200409787 玖、發明說明： 【發明所屬之技術領域】 本發明係關於聚酯之製造方法者。更詳細言之，本發 係關於具有優異之耐水解性、聚合性、以及色調之聚酯 製造方法者。 【先前技術】 聚酯由於具有優異之成形加工容易性，機械物性，耐 性，对藥品性，保香性，其他之物理特性及化學特性而 廣用於汽車零件、電機•電子零件、精密儀器零件、膜片 片材、單絲、纖維等。 聚酯在一般之情形，在原料為二羧酸之場合經過酯化 應，而在原料為二羧酸二烷酯之場合經過酯交換反應， 之施行聚縮合反應，藉此製造者，而愈往聚縮合之後期 反應點之數目（末端基濃度）愈減少，致使聚合速度降低 因此通常愈往後期，所設定之溫度及真空度愈高。然而 溫度愈高，副反應速度愈升高，造成末端雙鍵之增加， 調之惡化，聚合性之惡化，黏度之降低等之問題。 為了解決上述問題，例如有一種藉分批法在高溫下施 聚縮合後，降低内溫，拔取聚酯，而減低其拔取（抽出） 程前半與後半之間之產品聚合度差異之方法被倡議（參 例如π專利文獻” 1等）。然而，依照該公報所載述之分批 之聚縮合，無法完全消除拔取過程前半與後半之間之產 聚合度差異之問題，隨此亦造成末端乙烯基之增加，色 之惡化等之問題。又有下述缺點：由於分批法一旦提高 312/發明說明書(補件)/92-09/92115520 明 之 熱 被 反 繼 色 行 過 昭 i 法 品 調 反 5 200409787 應溫度後，若要降低反應溫度，則需要很多時間， 上在溫度降低之過程中發生末端羧基之增加等之副 進展。 [專利文獻1 ] 曰本專利特開平5 - 4 3 6 7 6號公報 本發明係在提供一種抑制聚縮合反應時之副反應 色調、耐水解性及聚合性之品質安定之聚酯及其製 為目的之下所創案者。更具體而言，提供一種已減 之成為色調惡化、聚合性惡化、水解性惡化等之原 端羧基、末端乙烯基之聚酯及其製造方法為其目的 【發明内容】 本案發明人等為了解決上述問題，潛心重覆研究 現，在特定之條件下施行聚縮合反應即可得到一 調、耐水解性及聚合性且品質安定之聚酯之事實， 成本發明。 即，本發明之要旨在於一種聚酯之製造方法，係 述步驟：（A )以二羧酸或二羧酸二烷酯及二醇作為主 在觸媒之存在下進行酯化反應或酯交換反應而製造 酯化率或酯交換率9 0 %以上之低聚合物之步驟，以』 用複數段之反應槽以使低聚合物在熔融狀態下連續 縮合反應之聚縮合步驟， 其特徵為，設（B )聚縮合步驟中，内溫最高之槽之 Τ μ λ X °C ，最終槽之内溫為T ( ω ) °C時，滿足 Tmax>T(CO)。 312/發明說明書(補件)/92-09/92115520 而實際 反應之 ，改良 造方法 少所含 因之末 0 結果發 改良色 於是完 具有下 原料且 一具有 “ B )使 進行聚 内温為 6 200409787 本發明之另一要旨在於一種聚酯樹脂，其特徵為，其為 由上述製造方法所得之具有鈦原子濃度 250ppm以下之聚 酯樹脂。 本發明之另一要旨在於一種聚酯樹脂，其特徵為，其為 由上述製造方法所得之具有末端乙烯基濃度 15peq/g以 下之聚酯樹脂。 本發明之另一要旨在於一種聚酯樹脂，其特徵為，其為 由上述製造方法所得之具有末端羧基濃度 1至 40peq /g 之聚酯樹脂。 【實施方式】 以下，關於本發明敘述詳細說明。 本發明之聚酯係指具有由二羧酸單元與二醇單元鍵結 之構造之高分子而言，只要滿足此一條件，其單體成分則 未受到限制，例如為二羧酸之具體例，可舉出如酞酸、對 酞酸、異酞酸、4, 4’-二苯二甲酸、4, 4’-二苯醚二甲酸、 4, 4’-二苯基酮二曱酸、4, 4’-二苯氧乙烷二曱酸、4, 4’-二苯砜二曱酸、2, 6 -萘二曱酸等之芳香族二羧酸，如1，2-環己烷二曱酸、1，3 -環己烷二甲酸、1，4 -環己烷二曱酸、 異佛爾酮二甲酸等之脂環式二羧酸，如丙二酸、丁二酸、 戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸等之 脂肪族二羧酸等。其中在耐熱性或機械物性之觀點上以脂 環式二羧酸，芳香族二羧酸較佳，而以芳香族二羧酸特別 合適。再者，在結晶性或耐熱性之觀點上，較佳的是，對 酞酸單元在全二羧酸單元中所佔之比率為5 0 m ο 1 %以上，以 7 312/發明說明書(補件)/92-09/92115520 200409787 70mol%以上進一步較佳，尤其以90niol%以上較合適，而以 95m〇l%以上最合適。 上述二羧酸成分可保持二羧酸或二羧酸二烷自旨之形式 供於反應。二羧酸二烷酯中之二烷基並未特別受到限制， 不過若烷基太長，則會招致酯交換時所產生之烷醇之沸點 上升，無法從反應液中揮發出去，其結果以末端停止劑起 作用，而阻礙聚合，因此以碳數4以下之烷基較佳，尤其 以甲基較佳。 作為二醇成分之具體例，可舉出如乙二醇、一縮貳（乙 二醇）、聚乙二醇、1，2-丙二醇、1,3 -丙二醇、聚丙二醇、 1，4 -丁二醇、聚四亞甲二醇、一縮貳（丁二醇）、1,5 -戊二 醇、新戊二醇、1，6 -己二醇、1，8 -辛二醇等之脂肪族二醇， 如1，2_環己二醇、1，4 -環己二醇、1，1_二經甲環己烧等之 脂環式二醇，如二甲苯二醇、4, 4’-二羥聯苯、2, 2-雙（4-羥苯）丙烷、雙（4 -羥苯）砜等之芳香族二醇。其中在機械特 性之觀點上以脂環式二醇、脂肪族二醇較佳，尤其在韌性 或機械物性之觀點上，較佳的是，脂肪族二醇單元在全二 醇單元中所佔之比率為 50mol%以上，70mol%以上更佳， 8 0 m 〇 1%以上特別合適，而以9 5 m ο 1 %以上最合適。此外，在 成形性或機械物性之觀點上以乙二醇、1，3 -丙二醇、1，4 -丁二醇較佳，而在結晶性之觀點上以1，4 - 丁二醇較合適。 再者，為二羧酸成分、二醇成分，使用構造不同之複數之 二羧酸成分、二醇成分以形成共聚物亦可。 在本發明中，可進一步使用如羥羧酸（如乳酸、羥乙酸、 8 312/發明說明書(補件)/92-09/92115520 200409787 間羥苯甲酸、對羥苯曱酸、6 -羥-2 -萘甲酸、對-/3 -羥乙氧 苯曱酸等）、烷氧羧酸、硬脂醇、苄醇、硬脂酸、苯曱酸、 第三丁苯曱酸、苯曱醯苯曱酸等之單官能成分，如丙三羧 酸偏苯三甲酸、均苯三甲酸、苯四甲酸、五倍子酸、三羥 甲基乙烷、三羥甲基丙烷、丙三醇、異戊四醇等之三官能 以上之多官能成分等以作為共聚合成分。 本發明之聚酯之分子量並未特別受到限制，而在機械物 性，丸粒化之安定性，成形性之觀點上，最好能具有數平 均分子量在 5 0 0 0至 6 0 0 0 0之範圍内，以1 0 0 0 0至4 0 0 0 0 之範圍内較佳。聚酯之數平均分子量可利用末端基滴定、 紅外線光譜測定、核磁共振（N M R )譜測定等之手法測定之。 在本發明中，聚酯之末端羧基濃度若太高，則有使聚酯 樹脂之财水解性惡化之傾向，而若太低，則有使聚合性惡 化之傾向，因此該濃度以1至4 0 μ e Q / g較佳，以2至3 0 μ e q /g進一步較佳，其中以3至25peq /g較合適，而以5至 2 0 μ e q / g特別合適。 聚酯之末端羧基濃度係可藉一種使樹脂溶於有機溶媒 而對此使用氫氧化鈉溶液等之鹼溶液以施行滴定之方法求 出者。 再者，本發明所得之聚酯之末端乙烯基濃度若太高，則 有招致色調惡化或聚合性惡化之傾向，因此該濃度以 1 5 μ e q / g以下較佳，其中以1 0 μ e q / g以下較合適，而以 7 μ e q / g以下特別合適。末端乙烯基濃度係可藉一種使聚 酯溶於溶媒而予以測定NMR之方法求出者。 9 312/發明說明書(補件)/92-09/92115520 200409787 本發明之聚酯之製造方法係基於習用之 項習知方法可粗略分為將二羧酸用作主原 合法，以及將二羧酸二烷酯用作主原料之 在初期之酯化反應產生水，而後者在初期 生醇，雖然有此差異，但在原料之取得安 處理容易性，原料之單位用量之高低，以 改良效果之觀點上，以直接聚合法較佳。 為直接聚合法之一例，可舉出下述方法 及二醇成分在單段或”複數段"（其定義在名 槽内，在酯化反應觸媒之存在下，在通常 2 0 0至2 8 0 °C較佳，而以2 1 0至2 7 0 °C特另 通常10至250kPa(以13至133kPa較佳， 特別合適）之壓力下，連續進行酯化反應I 1至3小時較佳），將所得到之酯化反應產 送至聚縮合反應槽，在複數段之聚縮合反 反應觸媒之存在下，在通常210至300 °C丨 較佳，而以2 3 0至2 8 0 °C特別合適，尤其 段時最好能比聚合物之熔點高5至3 0 °C ， 佳，而以7至1 5 °C特別合適）之溫度及通1 2 0 k P a以下較佳，而以1 3 k P a特別合適， 最終段時最好能在2 k P a以下之減壓下）之 拌下連續進行聚縮合反應2至1 2小時（以3 之方法。 在使用對酞酸為二羧酸成分且使用 1， 312/發明說明書(補件)/92-09/92115520 製造方法，而此 料之所謂直接聚 酯交換法。前者 之酯交換反應產 定性，餾出物之 及依照本發明之 :使二羧酸成分 I面）之S旨化反應 1 8 0 至 3 0 0 °C (以 J合適）之溫度及 j 以 60 至 lOlkPa 5至5小時（以 物即低聚合物移 應槽内在聚縮合 〔以 2 2 0 至 2 9 0 °C 在聚縮合之最終 以 5至20°C較 f 2 7 k P a以下（以 尤其在聚縮合之 壓力下，且在攪 丨至1 0小時較佳） 4 - 丁二醇為二醇 10 200409787 成分之場合，可舉出下述方法：在通常1 8 0至2 6 0 °C (以2 0 0 至2 5 0 °C較佳，而以2 1 0至2 4 5 °C特別合適）之溫度及通常 1 0至1 3 3 k P a (以1 3至1 0 1 k P a較佳，而以6 0至9 0 k P a特別 合適）之壓力下，連續進行酯化反應0 · 5至5小時（以1至 3小時較佳），將所得到之酯化反應產物即低聚合物移送至 聚縮合反應槽，在複數段之聚縮合反應槽内在聚縮合反應 觸媒之存在下，在通常2 1 0至2 6 0 °C (以2 2 0至2 5 0 °C較佳， 而以220至245 °C特別合適）之溫度及通常27kPa以下（以 2 0 k P a以下較佳，而以1 3 k P a特別合適，尤其在至少一個 聚縮合反應槽内，最好能在 2kPa以下之減壓下）之壓力 下，且在攪拌下連續進行聚縮合反應2至1 2小時（以2至 1 0小時較佳）之方法。 在另一方面，為酯交換法之一例，可舉出下述方法：使 二羧酸二烷酯成分及二醇成分在單段或複數段之酯化反應 槽内，在酯交換反應觸媒之存在下，在通常1 1 0至3 0 0 °C (以 1 4 0至2 8 0 °C較佳，而以1 8 0至2 6 0 °C特別合適）之溫度及 通常10至250kPa(以13至133kPa較佳，而以60至lOlkPa 特別合適）之壓力下，連續進行酯交換反應0 . 5至5小時（以 1至3小時較佳），將所得到之酯交換反應產物即低聚合物 移送至聚縮合反應槽，在複數段之聚縮合反應槽内在聚縮 合反應觸媒之存在下，在通常2 1 0至3 0 0 °C (以2 2 0至2 9 0 °C較佳，而以2 3 0至2 8 0 °C特別合適，尤其在聚縮合之最 終段時最好能比聚合物之熔點高5至3 0 °C ，以高5至2 ◦ °C較佳，而以高7至1 5 °C特別合適）之溫度及通常2 7 k P a 11 312/發明說明書(補件)/92-09/92115520 200409787 以下（以2 0 k P a以下較佳，而以1 3 k P a特別合適，尤其 少一個聚縮合反應槽内最好能在2kPa以下之減壓下） 力下，且在攪拌下連續進行聚縮合反應2至1 2小時| 至1 0小時較佳）之方法。 在使用對酞酸二甲酯為二羧酸二烷酯成分且使用 丁二醇為二醇成分之場合，可舉出下述方法：在通常 至2 6 0 °C (以1 4 0至2 4 5 °C較佳，而以1 8 0至2 2 0 °C特 適）之溫度及通常10至133kPa(以13至lOlkPa較佳 以6 0至9 0 k P a特別合適）之壓力下，連續進行酯交換 0 · 5至5小時（以1至3小時較佳），將所得到之酯交 應產物即低聚合物移送至聚縮合反應槽，在複數段之 合反應槽内在聚縮合反應觸媒之存在下，在通常2105 t：(以2 2 0至2 5 (TC較佳，而以2 2 0至2 4 5 °C特別合適） 度及通常27kPa以下（以20kPa以下較佳，而以13kPa 合適，尤其在至少一個聚縮合反應槽内，最好能在 以下之減壓下）之壓力下，且在攪拌下連續進行聚縮合 2至1 2小時（以2至1 0小時較佳）之方法。 再者，為了達成本發明抑制聚酯聚縮合反應時之副 而改良色調或聚合性之目的，對一在觸媒之存在下施 化反應後或酯交換反應後之酯化率或酯交換率 9 0 %以 低聚合物使用複數段反應槽以使在熔融狀態下連續進 縮合反應之步驟中，設内温最高之反應槽之内溫為 °C ，最終反應槽之内溫為T (ω ) °C時，必需滿足 Τ μ λ X〉T ( ω ) 312/發明說明書(補件)/92-09/92115 520200409787 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for manufacturing a polyester. More specifically, the present invention relates to a method for producing a polyester having excellent hydrolysis resistance, polymerizability, and color tone. [Prior technology] Polyester is widely used in automobile parts, electrical machinery, electronic parts, and precision instrument parts because of its excellent ease of forming and processing, mechanical properties, resistance, chemical resistance, fragrance retention, and other physical and chemical properties. , Membrane sheet, monofilament, fiber, etc. Under normal circumstances, the polyester undergoes esterification when the raw material is a dicarboxylic acid, and when the raw material is a dialkyl dicarboxylate through a transesterification reaction, a polycondensation reaction is performed. The number of reaction points (terminal group concentration) in the later stage of polycondensation decreases, resulting in a decrease in the polymerization rate. Therefore, the later the temperature, the higher the set temperature and vacuum. However, the higher the temperature, the higher the rate of side reactions, causing problems such as an increase in terminal double bonds, deterioration in tuning, deterioration in polymerizability, and decrease in viscosity. In order to solve the above problems, for example, a method of reducing the internal temperature and extracting polyester by batchwise polymerization and condensation at high temperature is used to reduce the difference in product polymerization between the first half and the second half of the extraction (extraction) process. (See, for example, π Patent Document "1" etc.) However, the batchwise polycondensation described in the bulletin cannot completely eliminate the problem of the difference in polymerization degree between the first half and the second half of the extraction process. The increase of the base, the deterioration of the color, etc. There are also the following disadvantages: once the batch method is increased 312 / Invention Specification (Supplements) / 92-09 / 92115520 The heat of Ming has been passed on by the successive colors. Inverse 5 200409787 If the reaction temperature is to be reduced after the temperature is applied, it takes a lot of time, and the secondary progress of the increase in the terminal carboxyl group occurs during the temperature decrease. [Patent Document 1] Japanese Patent Laid-Open No. 5-4 3 6 7 Publication No. 6 The present invention was created with the purpose of providing a polyester with stable quality that suppresses side reaction hue, hydrolysis resistance, and polymerizability during the polycondensation reaction and its production. Specifically, it is to provide an original carboxyl group, terminal vinyl group polyester which has reduced color tone deterioration, deterioration in polymerizability, deterioration in hydrolysis and the like, and a method for producing the same. [Summary of the Invention] In order to solve the above problems, the present inventors The problem has been studied intensively and repeatedly. The fact that a polycondensation reaction can be performed under specific conditions to obtain a polyester with a tune, hydrolysis resistance, polymerizability, and stable quality is an invention of the invention. That is, the purpose of the present invention is to The method for producing an ester is described in the following steps: (A) The esterification reaction or the transesterification reaction is carried out in the presence of a catalyst with dicarboxylic acid or a dialkyl dicarboxylic acid ester and a diol as the main agent to produce an esterification rate or transesterification. The step of low polymer having a rate of more than 90% is a polycondensation step using a plurality of reaction tanks to continuously condense the low polymer in a molten state, which is characterized in that (B) a polycondensation step, T μ λ X ° C of the tank with the highest internal temperature, when the internal temperature of the final tank is T (ω) ° C, Tmax > T (CO) is satisfied. 312 / Invention Specification (Supplement) / 92-09 / 92115520 and The actual response is less improved Containing the end of 0 results in improved color, so it is complete with lower raw materials and one with "B" so that the internal temperature is 6 200409787 Another object of the present invention is a polyester resin, which is characterized in that it is manufactured from the above A polyester resin having a titanium atom concentration of 250 ppm or less obtained by the method. Another aspect of the present invention is directed to a polyester resin characterized in that it is a polyester resin having a terminal vinyl group concentration of 15 peq / g or less obtained by the above-mentioned production method. Another aspect of the present invention is directed to a polyester resin characterized in that it is a polyester resin having a terminal carboxyl group concentration of 1 to 40 peq / g obtained by the above-mentioned production method. [Embodiment] Hereinafter, the present invention will be described in detail. The polyester of the present invention refers to a polymer having a structure in which a dicarboxylic acid unit and a diol unit are bonded. As long as this condition is satisfied, the monomer component is not limited. For example, it is a specific example of a dicarboxylic acid. Examples include phthalic acid, terephthalic acid, isophthalic acid, 4, 4'-diphthalic acid, 4, 4'-diphenyl ether dicarboxylic acid, 4, 4'-diphenyl ketone dicarboxylic acid, Aromatic dicarboxylic acids such as 4, 4'-diphenoxyethane dicarboxylic acid, 4, 4'-diphenylsulfone dicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, such as 1,2-cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophorone dicarboxylic acid, such as malonic acid, succinic acid, pentyl Dicarboxylic acids such as diacid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like. Among them, alicyclic dicarboxylic acids and aromatic dicarboxylic acids are preferred from the viewpoint of heat resistance and mechanical properties, and aromatic dicarboxylic acids are particularly suitable. Furthermore, from the viewpoint of crystallinity or heat resistance, it is preferable that the ratio of the terephthalic acid unit in the dicarboxylic acid unit is 50 m ο 1% or more. Pieces) / 92-09 / 92115520 200409787 70 mol% or more is more preferable, especially 90niol% or more is suitable, and 95mol% or more is most suitable. The dicarboxylic acid component may be supplied to the reaction in the form of a dicarboxylic acid or a dicarboxylic acid dioxane. The dialkyl group in the dialkyl dicarboxylic acid is not particularly limited, but if the alkyl group is too long, the boiling point of the alkanol generated during the transesterification will increase, and it will not be able to volatilize from the reaction solution. The terminal stopper acts to hinder polymerization, so an alkyl group having a carbon number of 4 or less is preferred, and a methyl group is particularly preferred. Specific examples of the diol component include ethylene glycol, acetone (ethylene glycol), polyethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, polypropylene glycol, and 1,4-butylene. Fatty acids such as diols, polytetramethylene glycols, monobutylene glycols, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, etc. Group diols, such as alicyclic diols such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-dicyclohexane, etc., such as xylene glycol, 4, 4 Aromatic diols such as' -dihydroxybiphenyl, 2,2-bis (4-hydroxybenzene) propane, and bis (4-hydroxyphenyl) sulfone. Among them, alicyclic diols and aliphatic diols are preferable from the viewpoint of mechanical properties, and particularly from the viewpoint of toughness or mechanical properties, it is preferable that the aliphatic diol units occupy the entire diol units. The ratio is 50 mol% or more, more preferably 70 mol% or more, 80 m 〇1% or more is particularly suitable, and 95 m ο 1% or more is most suitable. In addition, ethylene glycol, 1,3-propanediol, and 1,4-butanediol are preferred from the viewpoint of moldability and mechanical properties, and 1,4-butanediol is more appropriate from the viewpoint of crystallinity. In addition, as the dicarboxylic acid component and the diol component, a plurality of dicarboxylic acid components and diol components having different structures may be used to form a copolymer. In the present invention, for example, a hydroxycarboxylic acid (such as lactic acid, glycolic acid, 8 312 / Specification of the Invention (Supplement) / 92-09 / 92115520 200409787 m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy- 2-naphthoic acid, p- / 3-hydroxyethoxybenzoic acid, etc.), alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, phenylarsonic acid, tertiary butyl benzoic acid, phenylammonium benzene Monofunctional components such as gallic acid, such as trimellitic acid, trimellitic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, isoprene A trifunctional or higher polyfunctional component such as an alcohol is used as a copolymerization component. The molecular weight of the polyester of the present invention is not particularly limited, but from the viewpoints of mechanical properties, stability of pelletization, and moldability, it is preferable to have a number average molecular weight of 5 0 to 6 0 0 0 0 Within the range, a range of 1 0 0 0 to 4 0 0 0 is preferable. The number average molecular weight of the polyester can be measured by a method such as terminal group titration, infrared spectrum measurement, and nuclear magnetic resonance (N M R) spectrum measurement. In the present invention, if the concentration of the terminal carboxyl group of the polyester is too high, the hydrolyzability of the polyester resin tends to deteriorate, and if it is too low, the polymerizability tends to deteriorate, so the concentration is 1 to 4 0 μe Q / g is preferable, and 2 to 30 μeq / g is more preferable, among which 3 to 25peq / g is more suitable, and 5 to 20μeq / g is particularly suitable. The concentration of the terminal carboxyl group of the polyester can be obtained by dissolving the resin in an organic solvent and using an alkali solution such as a sodium hydroxide solution to perform titration. In addition, if the terminal vinyl concentration of the polyester obtained by the present invention is too high, the color tone or the polymerizability tends to deteriorate. Therefore, the concentration is preferably 15 μ eq / g or less, of which 10 μ eq / g / g is more suitable, and 7 μ eq / g or less is particularly suitable. The terminal vinyl group concentration can be obtained by a method of measuring NMR by dissolving a polyester in a solvent. 9 312 / Invention Specification (Supplement) / 92-09 / 92115520 200409787 The manufacturing method of the polyester of the present invention is based on the conventional method. The conventional method can be roughly divided into the law of using dicarboxylic acid as the main principle, and the method of using dicarboxylic acid as the main principle. Acid dialkyl ester is used as the main raw material to produce water in the initial esterification reaction, and the latter produces alcohol in the initial stage. Although there is a difference, it is easy to obtain and handle the raw material. The unit dosage of the raw material is used to improve the effect. From the viewpoint, a direct polymerization method is preferred. As an example of the direct polymerization method, the following method and the diol component in a single stage or "plurality" (defined in the name tank, in the presence of an esterification catalyst, usually from 200 to The temperature is preferably 2 8 0 ° C, and the esterification reaction is continued for 1 to 3 hours at a pressure of 2 1 0 to 2 7 0 ° C and usually 10 to 250 kPa (preferably 13 to 133 kPa, particularly suitable). (Preferred), the obtained esterification reaction is sent to a polycondensation reaction tank, in the presence of a plurality of stages of polycondensation reaction reaction catalyst, usually at 210 to 300 ° C, and preferably from 2 3 0 to 2 8 0 ° C is particularly suitable, especially at the stage, it is best to be 5 to 30 ° C higher than the melting point of the polymer, preferably, and 7 to 15 ° C is particularly suitable) temperature and 1 2 0 k P a The following is preferred, and 1 kPa is particularly suitable. In the final stage, the polycondensation reaction is preferably performed continuously under a reduced pressure of 2 kPa or less for 2 to 12 hours (in the method of 3). When using terephthalic acid as a dicarboxylic acid component and using 1,312 / Invention Specification (Supplement) / 92-09 / 92115520 manufacturing method, the so-called direct polyester exchange method is used. The former is esterified. The reaction yields qualitative, distillate and according to the present invention: the dicarboxylic acid component I side) S-specification reaction 1 80 to 3 0 0 ° C (appropriate J) temperature and j to 60 to lOlkPa 5 To 5 hours (with polycondensation in the low polymer transfer tank [at 2 2 0 to 2 9 0 ° C at the end of the polycondensation at 5 to 20 ° C below f 2 7 k P a (to especially Under the pressure of polycondensation, and it is better to stir for 10 hours) 4-butanediol is a diol 10 200409787 component, the following methods can be cited: usually 180 to 26 ° C (Preferably at 2 0 to 2 5 0 ° C, especially at 2 1 0 to 2 4 5 ° C) temperature and usually 10 to 1 3 3 k P a (at 1 3 to 1 0 1 k P a is preferable, and the esterification reaction is continuously performed under a pressure of 60 to 90 k P a) for 0.5 to 5 hours (preferably 1 to 3 hours), and the obtained esterification reaction is performed. The product, that is, the low polymer, is transferred to the polycondensation reaction tank. In the polycondensation reaction tank of the plurality of stages, in the presence of the polycondensation reaction catalyst, it is usually at 2 10 to 2 60 ° C (at 2 2 0 to 2 5 0 ° C is preferred, and 220 to 245 ° C is particularly suitable) Temperature and usually 27 kPa or less (preferably 20 kPa or less, and 13 kPa is particularly suitable, especially in at least one polycondensation reaction tank, preferably under 2kPa reduced pressure) And a method of continuously performing the polycondensation reaction under stirring for 2 to 12 hours (preferably 2 to 10 hours). On the other hand, as an example of the transesterification method, the following method can be mentioned: a dialkyl dicarboxylic acid component and a diol component are placed in a single-stage or multiple-stage esterification reaction tank, and the transesterification reaction catalyst is used; In the presence of it, it is usually at a temperature of 110 to 300 ° C (preferably 140 to 280 ° C, and particularly suitable to 180 to 260 ° C) and usually 10 to 250 kPa (It is preferably 13 to 133 kPa, and 60 to 10 kPa is particularly suitable.) Under a pressure of 0.5 to 5 hours (preferably 1 to 3 hours), the transesterification reaction is continuously performed. The obtained transesterification reaction product is The low polymer is transferred to the polycondensation reaction tank. In the polycondensation reaction tank of a plurality of stages, in the presence of the polycondensation reaction catalyst, it is usually 2 1 0 to 3 0 0 ° C (2 2 0 to 2 9 0 ° C is preferred, and it is particularly suitable at 230 to 280 ° C, especially in the final stage of polycondensation, it is better to be 5 to 30 ° C higher than the melting point of the polymer, and 5 to 2 ° C higher It is better, and the temperature is particularly suitable at a high of 7 to 15 ° C) and usually 2 7 k P a 11 312 / Invention Specification (Supplement) / 92-09 / 92115520 200409787 or less (more than 20 k P a Good, and with 1 3 k P a It is particularly suitable, especially in one of the polycondensation reaction tanks, preferably under a reduced pressure of less than 2 kPa), and continuously performing the polycondensation reaction under stirring for 2 to 12 hours | preferably to 10 hours). When dimethyl terephthalate is used as the dialkyl dicarboxylic acid component and butanediol is used as the diol component, the following methods can be cited: Normally to 2 60 ° C (at 1 40 to 2) 4 5 ° C is preferred, and a temperature of 180 to 220 ° C is suitable) and a pressure of usually 10 to 133 kPa (13 to 10 kPa is preferred and 60 to 90 k P a is particularly suitable) 5 to 5 hours (preferably 1 to 3 hours) for continuous transesterification, transfer the obtained transesterification product, ie, low polymer, to a polycondensation reaction tank, and polymerize in a plurality of synthesis reaction tanks. In the presence of a condensation reaction catalyst, at usually 2105 t: (at 2 2 0 to 2 5 (TC is preferred, and at 2 2 0 to 2 4 5 ° C)) and usually 27 kPa or less (at 20 kPa or less 13 kPa is suitable, especially in at least one polycondensation reaction tank, preferably under the pressure of the following pressure), and the continuous polycondensation under stirring for 2 to 12 hours (with 2 to 10 For hours, it is better.) In addition, in order to achieve the purpose of improving the hue or polymerizability when suppressing the polycondensation reaction of the polyester in the present invention, an application in the presence of a catalyst is performed. After the reaction or after the transesterification reaction, the esterification rate or transesterification rate is 90%. Multiple reaction tanks are used with low polymers to continuously advance the condensation reaction in the molten state. In the reaction tank with the highest internal temperature, When the temperature is ° C and the internal temperature of the final reaction tank is T (ω) ° C, it must satisfy T μ λ X> T (ω) 312 / Invention Specification (Supplement) / 92-09 / 92115 520
在至 之壓 :以3 1，4-110 別合 ，而 反應 換反 聚縮 .260 之溫 特別 2kPa 反應 反應 行酯 上之 行聚 Τ Μ Λ X 12 200409787 此外，為了反應速度之提高暨產品品質之提高及安定 最好能達到 ΪΜΛΧ-Τ(ω)^ 2°C ，其中以 T M A X - T ( ω ) ^ 4 °C 較合適，而以 Τμλχ-Τ(ω) — 5〇C 特別合適。 本發明所提之内溫乃在完全混合槽表示内液之溫度， 在具有活塞流動性之橫型反應器等之反應槽可設定複數 溫度之場合係表示最高之溫度，至於最終槽之T ( ω )係予 設定為反應槽出口近旁之溫度。 再者，在聚合物之抽出口數係複數之場合，最終槽之 溫Τ ( ω )則以複數存在，而至少其中之1個滿足上述關係 可。 本發明所提之π複數段η之聚縮合反應槽，一般指形狀 攪拌條件不同之複數之反應槽藉管系等所聯結成之構造 言，係指各反應槽之壓力可獨立設定者。 聚縮合反應槽之段數乃基於生產柔軟性之觀點，最好 為3段（3槽）以上。 再者，本發明所提之酯化率係表示二魏酸成分之全魏 中被酯化之羧基之比率之數值，再者，酯交換率係表示 料之二羧酸二烷酯中被原料二醇成分所取代之比率之 312/發明說明書(補件)/92-09/92115520 而 之 以 内 即 或 而 能 基 原 數 13 200409787 值，如下述界定： 酯化率二[(皂化價-酸價）/皂化價]X 1 0 0 酯交換率=[(二羧酸單元之莫耳濃度x2 -烷酯之當量） /(二羧酸單元之莫耳濃度χ2)]χ100 (式中，烷酯之烷基為原料二羧酸二烷酯由來之烷基） 酸價可藉一種使低聚合物溶於溶媒後施行鹼滴定之方 法來求出，而皂化價可藉一種使低聚合物經鹼加水分解後 用酸施行逆滴定之方法來求出。再者，為求出二羧酸單元 之莫耳濃度及烷酯之當量，例如可利用一種使低聚合物溶 於適當溶媒後測定 1 Η - N M R，而由各信號強度比求出之方 法。 ， 在本發明中，較佳的是，聚縮合步驟（Β)為使用串聯之3 槽以上之反應槽，以在熔融狀態下連續進行聚縮合反應之 步驟，而設反應槽内溫之最高溫度為 ΤMAX，反應槽内溫之 最低溫度為Τ Μ ! N，最終槽内溫為T ( ω )時，滿足 ΤΜΛΧ>Τ(ω)^ ΤμΙΝ ο 在本發明中，較佳的是，聚縮合步驟（Β )為使用串聯之3 槽以上之反應槽，以在熔融狀態下連續進行聚縮合反應之 步驟，而在未含最終槽之二個連續之反應槽中，擁有上游 側之内溫不低於下游側之内溫之連續槽。 此外，上述下游側之内溫最好能為高於最終槽内溫者。 再者，設聚縮合步驟（B )中從上游起第1槽之内溫為T ( 1 ) °C ，最終槽之内溫為T ( ω ) °C時，較佳的是 14 312/發明說明書(補件)/92_09/92115 52〇 200409787 Τ(1)^ Τ(ω) 再者，Τ μ Λ χ通常為低於2 8 0 °C ，以低於2 6 0 °C較佳， 步以低於2 5 0 °C較合適，而以低於2 4 5 °C特別合適。 在另一方面，Τ(ω)最好能為低於245 °C，其中以低於 °C較佳，進一步以低於2 3 9 °C較合適，而以低於2 3 8 °C 合適。 若未滿足上述之槽内溫度條件，則有使末端羧基量 端乙烯基量變多，造成色調惡化之傾向。 由聚縮合反應所得之樹脂通常從聚縮合反應槽之 被移送至聚合物拔取模，以帶條狀被拔出，在水冷期 水冷後，被切割機切斷，而成為丸粒狀、切屑狀之粒狀 為本發明中之酯化或酯交換反應觸媒，例如可舉出 三氧化二銻等之銻化合物，如二氧化鍺、四氧化鍺等 化合物，如烧氧鈦（如鈦酸四甲S旨、鈦酸四異丙S旨、鈦 丁酯等）、苯氧鈦（如鈦酸四苯酯等）等之鈦化合物，如 二丁錫、氧化甲基苯錫、四乙錫、氧化六乙二錫、氧 己基己二錫、氧化二（十二碳烷）錫、氫氧化三乙錫、 化三苯錫、乙酸三異丁錫、二乙酸二丁錫、二月桂酸 錫、三氯化一丁錫、氯化三丁錫、硫化二丁錫、氧化 錫、甲δ|ι酸、乙® I酸、丁轉酸等之錫化合物，如乙酸 氫氧化鎂、碳酸鎂、氧化鎂、烷氧鎂、磷酸氫鎂等之 合物，如乙酸鈣、氫氧化鈣、碳酸鈣、氧化鈣、烷氧 石粦酸氫#5等之妈化合物，以及ί孟化合物，鋅化合物等 312/發明說明書(補件)/92-09/92115520 進一 240 特別 、末 底部 間或 體。 ，如 之鍺 酸四 氧化 化環 氫氧 二苯 丁羥 鎂、 鎮化 1¾、 ，其 15 200409787 中以鈦化合物、錫化合物較佳，尤其以鈦酸四丁酯較合適。 觸媒之使用量並未特別受到限制，不過若太多，則不僅 成為異物混入之原因，亦成為聚合物熱滯留時之劣質化反 應之發生或產生氣體之原因，而若太少，主反應速度則降 低，而容易發生副反應，因此聚合物中之金屬濃度通常為 1至300ppm，以5至200ppm較佳，而以5至150ppm進一 步較佳，尤其以2 0至1 0 0 p p m較佳，其中以3 0至9 0 p p m 較合適。 再者，為聚縮合反應觸媒，將酯化反應或酯交換反應時 所添加之觸媒繼續使用以充作聚縮合反應觸媒而不添加新 觸媒亦可，進一步添加上述觸媒亦可，此時之使用量並未 特別受到限制，不過若太多，則會造成上述問題，因此聚 合物中之金屬濃度為300ppm以下，以200ppm以下較佳， 而以lOOppm以下進一步較佳，尤其以50ppm較合適。 再者，在使用有機鈦化合物為觸媒之場合，基於抑制異 物之觀點，最後達到之聚合物中之鈦金屬濃度最好能為 250ppm以下，以lOOppm以下較佳，其中以50ppm以下較 合適，而以3 3 p p m特別合適。上述金屬濃度可藉濕式灰化 等之方法回收聚合物中之金屬後，利用原子發光，或 I C P ( I n d u c e d C 〇 u p 1 e d P 1 a s m a )為光源之分析法等予以測 定。 再者，在上述酯化反應、酯交換反應、聚縮合反應中， 除了上述觸媒之外，亦可有其他添加劑（如下述）之存在： 反應助劑如磷化合物（如正磷酸，亞磷酸，次亞磷酸，多磷 16 312/發明說明書(補件)/92-09/92115 520 200409787 酸，以及其s旨或金屬鹽等）、驗金屬或驗土金屬化合物（如 氫氧化鈉、苯甲酸鈉、乙酸鎂、乙酸鈣等）等；抗氧化劑如 酚化合物（如2，6 -二第三丁 - 4 -辛苯酚、異戊四醇肆[3-(3 ’，5 ’ -第三丁 - 4 ’ -羥苯）丙酸酯]等）、硫醚化合物（如 3，3 ’ -硫二丙酸二月桂酯、異戊四醇肆[3 -月桂硫二丙酸酯] 等）、構化合物（如亞構酸三苯酯、亞礙酸叁（壬苯酯）、亞 磷酸叁（2，4 -二-第三丁苯酯）等）等；脫模劑如石蠟，微晶 蠟，聚乙烯蠟，褐煤酸或褐煤酸酯所代表之長鏈脂肪酸及 其酯，聚矽氧油等。 為聚縮合反應槽，可舉出縱型攪拌聚合槽、橫型攪拌聚 合槽、薄膜蒸發式聚合槽等之習知物，而由於聚縮合之後 期（在此時期，反應液之黏度會上升）物質移動比反應速度 更容易成為分子量增大之支配因子，為了在抑制副反應之 下推進主反應，儘量降低溫度而提高表面更新性係在達成 本發明之目的上有利之作法，因此最好能選定一種具有表 面更新性、栓流性、自淨性優異之薄膜蒸發功能之單一或 複數之橫型攪拌聚合機。 再者，使本發明之製法所得之聚酯繼續藉習知方法進行 固相聚合以提高分子量亦可。 在圖1及圖2展示實施態樣之例子。 在圖1中，2為完全混合型之酯化反應槽，P1為原料供 給管系，2 a為設在酯化反應槽2上部之通氣口，2 b為設在 酯化反應槽2上部之觸媒供給口。 在反應槽 2中，施行製造低聚合物之步驟（A )。再者， 17 312/發明說明書(補件)/92-09/92115520 200409787 在本實施態樣例中，聚縮合步驟（B )係在反應槽3至5之三 槽進行者。3為完全混合型之第一聚縮合反應槽，3 a為設 在第一聚縮合反應槽3上部之通氣口，4為完全混合型之 第二聚縮合反應槽，4 a為設在第二聚縮合反應槽4上部之 通氣口，5為在水平方向擁有2支攪拌軸及具有自淨性之 葉片之橫型之第三聚縮合反應槽，5 a為設在第三聚縮合反 應槽5上部之通氣口，P 2、P 3、P 4各為連接反應槽之管系， P 5為聚合物之抽出管系。在此場合，第三聚縮合反應槽5 由於具有二支旋轉軸，可選擇相同或不同方向之旋轉方 向，而為了提高表面更新性，最好能選擇不同方向之旋轉。 圖2為將圖1中之完全混合型之第二聚縮合反應槽變換 為一種在水平方向具有旋轉軸且有薄膜蒸餾性能之橫型反 應槽之態樣，即成為在容易滯留之旋轉軸中心部未具軸之 構造。 〈實施例〉 以下舉出實施例，以進一步詳細說明本發明，但本發明 並未受到上述實施例之限制。 又按，在實施例及比較例中，聚酯之評價係依照下述方 法施行者。 (1 )末端羧基濃度 使聚酯 0 . 5 g 溶於苄醇 2 5 m 1，對此使用氫氧化鈉之 0 . 0 1 m ο 1 / L苄醇溶液，以施行滴定。末端羧基濃度愈低， 表示对水解性愈佳。 (2)末端乙烯基濃度 18 312/發明說明書(補件)/92-09/92115520 200409787 使聚酯溶於六氟異丙醇/重氯仿=3 / 7 ( v / v )，以測定共振 頻率400MHz之1H-NMR而求出標的濃度。乙烯基濃度低， 表示製造中之副反應少，同時表示聚合性優異。 (3)末端二醇基濃度及末端烷基濃度 使聚酯溶於六氟異丙醇/重氯仿=3 / 7 ( v / v )，以測定共振 頻率400MHz之1H-NMR而求出標的濃度。 (4 )聚酯之數平均分子量 係由數平均分子量=2 /(總末端基濃度）求出者。但設定 總末端基濃度=末端羧基濃度+末端二醇濃度+末端乙烯基 濃度。 (5 )聚酯之色調 使用曰本電色（股）製之色差計（Z-300A型），算出黃色指 數b值而予以評價。此數值愈小，表示帶黃味愈少，色調 良好。 (6 )低聚合物之S旨化率 使用如下述求出之酸價及皂化價，藉此算出。 [酸價] 使低聚合物溶於二曱基甲醯胺，對此使用 0 . 1 N 之Κ Ο Η /曱醇溶液以施行滴定而求出酸價。 [皂化率] 用0 . 5 Ν之Κ Ο Η /乙醇溶液來施行低聚合物之水 解，然後用0 . 5 Ν之鹽酸以施行滴定而求出皂化價。 酯化率=[(皂化價-酸價）/皂化價]X 1 0 0 (7 )低聚合物之酯交換率 使用由利用共振頻率4 0 0 Μ Η ζ之1 Η - N M R所測定之殘存甲 酯之當量以及由皂化價所求出之二羧酸單元之莫耳濃度， 19 312/發明說明書(補件)/92-09/92115520 200409787 按照下述計算式算出： 酯交換率=[(二羧酸單元之莫耳濃度X 2 -曱酯之當量）/ (二魏酸單元之莫耳濃度χ2)]χ100 (實施例1 ) 圖3展示本實施例之流程圖。在圖3中，1為漿液調製 槽，1 a及1 b各為設在漿液調製槽1之上部之二羧酸成分 及二醇成分之各原料供給口，2為酯化反應槽（施行製造低 聚合物之步驟），2 a為設在酯化反應槽2上部之通氣口，2 b 為設在酯化反應槽2上部之觸媒供給口，2 c為設在酯化反 應槽之取樣口，3為第一聚縮合反應槽（在聚縮合反應槽 3，4，5施行聚縮合步驟），3 a為設在第一聚縮合反應槽3上 部之通氣口，3C為取樣口，4為第二聚縮合反應槽，4a為 設在第二聚縮合反應槽4上部之通氣口，4C為取樣口，5 為在水平方向擁有攪拌軸之橫型之第三聚縮合反應槽，5 a 為設在第三聚縮合反應槽5上部之通氣口，6為聚合物拔 取模，7為旋轉式切割機，Μ 1 , Μ 2，Μ 3，Μ 4，Μ 5各為攪拌裝置， G1，G2，G3，G4，G5各為齒輪泵，？1，卩2，卩3，？4，？5各為管系。 預先將酯化率 9 3 %之聚對酞酸丁二酯低聚合物裝填於酯 化反應槽2後，將按對酞酸1 . 0莫耳與1，4 - 丁二醇1 . 8莫 耳之比率製成之漿液以可成為5 0 L / h之方式從漿液調製槽 1藉齒輪泵G1通過管系P1内連續供給於一具有螺旋型攪 拌機之酯化反應槽2之同時，將酞酸四丁酯以聚合物每一 理論回收量基準之鈦濃度可成為 1 〇 0 p p m之方式從觸媒供 給口 2 b連續供給於酯化反應槽2。酯化反應槽2係一具備 20 312/發明說明書(補件)/92-09/92115520 200409787 攪拌裝置M2之縱型反應槽，該裝置M2為具有 並安裝有葉片直徑1 60πιπι之螺旋型攪拌葉片者 反應槽2之内溫為230 °C，其壓力為78kPa，將 及四氫呋喃暨未反應之 1，4 - 丁二醇從與減壓 連接之通氣口 2 a抽出，以通過精餾塔（未圖示 應之1，4 - 丁二醇一部分回流於第一酯化反應才! 餘之1，4 - 丁二醇，水及四氫呋喃抽出於反應系 進行酯化反應。此時以酯化槽2之實際液量可 之方式施加液面控制之同時將反應液抽出，以 第一聚縮合反應槽3。在反應系安定化起經過 由取樣口 2 c採取之低聚合物試樣得知，低聚合 為 9 8%。 第一聚縮合反應槽3為具備一擁有垂直旋轉 置M3之縱型反應槽，設定該反應槽3之内溫J 壓力為2. 7kPa，以實際液量可成為100升之方 控制，將所產生之水及四氫吱喃暨1，4 - 丁二醇 (未圖示）連接之通氣口 3a抽出之同時，施行初 應，而將所抽出之反應液連續供給於第二聚 4。此時從齒輪泵G 3出口之取樣口（未圖示）抽 試樣以測定數平均分子量，而得到該分子量為 果。 第二聚縮合反應槽4為具備一擁有垂直旋轉 置M4之縱型反應槽，設定該反應槽4之内溫J 壓力為200Pa，以實際液量可成為100升之方 312/發明說明書(補件)/92-09/92115520 垂直旋轉軸 ，設定酯化 所產生之水 機（未圖示） )後，使未反 ^ 2，而將殘 統外之同時 成為1 00升 連續供給於 1 2小時後， 物之ϊ旨化率 軸之攪拌裝 b 2 4 5 〇C，其 式施加液面 從與減壓機 期聚縮合反 縮合反應槽 取預聚合物 4 0 5 0之結 軸之攪拌裝 b 2 4 0 °C，其 式施加液面 21 200409787 控制，將所產生之水及四氫呋喃暨1，4 - 丁二醇從與減壓機 (未圖示）連接之通氣口 4 a抽出之同時，進一步施行聚縮合 反應，而將所抽出之反應液連續供給於第三聚縮合反應槽 5。此時從齒輪泵G 4出口之取樣口（未圖示）抽取預聚合物 試樣以測定數平均分子量，而得到該分子量為 9 7 0 0之結 果。 第三聚縮合反應槽5為具備一擁有2支自淨性水平旋轉 軸之攪拌裝置Μ 5之縱型反應槽，設定該反應槽5之内溫為 235 °C ，其壓力為200Pa，以實際液量可成為40升之方式 施加液面控制，將所產生之水及四氫呋喃暨1，4 - 丁二醇從 與減壓機（未圖示）連接之通氣口 5a抽出之同時，進行聚縮 合反應。使所得之聚合物藉齒輪泵G 5通過管系P 5内後， 從聚合物拔取模6按條帶狀予以連續拔出，而用旋轉式切 割機7予以切斷。所得聚合物之數平均分子量為 2 0 0 0 0， 末端羧基濃度為12peq/g，而末端乙烯基濃度為4peci/g。 將聚合物之分析值一併示於表1中。即得到一種少含末端 乙烯基且色調優異之聚對酞酸丁二酯樹脂。 (實施例2 ) 除了設定第一聚縮合反應槽3之内溫為240 °C ，第二聚 縮合反應槽4之内溫為2 4 5 °C ，第三聚縮合反應槽5之内 溫為2 3 5 °C之外，均與實施例1 一樣實施。第一聚縮合反 應槽3之出口預聚合物之數平均分子量為3 2 0 0，第二聚縮 合反應槽4之出口預聚合物之數平均分子量為8 5 0 0，所得 到之聚合物之數平均分子量為 1 9 5 0 0，末端羧基濃度為 22 312/發明說明書(補件)/92-09/92115520 200409787 14peq /g，而末端乙稀基濃度為 6peq /g。將聚合物 析值一併示於表1中。即得到一種少含末端乙烯基且 優異之聚對酞酸丁二酯樹脂。 (實施例3 ) 除了設定第一聚縮合反應槽3之内溫為 2 3 5 °C ，第 縮合反應槽4之内溫為2 4 5 °C ，第三聚縮合反應槽5 溫為2 4 0 °C之外，均與實施例1 一樣實施。第一聚縮 應槽3之出口預聚合物之數平均分子量為2 8 0 0，第二 合反應槽4之出口預聚合物之數平均分子量為8 4 0 0， 到之聚合物之數平均分子量為 1 9 7 0 0，末端羧基濃 17peq /g，而末端乙稀基濃度為 8peq /g。將聚合物 析值一併示於表1中。即得到一種少含末端乙烯基且 優異之聚對酞酸丁二酯樹脂。 (實施例4 ) 除了將酞酸四丁酯以聚合物每一理論收量基準之 可成為7 5 p p m之方式設定之外，均與實施例1 一樣實 第一聚縮合反應槽 3之出口預聚合物之數平均分子 4 0 5 0，第二聚縮合反應槽4之出口預聚合物之數平均 量為9 0 0 0，所得到之聚合物之數平均分子量為1 9 5 0 0 端羧基濃度為 9peq/g，而末端乙烯基濃度為 4με(ΐ 將聚合物之分析值一併示於表1中。即得到一種少含 乙烯基而尤其色調優異之聚對酞酸丁二酯樹脂。 (實施例5 ) 預先將酯化率 9 3%之聚對酞酸丁二酯低聚合物裝填 312/發明說明書(補件)/92-09/92115520 之分 色調 二聚 之内 合反 聚縮 所得 度為 之分 色調 鈦量 施。 量為 分子 ，末 /g 0 末端 於實 23 200409787 施例1之反應槽2後，將對酞酸二甲酯及1，4 - 丁二醇按對 酞酸二曱酯1.0莫耳與1,4 -丁二醇1.5莫耳之比率供給於 酯交換反應槽2，設定反應槽2之内溫為2 0 0 °C，其壓力為 1 0 1 k P a，此外均與實施例1 一樣實施。在反應系安定化起 經過1 2小時後之取樣口 2 c所採取之低聚合物之酯化率為 9 6 %。第一聚縮合反應槽3之出口預聚合物之數平均分子量 為3900，第二聚縮合反應槽4之出口預聚合物之數平均分 子量為9 5 0 0，所得到之聚合物之數平均分子量為2 0 0 0 0， 末端魏基濃度為18peq/g，而末端乙嫦基濃度為4peq/g。 將聚合物之分析值一併示於表1中。即得到一種少含末端 乙烯基且色調優異之聚對酞酸丁二酯樹脂。 (比較例1 ) 除了設定第一聚縮合反應槽3之内溫為 235 °C ，第二聚 縮合反應槽4之内溫為2 4 0 °C ，第三聚縮合反應槽5之内 溫為2 4 5 °C之外，均與實施例1 一樣實施。第一聚縮合反 應槽3之出口預聚合物之數平均分子量為2 8 0 0，第二聚縮 合反應槽4之出口預聚合物之數平均分子量為8 3 0 0，所得 到之聚合物之數平均分子量為 2 0 0 0 0，末端羧基濃度為 2 3 μ e q / g j而末端乙嫦基濃度為14peq/g。將聚合物之分 析值一併示於表1中。即末端乙烯基增加而色調惡化。 (比較例2 ) 除了設定第一聚縮合反應槽3之内溫為 240 °C ，第二聚 縮合反應槽4之内溫為2 3 5 °C ，第三聚縮合反應槽5之内 温為2 4 5 °C之外，均與實施例1 一樣實施。第一聚縮合反 24 312/發明說明書(補件)/92-09/92115520 200409787 應槽3之出口預聚合物之數平均分子量為3 2 0 0，第二聚細 合反應槽4之出口預聚合物之數平均分子量為8200’所知 到之聚合物之數平均分子量為1 9 6 0 0，末端羧基濃度為 22peq/g，而末端乙烯基濃度為i3peq/g。將聚合物之分 析值一併示於表1中。即末端乙稀基增加而色調惡化。 (比較例3 ) 除了設定第一聚縮合反應槽3之内溫為235。C，第二聚 縮合反應槽4之内溫為2 4 0 °C ，第三聚縮合反應槽5之内 溫為2 4 5 °c之外，均與實施例5 —樣實施。第一聚縮合反 應槽3之出口預聚合物之數平均分子量為2700,第二聚縮 合反應槽4之出口預聚合物之數平均分子量為8 2 0 0 ’所知 到之聚合物之數平均分子量為20000，末端羧基濃度為 28peq /g，而末端乙烯基濃度為14peq /g。將聚合物之分 析值一併示於表1中。即末端乙稀基增加而色調惡化。 表1 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 比較例 1 比較例 2 比較例 3 二羧酸成分原料 TPA TPA TPA TPA DMT TPA TPA DMT 觸媒濃度 piDm/聚合物 100 100 100 75 100 100 100 100 第一 聚縮合槽 __内溫 °C 245 240 235 245 245 235 240 235 數平均分子量 4050 3200 2800 4050 3900 2800 3200 2700 第二 聚縮合槽 内溫 °c 240 245 245 240 240 240 235 240 數平均分子量 9700 8500 8400 9000 9500 8300 8200 8200 第三 聚縮合槽 反應槽出口溫度 °c 235 235 240 235 235 245 245 245 數平均分子量 20000 19500 19700 19500 20000 20000 19600 20000 [COOH] geq/g 12 14 17 9 18 23 22 28 [CH2=CH] Meq/g 4 6 8 4 4 14 13 14 聚合物之色調 0.6 0.7 0.8 0.4 0.9 2.9 2.6 3.1 TPA :對酞酸 DMT :對酞酸二甲酯 (實施例6 ) 25 312/發明說明書(補件)/92-09/92115520 200409787 藉由圖4所示之S旨化步驟及圖5所示之聚縮合步驟，依 照下述要領施行P B T之製造。首先，將按對酞酸1 . 0 0莫耳 與1，4 - 丁二醇1 . 8 0莫耳之比率混合之6 0 °C漿液從漿液調 製槽通過原料供給管線（L 1 )以可成為 2 8 · 5 k g / h之方式連 續供給於酯化用反應槽（D )，其擁有螺旋型攪拌機且預先裝 填有酯化率9 9 %之P B T低聚物者。同時地，將1 8 5 °C之精餾 塔（E)之塔底成分按12. Okg/h從再循環管線（L2)供給於該 反應槽（D)，亦將充作觸媒之 65 °C之酞酸四丁酯 6.0\^%1，4-丁二醇溶液按69忌/11(聚合物理論收量基準之 鈦金屬濃度 3 0 p p m )從觸媒供給管線（L 3 )供給於該反應槽 (D)。此溶液中之水分為0.20wt%。 設定反應槽（D)之内溫為230 °C ，其壓力為78kPa，使所 產生之水及四氫呋喃暨剩餘之 1，4 - 丁二醇從餾出管線（L 5 ) 餾出，藉精餾塔（E )予以分離為高沸點成分與低沸點成分。 在反應系安定化後之塔底高沸點成分中 1，4 - 丁二醇所佔 之比率為98wt%以上，以精餾塔（E)之液面可達一定之方式 將其一部分藉由抽出管線（L 8 )抽出於外部。在另一方面， 將低沸點成分從塔頂以氣體形態抽出，用冷凝器（Η)使之凝 縮，而以儲槽（J )之液面可達一定之方式從抽出管線（L 1 3 ) 予以抽出於外部。 將反應槽（D )所產生之低聚合物之一定量在使用齒輪泵 (G 6 )之下從抽出管線（L 4 )抽出，而以反應槽（D )内液之平均 滯留時間可達3 . 3小時之方式予以控制液面。將從抽出管 線（L 4 )抽出之低聚合物連續供給於第一聚縮合反應槽 26 312/發明說明書(補件)/92-09/92115520 200409787 (Q )。在反應系安定化後，在反應槽（A )出口取樣， 定之低聚合物之酯化率為9 7 . 3 °/〇。 設定第一聚縮合反應槽（Q )之内溫為2 4 1 . 0 °C，其 2 · 1 k P a，以滯留時間可成為 1 5 0 分鐘之方式施行 制。將水、四氫呋喃、以及 1，4 - 丁二醇從與減壓d 示）連接之通氣管線（L 1 6 )抽出之同時，施行初期聚 應。將所抽出之反應液連續供給於第二聚縮合反應 設定第二聚縮合反應槽（R)之内溫為244.3 °C，其 1 6 0 P a，以滯留時間可成為1 2 0分鐘之方式施行液δ 而將水、四氫呋喃、以及1，4 - 丁二醇從與減壓機（； 連接之通氣管線（L 1 8 )抽出之同時，進一步施行聚 應。將所得之聚合物使用抽液齒輪泵（G 8 )藉由抽 (L 1 7 )連續供給於第三聚縮合反應槽（S )。 設定第三聚縮合反應槽（S)之反應器出口溫度為 °C ，其壓力為1 8 0 P a，以滯留時間可成為1 5 0分鐘 施行液面控制，而將水、四氫咬喃、以及1，4 - 丁二 減壓機（未圖示）連接之通氣管線（L 2 0 )抽出之同時， 施行聚縮合反應。將所得之聚合物使用抽液齒輪泵 由抽出管線（L 1 9 )從模頭（6 )以條帶狀連續拔出，而 式切割機（7 )予以切斷。所得聚合物之數平均分 28900，末端叛基濃度為 24peq /g，末端乙婦基 1 1 μ e q / g，而b值為-0 . 6。即得到一種少含末端羧 少含末端乙烯基，且色調優異之聚對酞酸丁二酯樹 將聚合物之分析值一併示於表2中。 312/發明說明書(補件)/92-09/92115520 而所測 壓力為 液面控 I (未圖 縮合反 槽（R ) 〇 壓力為 1控制， k圖示） 縮合反 出管線 2 3 8.6 之方式 醇從與 進一步 (G 9 )藉 用旋轉 子量為 濃度為 基，亦 脂0 27 200409787 (比較例4 ) 除了設定第三聚縮合反應槽（S )之反應器出口之溫度為 2 4 6 . 5 ° C及其壓力為2 6 0 P a之外，均與實施例6 —樣實施。 其末端羧基及末端乙烯基均有增加，色調亦惡化。 將聚合物之分析值一併示於表2中。 表2 實施例6 比較例4 二羧酸成分原料 TPA TPA 觸媒濃度 ppm/聚合物 30 30 第一聚縮合槽 内溫 °c 241.0 241.0 第二聚縮合槽 内溫 °c 244.3 244.3 第三 聚縮合槽 反應槽出口溫度 °c 238.6 246.5 數平均分子量 28900 28800 [C00H] peq/g 24 43 [ch2=ch] μeq/g 11 16 聚合物之色調 -0.6 3.5 TPA :對酞酸 〈產業上之可利用性〉 依照本發明之製造聚酯之方法，可抑制聚縮合反應時之 副反應而得到改善色調或聚合性之聚酯，因此其產業上之 利用價值很高。 【圖式簡單說明】 圖1為本發明較佳之一實施形態之聚酯製造裝置之概略 圖。 圖2為本發明較佳之一實施形態之聚酯製造裝置之概略 圖。 圖3為實施例1所用之聚酯製造裝置之概略圖。 圖4為實施例6所用之酯化步驟之概略圖。 28 312/發明說明書(補件)/92-09/92115 520 200409787 圖5為實施例6所用之聚縮合步驟之 概略圖。 元件符 號 說明 ) 1 漿 液 調 製 槽 1 a、1 b 原 料 供 給 口 2 酯 化 反 應 槽 2a 通 氣 口 2b 觸 媒 供 給 口 2 c 取 樣 口 3 第 一 聚 縮 合 反 應 槽 3 8. 通 氣 口 3c 取 樣 α 4 第 二 聚 縮 合 反 應 槽 4 a 通 氣 口 4 c 取 樣 α 5 第 三 聚 縮 合 反 應 槽 5 a 通 氣 π 6 聚 合 物 拔 取 模 7 旋 轉 式 切 割 機 M1、M2、M3、M4、M5 攪拌裝置 Gl 、 G2 、 G3 、 G4 、 G5 、 G6 、 G7 、 G8 、 P 1 原料供給管系 P 2、P 3、P 4 反應槽連接 P5 聚合物抽出管系 D 酯化反應槽 G 9 齒輪果 管系 312/發明說明書(補件)/92-09/92115520 29 200409787 E 精 餾 塔 F 泵 Η 冷 凝 器 J 儲 槽 K 泵 LI 原 料 供 給 管 線 L2 再 循 環 管 線 L3 觸 媒 供 給 管 線 L4 抽 出 管 線 L5 餾 出 管 線 L6 抽 出 管 線 L7 循 環 管 線 L8 抽 出 管 線 L9 氣 體 抽 出 管 線 LI 0 凝 縮 管 線 LI 1 抽 出 管 線 L 1 2 循 環 管 線 LI 3 抽 出 管 線 LI 4 通 氣 管 線 LI 5 抽 出 管 線 LI 6 通 氣 管 線 LI 7 抽 出 管 線 LI 8 通 氣 管 線 L 1 9 抽 出 管 線 31V發明說明書(補件)/92-09/92115520 200409787 L20 通氣管線 Q 第一聚縮合反應槽 R 第二聚縮合反應槽 S 第三聚縮合反應槽。The pressure at the end: 3 1,4-110, and the reaction is changed to inverse polycondensation. The temperature of 260 is a special 2kPa reaction. The reaction is performed on the ester. Poly Μ Λ X 12 200409787 In addition, in order to improve the reaction speed and products The quality improvement and stability should preferably reach ΪΜΛχ-Τ (ω) ^ 2 ° C, of which TMAX-T (ω) ^ 4 ° C is more suitable, and τμλχ-T (ω)-50 ° C is particularly suitable. The internal temperature mentioned in the present invention refers to the temperature of the internal liquid in the complete mixing tank. Where a plurality of temperatures can be set in a reaction tank such as a horizontal reactor with piston fluidity, the highest temperature is indicated. As for the final tank T ( ω) is set to a temperature near the outlet of the reaction tank. In addition, when the number of polymer outlets is plural, the final tank temperature T (ω) exists in plural, and at least one of them may satisfy the above relationship. The polycondensation reaction tanks of π plural sections η mentioned in the present invention generally refer to a structure in which a plurality of reaction tanks having different shapes and stirring conditions are connected by a piping system, etc., which means that the pressure of each reaction tank can be independently set. The number of stages of the polycondensation reaction tank is based on the viewpoint of production flexibility, and it is preferably three or more (three tanks). In addition, the esterification rate mentioned in the present invention is a numerical value indicating the ratio of carboxyl groups to be esterified in the whole Wei of the diweilic acid component. Furthermore, the transesterification rate indicates the raw material in the dialkyl dicarboxylic acid. The ratio of the diol component replaced by 312 / Invention Specification (Supplement) / 92-09 / 92115520 and the value of the original number is 13 200409787, as defined below: Esterification rate two [(Saponification value-acid Valence) / saponification value] X 1 0 0 transesterification rate = [(Molar concentration of dicarboxylic acid unit x 2-equivalent of alkyl ester) / (Molar concentration of dicarboxylic acid unit χ 2)] χ 100 (wherein the alkane The alkyl group of the ester is the alkyl group derived from the dialkyl dicarboxylic acid. The acid value can be obtained by a method of dissolving the low polymer in a solvent and then performing an alkali titration. The saponification value can be obtained by using a low polymer. After alkali hydrolysis, it is determined by acid titration. Further, in order to obtain the molar concentration of the dicarboxylic acid unit and the equivalent of the alkyl ester, for example, a method in which a low polymer is dissolved in an appropriate solvent and 1 Η -N M R is measured, and the signal intensity ratio can be obtained. In the present invention, it is preferable that the polycondensation step (B) is a step of using three or more reaction tanks in series to continuously perform the polycondensation reaction in a molten state, and the maximum temperature in the reaction tank is set. It is TMAX, the minimum temperature in the reaction tank is T M! N, and when the final tank temperature is T (ω), it satisfies TMΛ × > T (ω) ^ ΤμΙΝ ο In the present invention, preferably, the polycondensation step (B) is a step of using three or more reaction tanks in series to continuously perform the polycondensation reaction in a molten state, and in two continuous reaction tanks that do not include a final tank, the internal temperature of the upstream side is not low Continuous tank with internal temperature on the downstream side. In addition, it is preferable that the internal temperature on the downstream side is higher than the internal temperature of the final tank. Furthermore, when the internal temperature of the first tank from the upstream in the polycondensation step (B) is T (1) ° C, and the final internal temperature of the tank is T (ω) ° C, it is preferably 14 312 / invention Instruction (Supplement) / 92_09 / 92115 52〇200409787 Τ (1) ^ Τ (ω) Furthermore, T μ Λ χ is usually lower than 2 8 0 ° C, preferably lower than 2 6 0 ° C. Step A temperature below 25 ° C is more suitable, and a temperature below 25 ° C is particularly suitable. On the other hand, T (ω) is preferably below 245 ° C. Among them, it is preferably below ° C, more preferably below 2 3 9 ° C, and below 2 3 8 ° C. . If the above-mentioned temperature conditions in the tank are not satisfied, the amount of terminal carboxyl groups and the amount of terminal vinyl groups tend to increase, and the color tone tends to deteriorate. The resin obtained by the polycondensation reaction is usually transferred from the polycondensation reaction tank to the polymer extraction mold, and is pulled out in a strip shape. After water cooling in the water cooling period, it is cut by a cutting machine to become pellets and chips. The granular form is the catalyst for the esterification or transesterification reaction in the present invention, and examples thereof include antimony compounds such as antimony trioxide, such as germanium dioxide, germanium tetraoxide, and other compounds, such as titanium oxide (such as titanium titanate) A methyl compound, tetraisopropyl titanate, titanium butyl ester, etc.), titanium phenoxide (such as tetraphenyl titanate, etc.) and other titanium compounds, such as dibutyltin, methylphenyltin oxide, tetraethyltin, Hexaethylene tin oxide, oxohexylhexanotin, di (dodecane) tin oxide, triethyltin hydroxide, triphenyltin oxide, triisobutyltin acetate, dibutyltin diacetate, tin dilaurate, Tin compounds such as monobutyltin trichloride, tributyltin chloride, dibutyltin sulfide, tin oxide, δ | ι acid, ethyl® I acid, butyranoic acid, such as magnesium acetate, magnesium hydroxide, oxidized Compounds of magnesium, magnesium alkoxide, magnesium hydrogen phosphate, etc., such as calcium acetate, calcium hydroxide, calcium carbonate, calcium oxide, alkanoic acid Hydrogen # 5 and other mother compounds, as well as helium compounds, zinc compounds, etc. 312 / Invention Specification (Supplements) / 92-09 / 92115520 Into a 240 special, the bottom or the body. For example, the germanium tetroxide epoxidized dihydrogenated diphenyl butyroxol, the hydration 1¾, and the 15 200409787 are preferably titanium compounds and tin compounds, especially tetrabutyl titanate is more suitable. The amount of catalyst used is not particularly limited, but if it is too much, it will not only cause the foreign matter to enter, but also cause the deterioration of the polymer during thermal retention or the generation of gas. If it is too small, the main reaction The speed is reduced and side reactions are prone. Therefore, the metal concentration in the polymer is usually 1 to 300 ppm, preferably 5 to 200 ppm, and more preferably 5 to 150 ppm, especially 20 to 100 ppm. Among them, 30 to 90 ppm is more suitable. In addition, for the polycondensation reaction catalyst, the catalyst added during the esterification reaction or the transesterification reaction may continue to be used as a polycondensation reaction catalyst without adding a new catalyst, and the above-mentioned catalyst may be further added. At this time, the amount of use is not particularly limited, but if too much, it will cause the above problems, so the metal concentration in the polymer is 300 ppm or less, preferably 200 ppm or less, and further preferably 100 ppm or less, especially 50ppm is more suitable. Furthermore, in the case where an organic titanium compound is used as a catalyst, from the viewpoint of suppressing foreign matter, the titanium metal concentration in the polymer finally achieved is preferably 250 ppm or less, preferably 100 ppm or less, and 50 ppm or less is more suitable. Especially suitable is 3 3 ppm. The above metal concentration can be measured by wet ashing and other methods to recover the metal in the polymer, and then use atomic luminescence, or an analysis method such as I C P (I n d u c e d C o u p 1 e d P 1 a s m a) as a light source. In addition, in the above-mentioned esterification reaction, transesterification reaction, and polycondensation reaction, in addition to the above-mentioned catalyst, there may be other additives (such as the following): Reaction assistants such as phosphorus compounds (such as orthophosphoric acid, phosphorous acid) , Hypophosphite, polyphosphorus 16 312 / Invention Specification (Supplement) / 92-09 / 92115 520 200409787 acid, and its purpose or metal salt, etc., metal test or soil test metal compounds (such as sodium hydroxide, benzene Sodium formate, magnesium acetate, calcium acetate, etc.); antioxidants such as phenol compounds (such as 2,6-di-tert-butyl-4-octylphenol, isopentaerythritol [3- (3 ', 5'-tert-butyl) -4'-hydroxybenzene) propionate], etc.), thioether compounds (such as 3,3'-dilauryl thiodipropionate, isopentaerythritol [3-laurate thiodipropionate], etc.), Structural compounds (such as triphenylene acid, triphenylene acid (nonylphenyl), triphenylene acid (2,4-di-tert-butylphenyl), etc.); release agents such as paraffin, microcrystalline wax , Polyethylene wax, montanic acid or montanic acid represented by long-chain fatty acids and their esters, silicone oil, etc. As the polycondensation reaction tank, there are known things such as a vertical stirring polymerization tank, a horizontal stirring polymerization tank, and a thin-film evaporation polymerization tank. However, due to the later period of the polycondensation (the viscosity of the reaction solution will increase during this period) Substance movement is more likely to be the dominant factor for molecular weight increase than reaction speed. In order to promote the main reaction while suppressing side reactions, and to reduce the temperature as much as possible to improve the surface renewability, it is advantageous to achieve the purpose of the invention, so it is best to Select a single or multiple horizontal type agitation polymerization machine with thin film evaporation function with excellent surface renewability, plug flow and self-cleaning properties. Further, the polyester obtained by the production method of the present invention may be subjected to solid state polymerization by a conventional method to increase the molecular weight. Examples of implementation aspects are shown in FIGS. 1 and 2. In Fig. 1, 2 is a completely mixed type esterification reaction tank, P1 is a raw material supply pipe system, 2 a is an air vent provided on the upper part of the esterification reaction tank 2 and 2 b is provided on the upper part of the esterification reaction tank 2 Catalyst supply port. In the reaction tank 2, a step (A) of producing a low polymer is performed. Furthermore, 17 312 / Invention Specification (Supplement) / 92-09 / 92115520 200409787 In the example of this embodiment, the polycondensation step (B) is performed in three to five reaction tanks. 3 is the first polycondensation reaction tank of the complete mixing type, 3a is an air vent provided at the upper part of the first polycondensation reaction tank 3, 4 is the second polycondensation reaction tank of the completely mixed type, and 4a is provided in the second The air vent at the upper part of the polycondensation reaction tank 4, 5 is a horizontal third polycondensation reaction tank with two stirring shafts and self-cleaning blades in the horizontal direction, and 5a is the upper part of the third polycondensation reaction tank 5. The vents, P 2, P 3, and P 4 are the piping systems connected to the reaction tank, and P 5 is the extraction piping system of the polymer. In this case, since the third polycondensation reaction tank 5 has two rotation shafts, the rotation directions of the same or different directions can be selected, and in order to improve the surface renewability, it is better to select rotations of different directions. FIG. 2 shows a state in which the completely mixed second polycondensation reaction tank in FIG. 1 is transformed into a horizontal type reaction tank having a rotation axis in the horizontal direction and thin film distillation performance, that is, the center of the rotation axis that is easy to stay. No shaft structure. <Examples> Examples are given below to further describe the present invention in detail, but the present invention is not limited to the above examples. In addition, in Examples and Comparative Examples, the evaluation of polyester was performed according to the following method. (1) Terminal carboxyl group concentration: 0.5 g of polyester was dissolved in benzyl alcohol 2.5 m 1, and a 0.1% m / o benzyl alcohol solution of sodium hydroxide was used for titration. The lower the terminal carboxyl group concentration, the better the hydrolyzability. (2) Terminal vinyl concentration 18 312 / Invention specification (Supplement) / 92-09 / 92115520 200409787 Dissolve the polyester in hexafluoroisopropanol / dichloroform = 3/7 (v / v) to determine the resonance frequency The target concentration was determined by 1H-NMR at 400 MHz. A low vinyl group concentration means that there are few side reactions during production, and it also shows that the polymerizability is excellent. (3) Terminal diol group concentration and terminal alkyl group concentration The polyester was dissolved in hexafluoroisopropanol / dichloroform = 3/7 (v / v), and the target concentration was determined by measuring 1H-NMR at a resonance frequency of 400 MHz. . (4) Number average molecular weight of polyester The number average molecular weight was calculated from number average molecular weight = 2 / (total terminal group concentration). But set the total terminal group concentration = terminal carboxyl group concentration + terminal diol concentration + terminal vinyl group concentration. (5) Tint of polyester Using a color difference meter (Z-300A type) made by Japan Electric Color Co., Ltd., the yellow index b value was calculated and evaluated. The smaller the value is, the less yellowish the color is, and the better the color tone is. (6) S-specification ratio of low polymer Calculated using the acid value and saponification value obtained as described below. [Acid value] The oligomer was dissolved in dimethylformamide, and a KOOH / methanol solution of 0.1 N was used to perform titration to determine the acid value. [Saponification rate] A 0.5 Ν ΟΗΗ / ethanol solution was used to hydrolyze the low polymer, and then 0.5 Ν hydrochloric acid was used to perform titration to determine the saponification value. Esterification rate = [(saponification value-acid value) / saponification value] X 1 0 0 (7) The transesterification rate of the low polymer is determined by using a resonance frequency of 4 0 0 Μ Η ζ 1 Η-residual by NMR measurement The equivalent of methyl ester and the molar concentration of the dicarboxylic acid unit obtained from the saponification value are calculated according to the following formula: 19 312 / Invention Specification (Supplement) / 92-09 / 92115520 200409787: Transesterification rate = [( Molar concentration of dicarboxylic acid unit X 2-equivalent of fluorenyl ester) / (Molar concentration of diferulic acid unit χ2)] χ100 (Example 1) FIG. 3 shows a flowchart of this example. In FIG. 3, 1 is a slurry preparation tank, 1 a and 1 b are each a raw material supply port of a dicarboxylic acid component and a diol component provided on the upper part of the slurry preparation tank 1, and 2 is an esterification reaction tank (manufactured by the manufacturer) Low polymer step), 2 a is a vent provided in the upper part of the esterification reaction tank 2, 2 b is a catalyst supply port provided in the upper part of the esterification reaction tank 2, and 2 c is a sample set in the esterification reaction tank Port 3 is the first polycondensation reaction tank (the polycondensation step is performed in the polycondensation reaction tanks 3, 4, and 5), 3a is an air vent provided on the upper part of the first polycondensation reaction tank 3, 3C is the sampling port, 4 Is a second polycondensation reaction tank, 4a is an air vent provided at the upper part of the second polycondensation reaction tank 4, 4C is a sampling port, 5 is a third type of polycondensation reaction tank having a horizontal type with a stirring axis in the horizontal direction, 5a It is an air vent provided at the upper part of the third polycondensation reaction tank 5, 6 is a polymer extraction die, 7 is a rotary cutter, M1, M2, M3, M4, and M5 are each a stirring device, G1, G2, G3, G4, G5 are gear pumps? 1, 卩 2, 卩 3 ,? 4 ,? 5 are piping systems. The polybutylene terephthalate oligomer having an esterification rate of 93% was charged in the esterification reaction tank 2 in advance, and 1.0 mol of terephthalic acid and 1,4-butanediol 1.8 mol were added. The slurry produced by the ratio of ears can be continuously supplied from the slurry preparation tank 1 to the esterification reaction tank 2 with a spiral mixer through a pipe system P1 through a gear pump G1 so as to be 50 L / h. Tetrabutyl acid is continuously supplied to the esterification reaction tank 2 from the catalyst supply port 2 b so that the titanium concentration of the polymer can be 100 ppm based on the theoretical recovery amount. The esterification reaction tank 2 is a vertical reaction tank equipped with 20 312 / Invention Specification (Supplement) / 92-09 / 92115520 200409787 stirring device M2. The device M2 is a spiral stirring blade with a blade diameter of 1 60 μm. The internal temperature of the reaction tank 2 is 230 ° C, and the pressure is 78 kPa. The tetrahydrofuran and unreacted 1,4-butanediol are withdrawn from the vent 2a connected to the reduced pressure to pass through the rectification column (not The figure shows that some of the 1,4-butanediol is refluxed in the first esterification reaction! The remaining 1,4-butanediol, water and tetrahydrofuran are drawn out of the reaction system for esterification. At this time, the esterification tank 2 is used. The actual liquid volume can be controlled by way of applying the liquid level, and the reaction liquid is drawn out to the first polycondensation reaction tank 3. After the reaction system is stabilized, it passes through the low polymer sample taken from the sampling port 2c. The polymerization is 9 8%. The first polycondensation reaction tank 3 is provided with a vertical reaction tank having a vertical rotation M3, the internal temperature J pressure of the reaction tank 3 is set to 2. 7kPa, and the actual liquid volume can be 100 liters. Control of the formula, the generated water and tetrahydro squeaking and 1,4-butanediol (not (Shown) At the same time as the connected vent 3a is drawn out, the initial response is performed, and the extracted reaction solution is continuously supplied to the second poly 4. At this time, a sample is taken from a sampling port (not shown) at the outlet of the gear pump G 3 to The number average molecular weight is measured, and the molecular weight is obtained. The second polycondensation reaction tank 4 is provided with a vertical reaction tank having a vertical rotation M4. The internal temperature J pressure of the reaction tank 4 is set to 200 Pa, based on the actual liquid volume. Can be a 100 liter square 312 / Invention Manual (Supplement) / 92-09 / 92115520 Vertical rotation axis, set the water machine (not shown) generated by the esterification, make it not reverse ^ 2 and the residual system At the same time, it becomes 100 liters and is continuously supplied for 12 hours. After that, the material is agitated at b 2 450 ° C. The liquid level is applied from the polycondensation and anti-condensation reaction tank with the decompression stage. The pre-polymer 4 0 50 0 shaft mixing device b 2 4 0 ° C, which applies the liquid level 21 200409787 to control the produced water and tetrahydrofuran and 1,4-butanediol from the pressure reducer ( (Not shown) At the same time that the connected vent port 4a is withdrawn, a polycondensation reaction is further performed, and The extracted reaction solution is continuously supplied to the third polycondensation reaction tank 5. At this time, a pre-polymer sample was taken from a sampling port (not shown) at the outlet of the gear pump G 4 to determine the number average molecular weight, and a result of the molecular weight of 9700 was obtained. The third polycondensation reaction tank 5 is a vertical reaction tank equipped with a stirring device M 5 with two self-cleaning horizontal rotating shafts. The internal temperature of the reaction tank 5 is set to 235 ° C and the pressure is 200 Pa. The amount can be controlled in 40 liters, and the generated water and tetrahydrofuran and 1,4-butanediol are withdrawn from the vent 5a connected to a pressure reducer (not shown), and a polycondensation reaction is performed. . After the polymer obtained was passed through the pipe system P 5 by the gear pump G 5, the polymer was continuously pulled out in a strip shape from the polymer extraction die 6 and cut by a rotary cutter 7. The number average molecular weight of the obtained polymer was 20,000, the terminal carboxyl group concentration was 12 peq / g, and the terminal vinyl group concentration was 4 peci / g. The analysis value of the polymer is shown in Table 1. That is, a polybutylene terephthalate resin having less terminal vinyl groups and excellent color tone was obtained. (Example 2) In addition to setting the internal temperature of the first polycondensation reaction tank 3 to 240 ° C, the internal temperature of the second polycondensation reaction tank 4 to 2 4 5 ° C, and the internal temperature of the third polycondensation reaction tank 5 to Except for 2 3 5 ° C, it was carried out in the same manner as in Example 1. The number average molecular weight of the exit prepolymer of the first polycondensation reaction tank 3 is 3 2 0, and the number average molecular weight of the exit prepolymer of the second polycondensation reaction tank 4 is 8500. The number average molecular weight is 1950, the terminal carboxyl group concentration is 22 312 / Instruction of the Invention (Supplement) / 92-09 / 92115520 200409787 14peq / g, and the terminal ethyl group concentration is 6peq / g. The polymer analysis values are shown in Table 1. That is, an excellent polybutylene terephthalate resin containing few terminal vinyl groups and excellent was obtained. (Example 3) In addition to setting the internal temperature of the first polycondensation reaction tank 3 to 2 3 5 ° C, the internal temperature of the first polycondensation reaction tank 4 to 2 4 5 ° C, and the third polycondensation reaction tank 5 temperature to 2 4 Except for 0 ° C, it was carried out in the same manner as in Example 1. The average molecular weight of the number of prepolymers exiting the first polycondensation tank 3 is 2 800, and the average molecular weight of the number of prepolymers exiting the second synthesis reaction tank 4 is 8 400, the average number of polymers reaching the The molecular weight is 197 0, the terminal carboxyl group is 17peq / g, and the terminal ethyl group concentration is 8peq / g. The polymer analysis values are shown in Table 1. That is, an excellent polybutylene terephthalate resin containing few terminal vinyl groups and excellent was obtained. (Example 4) Except that tetrabutyl phthalate was set in such a way that the theoretical yield basis of the polymer could be 75 ppm, the exit of the first polycondensation reaction tank 3 was performed in the same manner as in Example 1. The average number of polymers is 4 0 50, the average number of pre-polymers at the outlet of the second polycondensation reaction tank 4 is 9 0 0 0, and the average molecular weight of the obtained polymer is 19 50 0 terminal carboxyl groups The concentration was 9 peq / g, and the terminal vinyl group concentration was 4 με (ΐ The analysis value of the polymer is shown in Table 1. A polybutylene terephthalate resin having less vinyl group and particularly excellent color tone was obtained. (Example 5) A polybutylene terephthalate oligomer with an esterification rate of 93% was pre-filled with 312 / Invention Specification (Supplement) / 92-09 / 92115520, which is a dichromatic inner dimerization and polycondensation. The obtained degree is divided by the amount of color of titanium. The amount is a molecule, and the end / g 0 is the end 23 200409787 After the reaction tank 2 of Example 1, the dimethyl terephthalate and 1,4-butanediol are selected as terephthalic acid. The ratio of 1.0 mol diacid to 1.5 mol of 1,4-butanediol was supplied to the transesterification reaction tank 2, and the internal temperature of the reaction tank 2 was set. It is 200 ° C, and its pressure is 101 kPa, and it is carried out in the same manner as in Example 1. The ester of the low polymer taken at the sampling port 2c after 12 hours from the stabilization of the reaction system. The chemical conversion rate is 96%. The number average molecular weight of the exit prepolymer of the first polycondensation reaction tank 3 is 3900, and the number average molecular weight of the exit prepolymer of the second polycondensation reaction tank 4 is 9500. The number-average molecular weight of the polymer was 20000 0, the terminal weikyl concentration was 18 peq / g, and the terminal ethyl fluorenyl group concentration was 4 peq / g. The analysis value of the polymer is shown in Table 1. A polybutylene terephthalate resin with few terminal vinyl groups and excellent color tone. (Comparative Example 1) Except for setting the internal temperature of the first polycondensation reaction tank 3 to 235 ° C and the second polycondensation reaction tank 4 The temperature is 2 40 ° C, and the inner temperature of the third polycondensation reaction tank 5 is other than 2 4 5 ° C, which is implemented in the same manner as in Example 1. The average number of prepolymers at the outlet of the first polycondensation reaction tank 3 The molecular weight is 2 800, and the number of the prepolymers at the outlet of the second polycondensation reaction tank 4 is an average molecular weight of 8 3 0. The obtained polymerization The number average molecular weight is 20000 0, the terminal carboxyl group concentration is 2 3 μ eq / gj and the terminal ethyl fluorenyl group concentration is 14 peq / g. The analysis value of the polymer is shown in Table 1. That is, the terminal vinyl group (Comparative Example 2) In addition to setting the internal temperature of the first polycondensation reaction tank 3 to 240 ° C, the internal temperature of the second polycondensation reaction tank 4 to 2 3 5 ° C, and the third polycondensation reaction tank 3 The internal temperature of 5 was 2 4 5 ° C, and the same procedure was performed as in Example 1. The first polycondensation reaction 24 312 / Invention Specification (Supplement) / 92-09 / 92115520 200409787 The number of prepolymers at the outlet of tank 3 has an average molecular weight of 3 2 0 0. The number average molecular weight of the polymer is 8200 '. The number average molecular weight of the known polymer is 1960, the terminal carboxyl group concentration is 22 peq / g, and the terminal vinyl group concentration is i3peq / g. The analysis value of the polymer is shown in Table 1. That is, the terminal vinyl group increases and the color tone deteriorates. (Comparative Example 3) Except that the internal temperature of the first polycondensation reaction tank 3 was set to 235. C. The internal temperature of the second polycondensation reaction tank 4 is 2 40 ° C, and the internal temperature of the third polycondensation reaction tank 5 is 2 4 5 ° c, all of which are performed in the same manner as in Example 5. The number average molecular weight of the outlet prepolymer in the first polycondensation reaction tank 3 is 2700, and the number average molecular weight of the outlet prepolymer in the second polycondensation reaction tank 4 is 8200. The molecular weight is 20,000, the terminal carboxyl group concentration is 28 peq / g, and the terminal vinyl group concentration is 14 peq / g. The analysis value of the polymer is shown in Table 1. That is, the terminal vinyl group increases and the color tone deteriorates. Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Dicarboxylic acid raw material TPA TPA TPA TPA DMT TPA TPA DMT Catalyst concentration pidm / polymer 100 100 100 75 100 100 100 100 First polycondensation tank __internal temperature ° C 245 240 235 245 245 235 240 240 235 Number average molecular weight 4050 3200 2800 4050 3900 2800 3200 2700 Inner temperature of second polycondensation tank ° c 240 245 245 240 240 240 240 235 240 Number average molecular weight 9700 8500 8400 9000 9500 8300 8200 8200 Third polycondensation tank reaction tank outlet temperature ° c 235 235 240 235 235 245 245 245 Number average molecular weight 20000 19500 19700 19500 20000 20000 19600 20000 [COOH] geq / g 12 14 17 9 18 23 22 28 [CH2 = CH] Meq / g 4 6 8 4 4 14 13 14 Tint of polymer 0.6 0.7 0.8 0.4 0.9 2.9 2.6 3.1 TPA: terephthalic acid DMT: dimethyl terephthalate (Example 6) 25 312 / Invention Specification (Supplement) / 92-09 / 92115520 200409787 The SBT process shown in FIG. 4 and the polycondensation process shown in FIG. 5 are used to perform PBT manufacturing according to the following procedure. First, a 60 ° C slurry mixed at a ratio of 1.0 mol of terephthalic acid and 1.8 mol of 1,4-butanediol was passed from a slurry preparation tank through a raw material supply line (L 1) to It is a 28. 5 kg / h continuous supply to the esterification reaction tank (D), which has a spiral mixer and is pre-filled with a PBT oligomer having an esterification rate of 99%. At the same time, the bottom component of the distillation column (E) at 18.5 ° C was supplied to the reaction tank (D) from the recirculation line (L2) at 12.0 kg / h, and 65 as a catalyst was also used. Tetrabutylphthalate 6.0 \ ^% 1,4-butanediol solution at ° C is supplied from the catalyst supply line (L 3) at 69 boil / 11 (the titanium metal concentration of 30 ppm based on the theoretical theoretical polymer yield). In this reaction tank (D). The water content in this solution was 0.20 wt%. The internal temperature of the reaction tank (D) was set to 230 ° C and its pressure was 78 kPa, so that the produced water and tetrahydrofuran and the remaining 1,4-butanediol were distilled from the distillation line (L 5), and rectified by The column (E) is separated into a high boiling point component and a low boiling point component. Among the high-boiling components at the bottom of the column after the stabilization of the reaction system, the proportion of 1,4-butanediol is 98% by weight or more, and a part of the rectification column (E) can be extracted by drawing out a part of it The pipeline (L 8) is drawn out. On the other hand, the low-boiling point component is extracted from the top of the tower in the form of gas, and it is condensed by a condenser (Η), and the extraction line (L 1 3) is obtained in such a way that the liquid level of the storage tank (J) can reach a certain level. Take it out. One of the low polymers produced in the reaction tank (D) is quantitatively extracted from the extraction line (L4) under the use of a gear pump (G6), and the average retention time of the liquid in the reaction tank (D) can reach 3 The level is controlled in 3 hours. The low polymer extracted from the extraction line (L 4) is continuously supplied to the first polycondensation reaction tank 26 312 / Invention Specification (Supplement) / 92-09 / 92115520 200409787 (Q). After the reaction system was stabilized, a sample was taken at the outlet of the reaction tank (A), and the esterification rate of the low polymer was determined to be 97.3 ° / 〇. The inner temperature of the first polycondensation reaction tank (Q) was set to 2 4 1.0 ° C, and its 2 · 1 k Pa was controlled so that the retention time could be 150 minutes. While the water, tetrahydrofuran, and 1,4-butanediol were drawn out from the ventilation line (L 1 6) connected to the reduced pressure (d), initial polymerization was performed. The extracted reaction solution was continuously supplied to the second polycondensation reaction. The internal temperature of the second polycondensation reaction tank (R) was set to 244.3 ° C, and its 16 0 Pa, so that the retention time could be 120 minutes. Liquid δ is used to extract water, tetrahydrofuran, and 1,4-butanediol from the venting line (L 1 8) connected to the pressure reducer, and further polymerization is performed. The obtained polymer is subjected to liquid extraction The gear pump (G 8) is continuously supplied to the third polycondensation reaction tank (S) by pumping (L 1 7). The reactor outlet temperature of the third polycondensation reaction tank (S) is set to ° C, and its pressure is 1 At 80 Pa, the liquid level control can be performed with a retention time of 150 minutes, and the ventilation line (L 2) that connects water, tetrahydrogen, and a 1,4-butane pressure reducer (not shown) 0) At the same time of extraction, a polycondensation reaction is performed. The obtained polymer is continuously pulled out from the die (6) by a drawing line (L 1 9) from the die (6) using a pumping gear pump, and the cutting machine (7) The average number of the obtained polymers was 28,900, the terminal group concentration was 24 peq / g, and the terminal ethyl group was 1 1 μ eq / g, and the b value is -0.6. That is, a polybutylene terephthalate tree with less terminal carboxyl groups and less terminal vinyl groups, and excellent hue is obtained. The analysis value of the polymer is shown in Table 2. 312 / Instruction of the Invention (Supplement) / 92-09 / 92115520 and the measured pressure is the liquid level control I (not shown in the condensation reverse tank (R) 〇 pressure is 1 control, k is shown) Condensation back out line 2 3 8.6 of Mode alcohol borrowed from further (G 9) the amount of rotator based on the concentration, also lipid 0 27 200409787 (Comparative Example 4) In addition to setting the temperature of the reactor outlet of the third polycondensation reaction tank (S) to 2 4 6 5 ° C and its pressure except for 260 P a were implemented in the same manner as in Example 6. Both the terminal carboxyl group and the terminal vinyl group were increased, and the color tone was also deteriorated. The analysis value of the polymer is also shown together. Table 2. Table 2 Example 6 Comparative Example 4 Dicarboxylic acid component raw material TPA TPA Catalyst concentration ppm / polymer 30 30 Inner temperature of the first polycondensation tank ° c 241.0 241.0 Inner temperature of the second polycondensation tank ° c 244.3 244.3 Third polycondensation tank reaction tank outlet temperature ° c 238.6 246.5 number average molecular weight 28900 28800 [C00H] peq / g 24 43 [ch2 = ch] μeq / g 11 16 Tint of polymer -0.6 3.5 TPA: terephthalic acid <Industrial availability> According to the method for producing a polyester according to the present invention, a side reaction during the polycondensation reaction can be suppressed The polyester with improved hue or polymerizability has high industrial use value. [Brief description of the drawings] Fig. 1 is a schematic diagram of a polyester manufacturing apparatus according to a preferred embodiment of the present invention. Fig. 2 is a schematic diagram of a polyester manufacturing apparatus according to a preferred embodiment of the present invention. FIG. 3 is a schematic diagram of a polyester manufacturing apparatus used in Example 1. FIG. FIG. 4 is a schematic diagram of an esterification step used in Example 6. FIG. 28 312 / Invention Specification (Supplement) / 92-09 / 92115 520 200409787 Figure 5 is a schematic diagram of the polycondensation step used in Example 6. Component symbol description) 1 slurry preparation tank 1 a, 1 b raw material supply port 2 esterification reaction tank 2a vent 2b catalyst supply port 2 c sampling port 3 first polycondensation reaction tank 3 8. vent 3c sampling α 4 Dimerization condensation reaction tank 4 a Vent 4 c Sampling α 5 Third polymerization condensation reaction tank 5 a Ventilation π 6 Polymer extraction die 7 Rotary cutting machine M1, M2, M3, M4, M5 Stirring device Gl, G2, G3 , G4, G5, G6, G7, G8, P1 Raw material supply pipe system P 2, P 3, P 4 Reaction tank connection P5 Polymer extraction pipe system D Esterification reaction tank G 9 Gear fruit pipe system 312 / Invention specification ( (Supplement) / 92-09 / 92115520 29 200409787 E Distillation column F Pump Η Condenser J Storage tank K Pump LI Raw material supply line L2 Recirculation line L3 Catalyst supply line L4 Extraction line L5 Distillation line L6 Extraction line L7 Circulation Pipeline L8 Extraction Pipeline L9 Gas extraction line LI 0 Condensation line LI 1 Extraction line L 1 2 Circulation line LI 3 Extraction line LI 4 Vent line LI 5 Extraction line LI 6 Vent line LI 7 Extraction line LI 8 Vent line L 1 9 Extraction line 31V (Supplement) / 92-09 / 92115520 200409787 L20 Ventilation line Q First polycondensation reaction tank R Second polycondensation reaction tank S Third polycondensation reaction tank.
312/發明說明書(補件)/92-09/92115520 31312 / Invention Specification (Supplement) / 92-09 / 92115520 31