerization has a number average molecular weight of u5 〇, 19,000 and 31,000. 10 200909472 The composition of the present invention can be used to make a melt, vinegar granule, sheet or container, and is particularly suitable for making preforms and bottles. Accordingly, the present invention also provides a preform prepared from the thermoplastic polymer composition of the present invention, and preferably has a strip to the crucible. The L* brightness, and a better haze, have an L* brightness of between 80% and Peng, and a haze of between 2 and 35. And preferably, the preform has an a* between _3 and +3, more preferably an a* between -2 and +2, and more preferably, the a* is a _2 The value to the day. Preferably, the preform has a b* between _5 and +7, more preferably a b* between -5 and +5, and optimally, the b* is a ❶ A value of up to 5. In each of the specific examples of the present invention, the prepared preform has a haze of between 3 and 5 and 8.1, a* is between "36 and 142", and is between 4.73 and 4.98. A bottle made from the thermoplastic polymer composition of the present invention is provided and the bottle preferably has an L* of between 88% and 5%, and a haze of between 1-4. And preferably, the bottle has an a* between 丨 and +1, more preferably between 〇·5 and +〇5, more preferably 'the a*疋为-约_〇 · 5 〇 value. Preferably, the bottle has a b* between -3 and +5, more preferably a b* between _ 丨 and 科, and more preferably, the b* is from about 〇 to 3 Value. In each of the specific examples of the present invention, the prepared container has a haze of between 2 Torr and 4, a range of -0.36 to -0.47, and a b* of between 2.41 and 2.59 (nearly colorless). 0 When used herein, the L* '# and b* values are measured according to a Macbeth color eye 2145 spectrometer using a color scheme of 1976 11 200909472 3 b, wherein the observation angle S 2 used in the operation. The illuminating source is D65. When the J-shaped enamel preform is used, the thickness of the sample is set to be; when the test sample is a bottle, the thickness is set to 〇35mm. Among them, the larger the L* value, the more the brightness is the same, a* >〇 represents a reddish color, a*<〇 represents a color greenish; b*>〇 represents a color partial page, b*<G represents a color blue; as for haze, a HAZESUGA instrument is used and according to ASTM The method for preparing the rapidly heated thermoplastic polymer composition of the present month is the following step: adding the step of the thermoplastic polymer to a stage selected from the group below Metal particles: polymerization advancement stage, liquid polymerization stage, solid state polymerization stage, and processing In the specific example of the present invention, the metal particles are in the liquid state of the thermoplastic polymer, and are added by a. In addition, the 'additional time can be added-added or added in stages. At the same time, the visual process is The metal particles are first dispersed in a liquid medium, and then added to the various stages of polymerization or processing of the above polymer. Preferably, the liquid medium is ethylene glycol. Furthermore, if the metal particles are in a processing stage For example, when the preform is shot, it is added, preferably, it is first subjected to a drying treatment. In addition, if the pollution of the production line is reduced and the particle dispersion is more uniform, the metal particles and the partial polymer s may be firstly used. The pellets are first mixed and the masterbatch containing the metal particles is prepared first, and then used in a large amount in the production line. [Examples] The present invention will be further described by way of examples, and the comparative examples and efficacy tests are combined to demonstrate the advantages of the present invention. 'But these examples are for illustrative purposes only 12 200909472, and are not intended to limit the present invention. <Test Method> Unless otherwise indicated, 'each test is at normal temperature and pressure, The method is carried out. The sample with viscosity H 〇 · 1 g is dissolved in 25 cc of solvent (volume ratio of 3:2 / tetrachlorof hospital solution), followed by Ub ( Ubbelohde) viscometer for testing. 2. L*, a* and b*: measured according to a Macbeth color eye 2145 spectrometer using the 1976 CIE L* a* b* color scheme, parameters related to operation and L *, a% b* The meaning of the numerical value is as described in the previous embodiment. 3. Haze: measured using the haze SUGA instrument according to the ASTM_m〇〇3 method. <Example 1> Liquid polymerization step was carried out by mixing 38 kg of terephthalic acid (TPA), ruthenium 9 kg between benzoic acid (IPA)' and 18.16 kg of 1.125 g of aluminum powder (purchased from Xintao). Applied Materials's name is aluminum powder and the model number is A1_H〇3_p〇2, and the particle size ((15〇) is 2±1 μm) of ethylene glycol (EG) is fed into the mixing tank to disturb the paste. Then, the paste is poured into an esterification tank to raise the temperature (the final temperature is 250. The enthalpy is simultaneously subjected to esterification for 6.5 hours, and when the esterification rate is more than 95%, a polymerization product can be obtained (the degree of polymerization of the acetate is about 7, the number average molecular weight is about 1350), transfer the polymerization product to the polymerization tank, add 1260g of catalyst (antimony trioxide, Sb2〇3), 35PPM of antioxidant (acid, H3P〇4), and then The temperature is increased by vacuuming to make the poly 13 200909472 to have an intrinsic viscosity of about 0.6 dL/g (the number average molecular weight is about 19,000), and then granulating to obtain a PET copolyester liquid polymerized ester particle doped with aluminum particles (based on PET weight, the amount of aluminum powder added is 25PPM) 〇 Solid state polymerization stage, the liquid polymerized ester particles are poured into the solidification reactor, and then heated Vacuuming, first heating to 85 ° C for drying for 2.5 hours, followed by heating to 105 ° C for 3 hours, followed by heating to 150 ° C for pre-crystallization for 2 hours, followed by heating to 235 ° C, polymerization to The intrinsic viscosity is about 0.85 dL/g (the number average molecular weight is 31,000), and then granulation is carried out to obtain a PET copolyester solid polymerized ester granule doped with aluminum particles. Repeated unit composition, because EG is added in excess during polymerization, and some ethylene glycol is dehydrated during the polymerization to form diethylene glycol (DEG), so by calculating the amount of TPA and IPA raw materials added (will completely react And using GC (Perkin Elmer auto system) to determine the amount of DEG in the copolymerized vinegar, it can be confirmed that in the PET copolyester, the structural unit A derived from TPA and IPA is based on the total number of moles of structural unit A. 97.7mol% and 2.3mol%, respectively, and the structural unit B derived from EG and DEG accounts for 97.6mol% and 2.4mol%, respectively, based on the total Moiré of structural unit B. The solid phase polymerized ester particles are in the embryo stage. Dip-out machine after drying at 160 ° C / 5 hours (Injection machine made by Yuji Machinery Co., Ltd.), the preform is shot at 275 ° C ~ 280 ° C. 14 200909472 The bottle preform is placed in a blow molding machine made by Jiaming Machinery Co., Ltd. After heating at a temperature of 105 ° C for 50 seconds, the surface temperature of the preform was measured by an infrared thermometer (the measured results are shown in Table 1), and then the softened and softened preform was placed in a blowing mold cavity. Nitrogen pressure (18~32Kg/cm3) was blown into the bottle. The physical properties of the measured preforms and bottles are shown in Tables 1 and 2. <Example 2> The same PET copolymer as in Example 1 was obtained after solid state polymerization, except that the amount of the powder mixed in the liquid polymerization stage was 50 PPM, and the same conditions as in <Example 1>. The ester repeat unit was composed, and the measured physical properties of the preform and the bottle are shown in Table 1 and Table 2. <Example 3> The same PET copolymer as in Example 1 was obtained after solid state polymerization except that the amount of the powder mixed in the liquid polymerization stage was 100 Torr, and the same conditions as in <Example 1> The ester repeat unit was composed, and the measured physical properties of the preform and the bottle are shown in Table 1 and Table 2. <Comparative Example> The same PET copolyester repeating unit as in Example i was obtained after solid state polymerization except that no aluminum powder was added in the liquid polymerization stage, and the same conditions as in <Example 1> Composition, measured physical properties of preforms and bottles are shown in Tables 1 and 2. Table 1 Preforms Aluminium powder addition amount (PPM) Preform surface, and field. Wideness of the dish CL* a* b* Haze comparison example 0 113 82. 43 -1. 36 4. 85 2. 2 ~ Example 1 25 118 a 81.0 -1. 37 4. 9 3. 5 15 200909472 Example 2 50 122 79. 94 -1. 41 4.98 5.6 Example 3 100 129 78. 31 -1. 42 4. 73 8. 1 Table 2 Addition of bottle in Lu powder (PPM) L* a wood b* Haze Comparative Example 0 89. 81 -0. 36 2. 9 1 Example 1 25 90. 94 -0. 47 2. 41 2. 1 Example 2 50 90. 5 -0· 46 2. 41 3 6 Implementation Example 3 100 89. 71 -0. 46 2. 59 4 Results and discussion: It can be seen from Tables 1 and 2 above that although the haze of the preforms obtained in Examples 2 and 3 is slightly smeared, it is blown into a bottle. After that, Comparative Example 1 and Example 3 to 3 have the range of bottle brightness (L, 9 〇) and haze (HaZeg 4) acceptable to the general industry, and it is known from the comparison of the surface temperature of the preform that aluminum powder is added. The embodiment can indeed shorten the preform heating time while maintaining the final product bottle nearly colorless and transparent, so that the preform of the embodiment can achieve a higher surface temperature for the same heating time. In summary, the present invention is a thermoplastic polymer composition prepared by adding metal hazel having high thermal conductivity characteristics in various stages of preparation of a thermoplastic polymer, not only in the process of reheating (process is aeronautical material) Heat) quickly heats up, while also obtaining a near-colorless and transparent final-assisted product (especially a bottle), which meets the market's broad demand for colorless containers, which is the addition of black or gray body absorbing particles to thermoplastic polymers. The prior art which has a high re-efficiency but loses color and transparency is far from being the only one described above, and is only a preferred embodiment of the present invention. Scope, that is, the simple equivalent changes and modifications made by the present invention in the scope of the invention and the scope of the invention are still within the scope of the invention. [Simple description of the diagram] None [Key component symbol description] None 17