TW585881B - Catalyst for polyester production, process for producing polyester using the catalyst, polyester obtained by the process, and uses of the polyester - Google Patents

Abstract

The present invention provides a catalyst for polyester production capable of producing a polyester with high catalytic activity and a process for producing a polyester using the catalyst. The catalyst for polyester production comprises a solid titanium compound which is obtained by dehydro-drying a hydrolyzate obtained by hydrolysis of a titanium halide and which has a molar ratio (OH/Ti) of a hydroxyl group (OH) to titanium (Ti) exceeding 0.09 and less than 4. The present invention also provides a method to obtain a polyester having a small increase of the acetaldehyde content during the molding. This method comprises bringing a polyester, which is obtained by the use of a titanium compound catalyst and in which the reaction has been completed, into contact with a phosphoric ester aqueous solution or the like having a concentration of not less than 10 ppm in terms of phosphorus atom. The present invention further provides a polyester having excellent transparency and tint and molded products of the polyester such as a blow molded article, a film, a sheet and a fiber. The polyester is obtained by polycondensing an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof in the presence of a catalyst for polyester production which comprises a polycondensation catalyst component comprising a solid titanium compound and a co-catalyst component comprising a magnesium compound. This polyester has a titanium content of 1 to 100 ppm, a magnesium content of 1 to 200 ppm and a weight ratio (Mg/Ti) of magnesium to titanium of not less than 0.01.

Description

585881 A7 B7 五、發明説明（1 ) 本發明乃聚酯製造用觸媒，使用該觸媒製造聚酯之方 法’以及由該製法所得聚酯和其用途有關者。 (請先閲讀背面之注意事項再填寫本頁) 聚醋’例如聚乙烯對苯二甲酸酯，由於具備優異之機 械強度、耐熱性、透明性和不透氣性，做爲果汁、淸涼飮 料' 酸飮料等飮料塡充容器用材料，以及其他薄膜、片 狀物、纖維等用材料而廣泛使用。 一般而言，聚酯以芳香族二羧類等二羧酸類和脂肪族 二元醇等爲原料而製造之。具體言之，首先，由二羧酸類 和二元醇類間之酯化反應而形成低級縮合物（低分子量之 聚酯）’然後在縮聚反應觸媒之存在下，將上述低級縮合 物施以去乙二醇反應（液相縮聚反應）而使之成爲高分子 量化合物。另外，有時也藉固相縮聚反應而提高其分子量 〇 上述聚酯之製造方法中，縮聚用觸媒已往均採用銻化 合物，鍺化合物等。 經濟部智慧財產局員工消費合作社印製 然而，使用銻化合物爲縮聚用觸媒製成之聚酯，在透 明性、耐熱性方面，較之使用鍺化合物爲縮聚用觸媒製造 之聚酯爲劣質。另外，使用銻化合物爲縮聚用觸媒時，也 希望能降低所謂聚酯中之乙醛含量。 另一方面，鍺化合物相當昂貴，有造成聚酯之製造成 本提升之經濟問題。因此，爲降低製造成本。在硏究縮聚 時會揮散之鍺化合物之回收再利用之步驟。 另外，鈦已知乃係促進低級聚合物之縮聚反應之作用 的元素，周知的縮聚用觸媒之鈦化合物有烷氧化鈦，四氯 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -4- 585881 A7 B7 五、發明説明（2 ) 化鈦，草酸氧鈦，原鈦酸等，爲了上述鈦化合物做爲縮聚 用觸媒利用曾經有不少硏究進行。 (請先閱讀背面之注意事項再填寫本頁) 然而，使用上述周知之鈦化合物爲縮聚用觸媒時，其 觸媒活性較之銻化合物，鍺化合物爲低劣，所得聚酯顯著 呈現黃色等問題存在，因此，迄今無法實際利用。又，利 用上述鈦化合物爲縮聚用觸媒而在工業上製造聚酯時，像 四氯化鈦或其局部水解產物等含多量之氯的觸媒，尙有隨 氯成分之溶出而產生腐蝕性問題存在，因此，更期待含氯 量少之觸媒出現。 因此，在上述情況下，現在期望具有高縮聚觸媒活性 而能製造聚酯用之聚酯製造用觸媒，或是在高觸媒活性下 ，能製成乙醛含量少，透明性高，色相優異等任意條件之 聚酯用之聚酯製造用觸媒急待開發硏究。 另外，在短時間內能具有所欲固有粘度（IV )之聚酯 之製造方法，具備高聚合活性而乙醛含量少之聚酯有關製 造方法，具備高聚合活性而能得色相優異之聚酯的聚醋製 造方法也急待硏發。 經濟部智慧財產局員工消費合作社印製 如以上所述’聚醋’特別是聚乙稀對苯二甲酸酯很適 用於果汁、淸涼飮料、碳酸飮料等飮料塡充容器之材料用 途。由聚酯製造中空成型物時，例如利用壓注模成型機械 等成型機中’供應聚醋原料而首先成型爲中空成型物用預 塑物，再將該預塑物***所定形狀之模體中進行拉伸吹塑 成型，再經熱處理而製成中空成型容器。 然而’已往之聚酯，例如由聚乙烯對苯二甲酸酯成型 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 585881 A7 B7 五、發明説明（3 ) 而得成型物，在成型時乙醛含量增加，而由於該乙醛殘留 在成型物中，會影響及塡充在該成型物中之內容物的風味 、香味等使其顯著劣變。 (請先閱讀背面之注意事項再填寫本頁} 製造成型時乙醛含量增加較少之聚乙烯對苯二甲酸酷 之方法，例如日本專利之特開昭5 9 — 2 5 8 1 5號公報 中報告在聚乙烯對苯二甲酸酯之固相縮聚反應之前’先將 該聚乙烯對苯二甲酸酯之粉粒狀物以1 1 〇 °C以上之加熱 水蒸汽處理之方法；另外，特開昭5 9 - 2 1 9 3 2 8號 公報中，也報告將固有粘度爲〇 · 4d Ι/g以上’密度 爲1 · 3 5 g / c m 3以下之聚乙烯對苯二甲酸酯，調濕到 水分含率在〇 · 2重量％以上之調濕過程，使用1 4 0 °C 以上溫度加以預結晶化步驟，以及在1 8 0 °C以上而 2 4 0 °C以下溫度在不活性氣體環境下或減壓下進行固相 縮聚反應步驟等包括在內的高聚合度聚乙烯對苯二甲酸酯 之製造方法。然而，上述方法所得聚乙烯對苯二甲酸酯在 成型之際，還是無法將其乙醛增加量減少到一定量以下。 經濟部智慈財產局員工消費合作社印製 特開平5 - 9 7 9 9 0號公報中，公開有固相聚合之 聚乙烯對苯二甲酸酯之顆粒和濃度1 p p m以上之磷酸水 溶液接觸而成聚乙烯對苯二甲酸酯之處理方法。然而，上 述方法中，磷酸成爲酸性觸媒而表現水解作用，所以溶融 成型時有促進固有粘度降低之缺點。 又，已往之聚酯中，例如聚乙烯對苯二甲酸酯中還含 有環狀三聚物等低聚物類，這些環狀三聚物等低聚物類在 吹塑成型模內面或模之排氣口、排氣管等處附著而造成模 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 585881 A7 B7 五、發明説明（4 ) (請先閱讀背面之注意事項再填寫本頁) 之污染、或低聚物類附著在壓注模成型機之通風孔部分等 問題存在。上述模之污染會成爲所得中空成型物表面粗糙 或白化之原因。倘若中空成型物白化時，該中空成型物就 得廢棄而損失。因此，使用已往周知之聚酯製造中空成型 物時，必須經常淸除模上之污染物，顯著降低中空成型物 之生產率成爲很嚴重問題。 另外，使用銻化合物或鍺化合物做爲縮聚用觸媒時， 所得聚酯之溶融流動性低，成型性不足之情形存在。 在上述情況下，期待有乙醛含量少，且成型時乙醛含 量不容易增加之聚酯，不容易導致模之污染的聚酯，或溶 融流動性高而成型性優異的聚酯出現。 另外也期待具有優異之透明性，色相等特性之聚酯成 型物，或中空成型物用預塑物以及中空成型物等成型物， 例如環狀三聚物含量較少之聚酯製中空成型物之出現。 經濟部智慧財產局員工消費合作社印製 又，本發明申請人發現成型時發生模污染之主要原因 ，乃係聚酯成型時產生大量之環狀三聚物等低聚物，以致 聚酯中所含環狀三聚物等低聚物類之總量增加所引起，更 發現經過固相縮聚反應步驟所得聚酯和水等接觸，可顯著 抑制成型時之環狀三聚物等低聚物量之增加，曾經公開在 特開平5 — 97990號公報，特開平8 - 283393 號公報等專利中。 本發明乃有鑑於上述已往技術上之問題，以提供具有 高觸媒活性而能製造聚酯用之聚酯製造用觸媒，或將具有 滿足乙醛含量少，透明性高，色相優異等任意特性之品質 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 585881 A7 B7 五、發明説明（5 ) 的聚酯加以在高觸媒活性下製造使用之聚酯製造用觸媒的 目的。 又，本發明也以提供短時間內就能具有所期待固有粘 度之聚酯的製造方法，以高聚合活性而能製造乙醛含量少 的聚酯之製造方法，以高聚合活性而能製造色相優異的聚 酯之製造方法爲其目的。 本發明更進而提供成型時乙醛含量增加較少之聚酯， 特別是乙醛含量少，且成型時乙醛之增加量少的聚酯，不 容易發生模污染之聚酯，具有優異之透明性、色相等特性 之聚酯，或溶融時流動性高而成型性優異之聚酯爲其目的 〇 又，本發明也提供具有優異之透明性、色相等特性之 聚酯成型體，或中空成型物用預塑物以及中空成型物等成 型物，例如環狀三聚物含量少之聚酯製中空成型物爲其另 一種目的。 本發明之形態之一有關聚酯製造用觸媒，乃由鹵化鈦 化合物水解而成水解產物再加以脫水乾燥而得，其中所含 羥基（〇H)或鈦（Ti)之莫耳比率（〇H/Ti)在 〇 · 0 9以上而4以下範圍之固態狀鈦化合物（；[一 a ) 所構成爲特徵， 或由鹵化鈦化合物和鈦以外之其他元素中所選擇至少 一種元素之化合物或該化合物之前驅物間之混合物，經水 解而成水解產物脫水乾燥而得，其中所含羥基（〇 Η )和 鈦（Τ!)之莫耳比率（ΟΗ/Τι)在〇 · 〇9以上而 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------0_丨 (請先閱讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局g(工消費合作社印製 -8 - 585881 A7 B7 五、發明説明（6 ) 4以下之固態狀含鈦化合物（I 一 b )所構成爲特徵， (請先閱讀背面之注意事項再填寫本頁) 或由（I )，上述固態狀鈦化合物（1 一 a )和/或 上述固態狀含鈦化合物（I - b )所構成縮聚反應用觸媒 成分， 和（Π )，鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、 銘、鋅、鍺、銻和磷所構成群中至少選擇一種元素的化合 物所構成輔觸媒成分而成爲其特徵。 本發明之另一種形態有關之聚酯製造用觸媒有： (I )由鹵化鈦化合物水解而成水解產物再經脫水乾 燥而得固態狀鈦化合物（I - c )所構成縮聚反應用觸媒 成分，和 (Π )由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷 、鋅、鍺、銻和磷所構成群中至少選擇一種元素的化合物 所構成輔觸媒成分而成爲其特徵。 由鹵化鈦化合物和鈦以外之其他元素中選擇至少一種 元素之化合物或該化合物之前驅物之混合物，經水解而成 水解產物再脫水乾燥而得之固態狀含鈦化合物（I - b ) 所構成爲其特徵者。 經濟部智慧財產局員工消費合作社印製 又有（I )，固態狀含鈦化合物（I 一 d )所構成縮 聚反應觸媒成分，和 (Π )由皴、錶、弼、總、鎖、棚、銘、嫁、鐘、銘 、鋅、鍺、銻和鱗所構成群中至少選擇一種元素之化合物 而成輔觸媒成分所構成爲其特徵。 上述聚酯製造用觸媒中，上述輔觸媒成分（π )以鎂 -9 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 585881 A7 經濟部智慧財產局g(工消費合作社印製 B7五、發明説明（7 ) 化合物爲較宜。 又，本發明之另一種形態有關之聚酯製造用觸媒’乃 有使鹵化鈦化合物和水接觸下，將鹵化鈦化合物水解所得 含有鹵化鈦化合物之水解產物之酸性溶液，再用鹼改變成 鹼性，然後用酸調整爲P Η 2〜6 ，所產生沈澱物加以脫 水乾燥所得固態狀鈦化合物（I - e )而構成爲其特徵者 另有使鹵化鈦化合物和水接觸下，將鹵化鈦化合物水 解所得含有鹵化鈦化合物之水解產物的酸性溶液，用鹼調 整爲p Η 2〜6 ，所產生沈澱物經脫水乾燥所得固態狀鈦 化合物（I 一 f )而構成爲其特徵者， 尙有（I )，由上使固態狀鈦化合物（I 一 e )或固 態狀鈦化合物（I - f )而構成縮聚反應觸媒成分，和 (Π )，由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、 鈷、鋅、鍺、銻和磷所構成群中至少選擇一種元素之化合 物所構成輔觸媒成分而構成爲其特徵者， 還有由鹵化鈦化合物和鈦以外之其他元素中至少選擇 一種元素之化合物或該化合物之前驅物間之混合物，和水 接觸下，將鹵化鈦化合物水解所得含有鹵化鈦化合物之水 解產物的酸性溶液，用鹼變成鹼性，然後用酸調製爲p Η 2〜6，將所產生之沈澱物脫水乾燥而得固態狀含鈦化合 物（I 一 g )所構成爲其特徵者， 還有由鹵化鈦化合物，和鈦以外之其他元素中至少選 擇一種元素之化合物或該化合物之前驅體間之混合物，和 ---------Φ|丨 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -10- 585881 A7 B7 五、發明説明（8 ) (請先閱讀背面之注意事項再填寫本頁) 水接觸下，將鹵化鈦化合物水解所得含有鹵化鈦化合物之 水解產物的酸性溶液，用鹼調整爲p Η 2〜6 ，將所產生 之沈澱物加以脫水乾燥所得固態狀含鈦化合物（I 一 h ) 而構成爲其特徵者， 又有由（I )，上述固態狀含鈦化合物（I — g )， 或（I 一 h )所構成縮聚反應觸媒成分，和 (Π )，由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、 鈷、鋅、鍺、銻和磷所構成群中至少選擇一種元素之化合 物所構成輔觸媒成分而構成爲其特徵者。 上述聚酯製造用觸媒中，上述輔觸媒成分（Π )以鎂 化合物爲較宜。 又’本發明之另一種形態有關之聚酯製造用觸媒，有 使鈦之氫氧化物脫水乾燥而得，其2 β (衍射角度）係在 1 8〜3 5之軺圍的X光衍射象所g十算結晶化度在5 0 % 以下之固態狀鈦化合物（I - i )所構成爲其特徵者， 另有由（I )，上述固態狀鈦化合物（I — 1 )所構 成之縮聚反應觸媒成分，和 經濟部智慧財產局g(工消費合作社印製 (Π )，由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、 鈷、鋅、鍺、銻和磷所構成群中至少選擇一種元素之化合 物所構成之輔觸媒成分而構成者爲其特徵。 又，本發明之另一種形態有關之聚酯製造用觸媒有如 將（A - 1 )，鈦化合物水解而成水解產物（I 一 j )或 鈦化合物和鈦以外之其他元素中選擇至少一種元素之化合 物或該化合物之前驅物間之混合物加以水解而成水解產物 -11 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 585881 Α7 Β7 五、發明説明（9 ) (I — k )，和 (B )，鹼性化合物，以及 (請先閱讀背面之注意事項再填寫本頁) (C )，脂肪族二元醇之混合物加熱而得淤漿所構成爲 其特徵者。 上述聚酯製造用觸媒中，上述鹼性化合物（B )以四 乙基銨羥基化合物，四甲基銨羥基化合物，氨水，氫氧化 鈉’氫氧化鉀，N -乙基嗎啉，N -甲基嗎啉中至少選擇 一種化合物爲較宜。 上述脂肪族二元醇（C )以乙二醇爲較宜。 又，本發明之其他形態有關之聚酯製造用觸媒尙有如 將（A — 2 )，鹵化鈦化合物水解而成水解產物（I 一 m )或鹵化鈦化合物和鈦以外之其他元素中選擇至少一種元 素之化合物或該化合物之前驅物間之混合物加以水解而成 水解產物（I 一 η )，和 (D ) ’含有由由敍、錶、錦、緦、硼、銘、鎵、猛、鈷 和鋅中所選擇至少一種元素之磷酸金屬鹽所構成爲特徵者 ， 經濟部智慧財產局S工消費合作社印製 另有如將（Α - 2 )，鹵化鈦化合物水解而成水解產 物（I - m )或鹵化鈦化合物和鈦以外之其他元素中至少 選擇一種元素之化合物或該化合物之前驅物間之混合物加 以水解而成水解產物（I 一 η )，和 (Ε )，含有由鈹、鎂、鈣、緦、硼、鋁、鎵、錳、鈷、 和鋅中至少選擇一種元素之金屬化合物，和 (F )由磷酸和磷酸酯中至少選擇一種磷化物，以及 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 585881 ΑΊ Β7 五、發明説明（1〇 ) (G )脂肪族二元醇間之混合物加熱而得淤漿所構成爲其 特徵者。 (請先閱讀背面之注意事項再填寫本頁) 上述聚酯製造用觸媒中，上述磷酸金屬鹽（D )以碟 酸氫鎂或二磷酸三鎂爲較宜。又，上述金屬化合物（E ) 爲鎂化合物，上述磷化合物（F )爲磷酸或三甲基磷酸鹽 ，上述脂肪族二元醇（G )爲乙二醇爲較佳。 上述（A — 2) ， （E) ’ （F)和（G)之混合物 之加熱溫度以1 0 0〜2 0 〇 °C，加熱時間以3分鐘至5 小時爲較佳。 上述本發明有關之聚酯製造用觸媒中，上述鈦以外之 其他元素中至少選擇一種元素之化合物或該化合物之前驅 物，可舉由鈹、鎂、鈣、鋸、鋇、銃、釔、鑭、鉻、飴、 釩、鈮、鉬、鉻、鉬、鎢、錳、鐵、釕、鈷、铑、鎳、鈀 、銅、鋅、硼、鋁、鎵、矽、鍺、錫、銻和磷所構成群中 至少選擇一種元素之化合物或該化合物之前驅物。 經濟部智慧財產局員工消費合作社印製 本發明有關一種形態有關聚酯之製造方法，有如在上 述聚酯製造用觸媒之存在下，將芳香族二羧酸或其酯形成 性衍生物和脂肪族二元醇或其酯形成性衍生物縮聚反應而 製成聚酯爲其特徵者。 本發明有關另一種形態之聚酯之製造方法，包括將芳 香族二羧酸或其酯形成性衍生物和脂肪族二元醇或其酯形 成性衍生物加以酯化而形成低級縮合物之酯化步驟，以及 在縮聚反應觸媒之存在下，將該低級縮合物縮聚反應而成 爲高分子化合物之縮聚反應步驟，上述聚酯之製造方法中 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公H " -13- 585881 Α7 Β7 五、發明説明（11) ’縮聚反應觸媒使用。 (請先閱讀背面之注意事項再填寫本頁) (I )將鈦化合物水解而成水解產物（I - j )或鈦 化合物和鈦以外之其他元素中至少選擇一種元素之化合物 或該化合物之前驅物之混合物加以水解而成水解產物（I - k )所構成之縮聚反應觸媒成分，和 (Π )由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、銘 、鋅、鍺、銻和磷所構成群中至少選擇一種元素之化合物 而構成之輔觸媒成分所構成之觸媒’且， 將上述縮聚反應觸媒成分（I )在酯化反應開始前或 酯化反應開始後立即添加在酯反應容器中爲其特徵者。 上述聚酯製造用觸媒中，上述輔觸媒成分（Π )以採 用鎂化合物爲較佳。 又，本發明之其他形態有關之聚酯之製造方法，尙有 將芳香族二羧酸或其酯形成性衍生物和脂肪族二元醇或其 酯形成性衍生物，在下列（1 )至（3 )中所選擇縮聚合 反應觸媒，以及磷酸酯之共存下進行縮聚反應而製造爲其 特徵者； 經濟部智慧財產局員工消費合作社印製 (1 )由鹵化鈦化合物水解而得水解產物（I 一 m ) 所構成縮聚反應觸媒， (2 )由鹵化鈦化合物和鈦以外之其他元素中至少選 擇一種元素之化合物或該化合物之前驅物間之混合物加以 水解而成水解產物（I - η )所構成之縮聚反應觸媒， (3)由上述（I— m)或（I— η)和皴、錶、錦 、緦、鋇、硼、絕、鎵、猛、銘、鋅、鍺、鍊所構成群中 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -14 - 585881 Α7 Β7 五、發明説明（12) 至少選擇一種元素之化合物或磷酸鹽，或亞磷酸鹽而構成 之縮聚反應觸媒， 上述聚酯製造用觸媒中，上述磷酸鹽以三丁基磷酸鹽 ，三辛基磷酸鹽或三苯基憐酸鹽爲較宜。 又’本發明之另一形態有關聚酯之製造方法，尙有將 芳香族二殘酸或其酯形成性衍生物和脂肪族二元醇或其醋 形成性衍生物，在下列（1 )至（3 )中所選擇縮聚反應 觸媒’以及由環狀內酯系化合物和受阻酚系化合物中至少 選擇一種化合物之共存下進行縮聚反應而製造聚酯爲其特 徵者； (1 )由鹵化鈦化合物水解而成水解產物（I 一 m ) 所構成縮聚反應觸媒， (2 )由鹵化鈦化合物和鈦以外之其他元素中至少選 擇一種元素之化合物或該化合物之前驅物之混合物加以水 解而成水解產物（I - η )所構成縮聚反應觸媒， (3)上述（I— m)或（I 一 η)和由鈹、鎂、鈣 、緦、鋇、硼、鋁、鎵、錳 '鈷、鋅、鍺、銻構成群中至 少選擇一種元素之化合物或磷酸鹽，或亞磷酸鹽所構成縮 聚反應觸媒。 上述聚酯製造用觸媒，尙可倂用由磷酸和磷酸酯中至 少選擇一種之磷化合物。 上述環狀內酯系化合物和受阻酚系化合物中至少選擇 一種之化合物，其中尤以5，7 —二第三丁基一 3 -（3 ，4 一二甲基苯基）一 3Η —苯駢呋喃一 2 —酮，四個（ ϋ張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -- (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -15- 585881 經濟部智慧財產局S工消費合作社印製 A7 五、發明説明（13 ) 亞甲基一 3 — (3 ，5 —二—第三丁基一 4 —羥基苯基） 丙酸酯）甲烷和三（2 ，4 一二第三丁基苯基）磷酸酯之 混合物爲較宜。 又，本發明之其他形態有關之聚酯之製造方法’其中 含有由芳香族二羧酸或其酯形成性衍生物和脂肪族二元醇 或其酯形成性衍生物加以酯化而成爲低聚物之酯化步驟’ 以及在縮聚反應觸媒之存在下，將該低聚物再行縮聚反應 而高分子量化之縮聚反應步驟之聚酯之製造方法中’尙有· 使用下述縮聚反應觸媒， (I )由鹵化鈦化合物水解而成水解產物（I 一 m ) 或鹵化鈦化合物和鈦以外之其他元素中至少選擇一種元素 之化合物或該化合物之前驅物之混合物加以水解而成水解 產物（I - η )所構成縮聚反應觸媒成分，和 (Π )由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、銘 、鋅、鍺、銻和磷所構成群中至少選擇一種元素之化合物 而成輔觸媒成分所構成觸媒，並且 在上述酯化步驟或縮聚反應步驟之任意步驟中’添加 色相調整劑爲其特徵者。 上述聚酯之製造方法中，上述色相調整劑以藍色溶劑 1 0 4 ( Solvent Blue 104)，紅色素 2 6 3 ( Pigment Red 263 )，紅色溶劑 1 3 5 ( Solvent Red 135 ) ’ 藍色 素 2 9 ( Pigment Blue 29)，藍色素 1 5 ·· 1 ( Pl2ment585881 A7 B7 V. Description of the invention (1) The present invention is a catalyst for polyester production, a method for producing polyester using the catalyst ', and a polyester obtained by the production method and its use. (Please read the precautions on the back before filling out this page) Polyvinyl acetate, such as polyethylene terephthalate, has excellent mechanical strength, heat resistance, transparency and air tightness. 'Widely used materials for filling containers, such as acid materials, and other materials for films, sheets, and fibers. Generally, polyesters are manufactured using dicarboxylic acids such as aromatic dicarboxylic acids and aliphatic diols as raw materials. Specifically, first, a lower condensate (low-molecular-weight polyester) is formed by an esterification reaction between a dicarboxylic acid and a diol, and then the above-mentioned lower condensate is applied to a polycondensation reaction catalyst. Deglycol reaction (liquid phase polycondensation reaction) to make it a high molecular weight compound. In addition, the molecular weight may be increased by a solid-phase polycondensation reaction. In the above-mentioned polyester production method, antimony compounds and germanium compounds have been used as polycondensation catalysts. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. However, polyesters made of antimony compounds for polycondensation catalysts are inferior to polyesters made of germanium compounds for polycondensation catalysts in terms of transparency and heat resistance. . When an antimony compound is used as a polycondensation catalyst, it is desirable to reduce the acetaldehyde content in the so-called polyester. On the other hand, germanium compounds are quite expensive, which has the economic problem of increasing the manufacturing cost of polyester. Therefore, in order to reduce manufacturing costs. The steps of recovery and reuse of germanium compounds that are volatile during polycondensation are studied. In addition, titanium is known to be an element that promotes the polycondensation reaction of lower polymers. The known titanium compounds for polycondensation catalysts are titanium alkoxides. The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X). 297 mm) -4- 585881 A7 B7 V. Description of the invention (2) Titanium oxide, titanyl oxalate, orthotitanic acid, etc., have been studied a lot for the use of the above-mentioned titanium compounds as catalysts for polycondensation. (Please read the precautions on the back before filling this page) However, when using the well-known titanium compound as a polycondensation catalyst, its catalyst activity is inferior to that of antimony compounds, germanium compounds, and the resulting polyester appears significantly yellow. Exist, so it has not been practically used so far. Moreover, when the above-mentioned titanium compound is used as a polycondensation catalyst for industrial production of polyester, a catalyst containing a large amount of chlorine, such as titanium tetrachloride or a local hydrolysate thereof, is corrosive due to the elution of the chlorine component. The problem exists. Therefore, it is more expected that a catalyst containing less chlorine will appear. Therefore, under the above circumstances, it is now desired to have a polyester production catalyst that has high polycondensation catalyst activity and can be used to manufacture polyester, or under high catalyst activity, it can be made with low acetaldehyde content and high transparency. Polyester manufacturing catalysts for polyesters with excellent hue and other conditions are in urgent need of development. In addition, a method for producing a polyester having a desired intrinsic viscosity (IV) in a short period of time, a method for producing a polyester having high polymerization activity and low acetaldehyde content, and a polyester having high polymerization activity and excellent hue The manufacturing method of polyacetic acid is also anxious. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs As mentioned above, 'Polyvinegar', especially polyethylene terephthalate, is very suitable for filling materials such as fruit juices, cold sauces, carbonated sauces, etc. for filling containers. When a hollow molded article is produced from polyester, for example, a polyacetate raw material is supplied from a molding machine such as an injection molding molding machine, and then the preform for the hollow molded article is first molded, and then the preplastic is inserted into a mold body of a predetermined shape. It is stretch-blow-molded and then heat-treated to form a hollow-molded container. However, 'the past polyester, for example, formed from polyethylene terephthalate, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 585881 A7 B7 V. Invention description (3) The acetaldehyde content of the molded article is increased during the molding, and because the acetaldehyde remains in the molded article, the flavor and aroma of the contents filled in the molded article are significantly deteriorated. (Please read the precautions on the back before filling in this page} A method for manufacturing polyethylene terephthalate with a small increase in acetaldehyde content during molding, such as Japanese Patent Laid-Open No. 5 9 — 2 5 8 1 5 In the report, prior to the solid-phase polycondensation reaction of polyethylene terephthalate, the method of first treating the powder and granules of polyethylene terephthalate with heating steam above 110 ° C; Japanese Unexamined Patent Publication No. 5 9-2 1 9 3 2 8 also reports polyethylene terephthalic acid having an intrinsic viscosity of 0.4 d / l or more and a density of 1.35 g / cm 3 or less. Ester, conditioning process to a moisture content of 0.2% by weight or more, using a temperature above 140 ° C for a pre-crystallization step, and a temperature above 180 ° C and below 240 ° C A method for producing a highly polymerized polyethylene terephthalate, including a solid-phase polycondensation reaction step under an inert gas environment or under reduced pressure. However, the polyethylene terephthalate obtained by the above method is At the time of molding, it was still impossible to reduce the amount of acetaldehyde increase below a certain amount. Printed in Japanese Unexamined Patent Publication No. 5-9 7 9 9 0 by the Consumer Affairs Cooperative of the Property Bureau, a polyethylene pair made of solid phase polymerized polyethylene terephthalate and a phosphoric acid aqueous solution having a concentration of 1 ppm or more is disclosed. Phthalate treatment method. However, in the above method, phosphoric acid acts as an acidic catalyst and exhibits hydrolysis. Therefore, it has the disadvantage of promoting the reduction of inherent viscosity during melt molding. In addition, conventional polyesters such as polyethylene terephthalate Diformate also contains oligomers such as cyclic trimers. These oligomers such as cyclic trimers are attached to the inner surface of the blow molding die, the exhaust port of the die, and the exhaust pipe. Contamination or oligomer that caused the size of the mold paper to comply with the Chinese National Standard (CNS) A4 (210X 297 mm) 585881 A7 B7 V. Description of the invention (4) (Please read the precautions on the back before filling this page) There are problems such as adhesion to the ventilation hole of the injection molding machine. The pollution of the above mold will cause the surface of the obtained hollow molding to be rough or white. If the hollow molding is whitened, the hollow molding must be discarded and discarded. Therefore, when manufacturing hollow molded articles using conventionally known polyesters, it is necessary to frequently remove the contaminants on the mold, which significantly reduces the productivity of the hollow molded articles. In addition, the use of antimony compounds or germanium compounds for polycondensation When the catalyst is used, the melted fluidity of the obtained polyester is low and the moldability is insufficient. In the above case, it is expected that a polyester with a low acetaldehyde content and which does not easily increase the acetaldehyde content during molding will not easily lead to molding. Contaminated polyesters or polyesters with high melt fluidity and excellent moldability appear. In addition, polyester moldings with excellent transparency and color equivalent properties, preforms for hollow moldings, and hollow moldings are also expected. The appearance of shaped articles, such as polyester hollow shaped articles with a small amount of cyclic trimer, has appeared. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the applicant found that the main reason for mold contamination during molding is that a large number of oligomers such as cyclic terpolymers are produced during the molding of the polyester. It is caused by the increase in the total amount of oligomers such as cyclic trimers. It has been found that the contact between polyester and water obtained through the solid-phase polycondensation reaction step can significantly reduce the amount of oligomers such as cyclic trimers during molding. The increase has been disclosed in patents such as Japanese Patent Application Laid-Open No. 5-97990 and Japanese Patent Application Laid-open No. 8-283393. The present invention has been made in view of the above-mentioned technical problems in order to provide a polyester manufacturing catalyst having high catalytic activity and capable of manufacturing polyesters, or to satisfy the requirements of less acetaldehyde content, high transparency, and excellent hue. The quality of the characteristics This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 585881 A7 B7 V. Description of the invention (5) The polyester used in the manufacture of catalysts with high catalyst activity is used as a catalyst for polyester manufacturing the goal of. In addition, the present invention also provides a method for producing a polyester having a desired intrinsic viscosity in a short time, a method for producing a polyester with a low acetaldehyde content with high polymerization activity, and a hue with a high polymerization activity. Excellent polyester manufacturing methods are used for this purpose. The present invention further provides a polyester with less increase in acetaldehyde content during molding, especially a polyester with less acetaldehyde content and less increase in acetaldehyde during molding, a polyester that is less prone to mold contamination, and has excellent transparency. For the purpose of polyesters with equal properties and color, or polyesters with high fluidity and excellent moldability at the time of melting, the present invention also provides polyester molded bodies with excellent transparency and color equivalent properties, or hollow molding. Pre-molded articles and molded articles such as hollow molded articles, such as polyester-made hollow molded articles with a small cyclic trimer content, serve another purpose. One aspect of the present invention relates to a catalyst for manufacturing polyester, which is obtained by hydrolyzing a hydrolyzed product of a titanium halide compound and then dehydrating and drying it. The molar ratio (OH) of the hydroxyl group (OH) or titanium (Ti) contained therein H / Ti) is a solid titanium compound (; [a]) characterized by being in the range of 0.09 to 4, or a compound of at least one element selected from the group consisting of a titanium halide compound and an element other than titanium, or The mixture of the precursors of the compound is hydrolyzed to obtain a hydrolysate which is dehydrated and dried. The molar ratio (OH / Ti) of the hydroxyl group (〇Η) and titanium (Τ!) Is more than 0.09. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) --------- 0_ 丨 (Please read the precautions on the back before filling this page), 11 Intellectual Property Bureau of the Ministry of Economic Affairsg (Printed by the Industrial and Consumer Cooperatives-8-585881 A7 B7 V. Description of the invention (6) The solid titanium-containing compound (I-b) below 4 is a feature, (Please read the precautions on the back before filling this page) Or by (I), the above-mentioned solid titanium compound (1-a) and / or Catalyst components for polycondensation reactions composed of the above-mentioned solid titanium-containing compounds (I-b), and (Π), beryllium, magnesium, calcium, thorium, barium, boron, aluminum, gallium, manganese, metal, zinc, germanium, antimony It is characterized by the auxiliary catalyst component composed of at least one element selected from the group consisting of phosphorus and phosphorus. The catalyst for polyester production related to another aspect of the present invention is: (I) Hydrolyzed by hydrolysis of a titanium halide compound The product is then dehydrated to obtain a solid titanium catalyst (I-c) as a catalyst component for polycondensation reaction, and (Π) consists of beryllium, magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, cobalt, It is characterized by a co-catalyst composed of a compound of at least one element selected from the group consisting of zinc, germanium, antimony, and phosphorus. A compound selected from at least one element among titanium halide compounds and elements other than titanium or a precursor of the compound It is a mixture of substances, which is a solid titanium compound (I-b) obtained by hydrolysis to hydrolysate and then dehydrated and dried. It is characterized by it. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs (I), solid State The catalyst component of the polycondensation reaction composed of titanium compound (I-d), and (Π) is composed of 皴, watch, 弼, total, lock, shed, inscription, marriage, bell, inscription, zinc, germanium, antimony, and scale It is characterized by selecting a compound of at least one element to form a secondary catalyst component. Among the above-mentioned polyester manufacturing catalysts, the secondary catalyst component (π) is magnesium-9-this paper is in accordance with the Chinese National Standard (CNS) ) A4 specification (210X 297 mm) 585881 A7 Intellectual Property Bureau of the Ministry of Economic Affairs (printed by Industrial and Consumer Cooperatives B7 V. Invention description (7)) The compound is more suitable. Also, for the manufacture of polyester related to another form of the present invention The catalyst 'is an acidic solution containing a hydrolyzate of a titanium halide compound obtained by hydrolyzing the titanium halide compound under contact with water, and then changing the alkali to alkali with an alkali, and then adjusting it to P Η 2 ~ 6 with an acid, The resulting precipitate is dehydrated to obtain a solid titanium compound (I-e), which is characterized in that the titanium halide compound is hydrolyzed with the titanium halide compound and the titanium halide compound is hydrolyzed by contacting the titanium halide compound with water. The alkaline solution is adjusted to p Η 2 ~ 6 with alkali, and the resulting precipitate is dehydrated and dried to obtain a solid titanium compound (I-f), which is characterized by (I). The solid titanium compound is made from above. (I-e) or solid titanium compound (I-f) to form a polycondensation reaction catalyst component, and (Π), consisting of beryllium, magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, cobalt, zinc A compound consisting of at least one element selected from the group consisting of germanium, antimony, and phosphorus is characterized by a secondary catalyst component, and a compound selected from at least one element among titanium halide compounds and elements other than titanium or the The mixture of the precursors of the compound is contacted with water to hydrolyze the titanium halide compound to obtain an acidic solution containing the hydrolysate of the titanium halide compound, which is made alkaline with a base, and then adjusted to p p 2 ~ 6 with an acid. The precipitate is dehydrated and dried to obtain a solid titanium-containing compound (I-g), which is characterized by a titanium halide compound and a compound selected from at least one element of titanium or other elements or a compound of the compound. The mixture between the precursors, and --------- Φ | 丨 (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) -10- 585881 A7 B7 V. Description of the invention (8) (Please read the precautions on the back before filling this page) Under water contact, hydrolyze the titanium halide compound to obtain an acid solution containing the hydrolyzate of the titanium halide compound, and adjust it with alkali. It is p Η 2 ~ 6, and the resulting precipitate is dehydrated and dried to obtain a solid titanium-containing compound (I-h), which is characterized by (I). The solid titanium-containing compound (I — g), or (I-h) catalyst components for polycondensation reaction, and (Π), consisting of beryllium, magnesium, calcium, rubidium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, germanium, antimony and phosphorus In the constituent group, at least one element selected from the group consisting of a compound and a secondary catalyst component is characterized. Among the catalysts for polyester production, the auxiliary catalyst component (Π) is preferably a magnesium compound. The catalyst for polyester production according to another aspect of the present invention is obtained by dehydrating and drying titanium hydroxide. The 2 β (diffraction angle) is an X-ray diffraction in the range of 1 8 to 3 5 It is characterized by a solid titanium compound (I-i) having a crystallinity of 50% or less as indicated by g, and it is further composed of (I) and the above solid titanium compound (I-1). Polycondensation catalyst components, and the Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperatives (Π)), made of beryllium, magnesium, calcium, thallium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, germanium, antimony and Among the groups consisting of phosphorus, at least one element is selected from the group consisting of auxiliary catalyst components composed of compounds. In addition, the catalyst for polyester production according to another aspect of the present invention is such as (A-1), titanium Hydrolysate of compound to produce hydrolysate (I-j) or a compound selected from at least one element of titanium compound and other elements other than titanium or a mixture of precursors of the compound and hydrolyzed to produce hydrolysate-11-This paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) 585881 Α7 Β7 V. Description of the invention (9) (I-k), and (B), basic compounds, and (Please read the precautions on the back before filling this page) (C), a mixture of aliphatic diols The slurry composition is obtained by heating. Among the catalysts for polyester production, the basic compound (B) includes a tetraethylammonium hydroxyl compound, a tetramethylammonium hydroxyl compound, ammonia water, and sodium hydroxide 'hydrogen. It is preferable to select at least one compound among potassium oxide, N-ethylmorpholine, and N-methylmorpholine. The aliphatic diol (C) is preferably ethylene glycol. Furthermore, other aspects of the present invention are related The catalyst for polyester production is as follows: (A-2), a titanium halide compound is hydrolyzed to form a hydrolysate (I-m), or at least one compound of titanium halide compound and other elements other than titanium is selected or the compound Hydrolysate (I-η) is formed by hydrolyzing the mixture between flooding materials, and (D) 'contains at least one element selected from the group consisting of Syria, Japan, Japan, Japan, Korea, Boron, Ming, Gallium, Mg, Cobalt and Zinc. Characterized by the formation of a metal phosphate Printed by the Ministry of Intellectual Property Bureau, Industrial Cooperative Cooperative, and other compounds such as (A-2), titanium halide compounds are hydrolyzed to produce hydrolysates (I-m) or titanium halide compounds and at least one element other than titanium is selected. The precursor mixture of the compound is hydrolyzed to produce hydrolysates (I-η), and (E), containing at least one selected from beryllium, magnesium, calcium, thallium, boron, aluminum, gallium, manganese, cobalt, and zinc. A metal compound of an element, and (F) at least one phosphide selected from phosphoric acid and phosphate ester, and this paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) 585881 ΑΊ B7 5. Description of the invention (1〇 (G) A mixture of aliphatic diols is heated to obtain a slurry which is characterized by it. (Please read the precautions on the back before filling this page.) Among the above polyester manufacturing catalysts, the metal phosphate (D) is preferably magnesium diphosphate or trimagnesium diphosphate. The metal compound (E) is a magnesium compound, the phosphorus compound (F) is phosphoric acid or trimethyl phosphate, and the aliphatic diol (G) is preferably ethylene glycol. The heating temperature of the mixture of (A-2), (E) '(F) and (G) is 100 ° C to 200 ° C, and the heating time is preferably 3 minutes to 5 hours. In the above-mentioned catalyst for polyester production according to the present invention, a compound or precursor of at least one element selected from the above-mentioned elements other than titanium may be beryllium, magnesium, calcium, saw, barium, scandium, yttrium, Lanthanum, chromium, thorium, vanadium, niobium, molybdenum, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, boron, aluminum, gallium, silicon, germanium, tin, antimony, and A compound of at least one element or a precursor of the compound is selected from the group consisting of phosphorus. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on a method for producing a polyester related to the present invention, in the presence of the above-mentioned polyester manufacturing catalyst, aromatic dicarboxylic acid or its ester-forming derivative and fat are produced. Group diols or ester-forming derivatives thereof are characterized by polycondensation to produce polyesters. The present invention relates to a method for producing another form of polyester, comprising esterifying an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof to form a lower condensate ester. Step of polycondensation and the condensation reaction of the lower polycondensate in the presence of a polycondensation reaction catalyst to form a polycondensation reaction step for the polymer compound. The paper size in the above-mentioned polyester manufacturing method applies the Chinese National Standard (CNS) A4 specification ( 210X297 Male H " -13- 585881 Α7 Β7 V. Description of the invention (11) 'Use of polycondensation reaction catalyst. (Please read the precautions on the back before filling out this page) (I) Hydrolyze the titanium compound into a hydrolysate ( I-j) or a compound of a polycondensation reaction composed of a compound selected from at least one element of titanium compound and other elements other than titanium or a precursor of the compound and hydrolyzed to form a hydrolysate (I-k), and ( Π) Auxiliary catalyst composed of at least one element selected from the group consisting of beryllium, magnesium, calcium, rubidium, barium, boron, aluminum, gallium, manganese, zinc, germanium, antimony and phosphorus A catalyst composed of ingredients' is characterized in that the polycondensation reaction catalyst component (I) is added to an ester reaction container immediately before the start of the esterification reaction or immediately after the start of the esterification reaction. The catalyst for polyester production described above In the above-mentioned auxiliary catalyst component (Π), a magnesium compound is preferably used. In addition, the method for producing a polyester according to another aspect of the present invention includes an aromatic dicarboxylic acid or an ester-forming derivative thereof and a fat. Group glycols or ester-forming derivatives thereof are characterized by being subjected to a polycondensation reaction in the coexistence of a polycondensation catalyst selected in the following (1) to (3), and a phosphate ester; the intellectual property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperative (1) A polycondensation catalyst composed of a hydrolysate (I-m) obtained by hydrolysis of a titanium halide compound, (2) a compound selected from at least one element of the titanium halide compound and other elements other than titanium Or a mixture of precursors of the compound is hydrolyzed to form a hydrolysate (I-η), a polycondensation catalyst, (3) the above (I-m) or (I-η) and 皴, table, brocade , Thorium, barium, Boron, absolute, gallium, manganese, inscription, zinc, germanium, and chain The paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -14-585881 Α7 Β7 V. Description of the invention (12) At least A polycondensation catalyst composed of an elemental compound or phosphate or phosphite. Among the above-mentioned polyester manufacturing catalysts, the phosphate is tributyl phosphate, trioctyl phosphate, or triphenyl phosphate. An acid salt is more suitable. Also, according to another aspect of the present invention, a method for producing a polyester includes an aromatic diresidual acid or an ester-forming derivative thereof, and an aliphatic diol or an vinegar-forming derivative thereof. The characteristics of polycondensation reaction catalysts selected from the following (1) to (3) and the polycondensation reaction performed in the coexistence of at least one compound selected from cyclic lactone compounds and hindered phenol compounds; (1) a polycondensation catalyst composed of a hydrolysate (I-m) formed by hydrolysis of a titanium halide compound, (2) a compound selected from at least one element of the titanium halide compound and other elements other than titanium or a precursor of the compound The mixture is hydrolyzed to form a polycondensation catalyst consisting of a hydrolysate (I-η). (3) The above (I-m) or (I-η) and a beryllium, magnesium, calcium, scandium, barium, boron, aluminum , Gallium, manganese, cobalt, zinc, germanium, antimony, at least one element selected from the group consisting of compounds or phosphates, or phosphite catalysts. As the catalyst for polyester production, a phosphorus compound selected from at least one of phosphoric acid and phosphate ester may be used. A compound selected from at least one of the above-mentioned cyclic lactone-based compound and hindered phenol-based compound, and among them, 5,7-di-third-butyl-3- (3,4-dimethylphenyl) -3Η-benzene 骈Furan 2-ketone, four (Flat scales are applicable to Chinese National Standards (CNS) A4 specifications (210X297 mm)-(Please read the precautions on the back before filling out this page)) Order the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed -15- 585881 Printed A7 printed by S Industrial Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs. 5. Description of the invention (13) Methylene-3-(3, 5-di-third-butyl-4-hydroxyphenyl) C Mixtures of the esters) methane and tris (2,4-di-tert-butylphenyl) phosphate are preferred. In addition, the method for producing a polyester according to another aspect of the present invention includes an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof. In the esterification step of the substance, and in the presence of a polycondensation reaction catalyst, a method for producing a polyester in which the oligomer is subjected to a polycondensation reaction and a high-molecular-weight polycondensation reaction step is used. The following polycondensation reaction catalyst is used: (I) Hydrolysate produced by hydrolysis of titanium halide compound (I-m) or a compound selected from at least one element of titanium halide compound and other elements other than titanium or a mixture of precursors of the compound and hydrolyzed to produce hydrolysate. (I-η) catalyst component of polycondensation reaction, and (Π) at least in the group consisting of beryllium, magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, zinc, germanium, antimony and phosphorus A catalyst consisting of a compound of one element is selected as the auxiliary catalyst component, and a hue adjusting agent is added as a feature in any of the above-mentioned esterification step or polycondensation reaction step. In the method for manufacturing the polyester, the hue adjusting agent includes blue solvent 10 (Solvent Blue 104), red pigment 2 6 3 (Pigment Red 263), and red solvent 1 3 5 (Solvent Red 135). 9 (Pigment Blue 29), blue pigment 1 5 ·· 1 (Pl2ment

Blue 15:1)，藍色素 1 5 : 3 (Pigment Blue 15:3) ’ 紅 色素 1 8 7 ( Pigment Red 187)，紫色素 1 9 ( pigmeni 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------嫌----"—訂------ (請先閱讀背面之注意事項再填寫本頁) -16 · 五、發明説明（14 )Blue 15: 1), Blue Pigment 15: 3 (Pigment Blue 15: 3) 'Red Pigment 1 8 7 (Pigment Red 187), Purple Pigment 1 9 (pigmeni) 210X297 mm) --------- Suspect ---- " —Order ------ (Please read the precautions on the back before filling this page) -16 · V. Description of the invention (14 )

Violet 19)中至少選擇一種爲較宜。 上述輔觸媒成分（Π )以鎂化合物爲較佳。 本發明有關聚酯之處理方法，例如有利用鈦化合物觸 媒，且反應結束之聚酯，以磷原子換算濃度爲1 0 p p m 以上之亞碟酸水溶液，次磷酸水溶液，磷酸酯水溶液，亞 磷酸酯水溶液或次磷酸酯水溶液接觸爲其特徵之方法， 另有利用鈦化合物觸媒，且反應結束之聚酯，以有機 溶劑接觸爲其特徵之方法， 又有利用鈦化合物觸媒，且反應結束之聚酯，以磷原 子換算濃度爲1 0 p P m以上之磷酸之有機溶媒溶液，磷 酸酯之有機溶媒溶液，亞磷酸之有機溶媒溶液，次磷酸之 有機溶媒溶液，亞磷酸酯之有機溶媒溶液或次磷酸酯之有 機溶媒溶液接觸爲其特徵之方法。 上述聚酯以固有粘度爲〇 · 50d Ι/g以上，密度 在1·37g/cm3以上，且乙醛含量在5ppm以下爲 較宜。 上述有機溶媒有醇類，飽和碳化氫，酮類中所選擇之 溶劑，其中以異丙醇或丙酮爲較宜。 經濟部智慧財產局員工消費合作社印製 上述磷酸酯以三丁基磷酸鹽，三苯基磷酸鹽或三甲基 磷酸鹽爲較宜。 上述處理中所使用聚酯以聚乙烯對苯二甲酸酯爲較宜 〇 本發明之一種形態的聚酯，例如有 在（I )，上述固態狀鈦化合物（I 一 c )或上述固 ________^ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17 - 585881 A7 B7 五、發明説明（15) (請先閱讀背面之注意事項再填寫本頁) 態狀含鈦化合物（I - d )所構成縮聚反應觸媒成分，和 (Π )，鎂化合物所構成輔觸媒成分所構成之聚酯製 造用觸媒之存在下，將芳香族二羧酸或其酯形成性衍生物 和脂肪族二元醇或其酯形成性衍生物加以縮聚反應而得之 聚酯，其含鈦量在1〜lOOppm，含鎂量在1〜 2 0 〇 P pm，該聚酯中所含鈦和鎂之重量比率（Mg/ Τι)在0.01以上爲其特徵之聚酯（P— 1)。 上述聚酯（Ρ — 1 )以聚乙烯對苯二甲酸酯爲較宜。 本發明有關之另一形態之聚酯，尙有含鈦原子在 0 · 1〜2 0 0 p p m，其鈹、鎂、鈣、緦、鋇、硼、鋁 、鎵、錳、鈷、鋅和銻中所選擇金屬原子（M)之含量爲 0 · 1 〜500ppm， 前述欽原子和前述金屬原子（Μ)之莫耳比率（欽原 子/金屬原子（Μ))在1/50〜50/1之範圍，而 且 含有0 · 0 1〜1 OOP pm量之色相調整劑爲其特 徵之聚酯（P — 2 )。 上述聚酯（P — 2 )以聚乙烯對苯二甲酸酯爲較宜。 經濟部智慧財產局員工消費合作社印製 又，本發明之另一種形態有關之聚酯，尙有固有粘度 在0 · 50d Ι/g以上。 鈦原子含量在0·1〜200ppm。 鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷、鋅和銻 中所選擇金屬原子（M)之含量在0 · 1〜500ppm 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） -18- 8 A7 B7_ 五、發明説明（16 ) 上述鈦原子和上述金屬原子（M )之莫耳比率（鈦原 子/金屬原子（M)在〇·05〜50範圍， (請先閱讀背面之注意事項再填寫本頁} 乙醛含量在4 p p m以下，且以該含量爲W。p p m， 在2 7 5 °C之溫度下加熱熔融而形成階梯式矩形成型物之 後的乙醛含量爲p 口爪時’ Wi 一 w°在1 〇 p pm以 下爲其特徵之聚酯（P—3)。 上述聚酯（P — 3 )中，上述鈦原子以來源於由鹵化 鈦化合物水解而得縮聚反應觸媒者爲較宜。 上述聚酯（P — 3 )以聚乙烯對苯二甲酸酯爲較宜。 又，本發明之其他形態有關之聚酯’尙有 固有粘度在0.50dl/g以上， 鈦原子含量在0.1〜200PPm’ 皴、錢、銘、總、鎖、砸、銘、録、猛、銘、辞和鍊 中所選擇金屬原子（M)含量在0· 1〜500ppm’ 上述鈦原子和前述金屬原子（Μ)之莫耳比率（鈦原 子/金屬原子（Μ))在0 · 05〜50範圍’ 經濟部智慧財產局員工消費合作社印製 環狀三聚物含量在0 · 5重量％以下’且以該含量爲 X重量％，而2 9 0 °C之溫度下加熱熔融成形爲階梯式矩 形成形物後之環狀三聚物含量之增加量爲y重量％時’ x 和y能滿足下式關係爲其特徵之聚酯（P - 4 )。 y^-〇.2x + 〇.2 該時，上述鈦原子以來源於鹵化鈦化合物之水解而 之縮聚反應觸媒爲較宜。 上述聚酯（Ρ - 4 )以聚乙烯對苯二甲酸酯爲較隻：° 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -19- 585881 A7 _____ B7 五、發明説明（17 ) 又，本發明之另一種形態有關聚酯，尙有在2 9 0 °C 下壓注模成型之際，其流動長（L )和流動厚（T )之比 率（L/T)爲Y，而上述壓注模成型所得之成型物之固 有粘度爲X ( d 1 / g )時，上述X和γ保持下式所示關 係爲其特徵之聚酯（P — 5)。Violet 19) is preferred. The auxiliary catalyst component (Π) is preferably a magnesium compound. The method for treating polyesters of the present invention includes, for example, polyesters using a titanium compound catalyst and the reaction is completed, and a phosphorous acid solution having a concentration of 10 ppm or more in terms of phosphorus atom conversion, an aqueous solution of hypophosphorous acid, an aqueous solution of phosphoric acid ester, and phosphorous acid A method characterized by contacting an aqueous solution of an ester or an aqueous solution of hypophosphite is another feature. A method using a titanium compound catalyst and the reaction is completed is characterized by contacting an organic solvent. Another method uses a titanium compound catalyst and the reaction is completed. Polyester, organic solvent solution of phosphoric acid with a phosphorus atom-concentrated concentration of 10 p P m or more, organic solvent solution of phosphate ester, organic solvent solution of phosphorous acid, organic solvent solution of hypophosphorous acid, organic solvent of phosphite The method is characterized by contacting a solution or an organic solvent solution of hypophosphite. The above-mentioned polyester preferably has an intrinsic viscosity of 0.550 d / g or more, a density of 1.37 g / cm3 or more, and an acetaldehyde content of 5 ppm or less. The organic solvents include alcohols, saturated hydrocarbons, and ketones. Among these solvents, isopropyl alcohol or acetone is preferred. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The above phosphates are preferably tributyl phosphate, triphenyl phosphate or trimethyl phosphate. The polyester used in the above treatment is preferably polyethylene terephthalate. The polyester in one form of the present invention includes, for example, (I), the solid titanium compound (I-c), or the solid _______ ^ This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -17-585881 A7 B7 V. Description of the invention (15) (Please read the precautions on the back before filling this page) State of titanium-containing compounds In the presence of a catalyst component for the polycondensation reaction composed of (I-d) and a polyester production catalyst composed of (Π) and a secondary catalyst component composed of a magnesium compound, an aromatic dicarboxylic acid or an ester thereof is formed. A polyester obtained by polycondensation of a derivative with an aliphatic diol or an ester-forming derivative thereof. The polyester contains titanium in an amount of 1 to 100 ppm and magnesium in an amount of 1 to 2000 pm. It is a polyester (P-1) with a weight ratio (Mg / Ti) of titanium and magnesium of 0.01 or more. The polyester (P-1) is preferably polyethylene terephthalate. In another form of the polyester according to the present invention, there are titanium atoms containing 0.1 to 200 ppm of beryllium, magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, and antimony. The content of the selected metal atom (M) is from 0.1 to 500 ppm, and the Mohr ratio (Qin atom / metal atom (M)) of the aforementioned Qin atom and the aforementioned metal atom (M) is between 1/50 and 50/1. Range, and contains 0 · 0 1 ~ 1 OOP pm amount of hue adjusting agent as its characteristic polyester (P-2). The polyester (P-2) is preferably a polyethylene terephthalate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Another aspect of the polyester of the present invention has an inherent viscosity of 0.550d Ι / g or more. The titanium atom content is from 0.1 to 200 ppm. The content of the selected metal atom (M) in beryllium, magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, cobalt, zinc and antimony is in the range of 0.1 · 500 ppm This paper is applicable to the Chinese National Standard (CNS) A4 Specifications (210X29 * 7mm) -18- 8 A7 B7_ V. Description of the invention (16) Molar ratio of the above titanium atom to the above metal atom (M) (the titanium atom / metal atom (M) is in the range of 0.05 to 50 Range, (Please read the precautions on the back before filling in this page} The acetaldehyde content is less than 4 ppm, and the content is W. ppm, heated and melted at a temperature of 2 7 5 ° C to form a stepped rectangular shaped article The subsequent acetaldehyde content is a polyester (P-3) which is characterized by 'Wi-w °' at 10 ppm or less when p is claws. In the polyester (P-3), the titanium atom is derived from It is preferable to obtain a polycondensation catalyst by hydrolysis of a titanium halide compound. The polyester (P-3) is more preferably a polyethylene terephthalate. In addition, polyesters related to other aspects of the present invention include: The intrinsic viscosity is above 0.50dl / g, and the titanium atom content is 0.1 ~ 200PPm '皴, money, Ming, total, lock, smash, Ming, The content of the selected metal atom (M) in the chain, Meng, Ming, Ci and chain is from 0.1 to 500 ppm '. The molar ratio (titanium atom / metal atom (M)) of the titanium atom to the metal atom (M) is 0. 05 ~ 50 range 'The content of the cyclic trimer printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 0.5% by weight or less' and the content is X% by weight, and it is heated and melted at a temperature of 290 ° C When the increase in the content of the cyclic trimer after forming into a stepped rectangular shaped article is y wt%, x and y can satisfy the polyester (P-4) whose characteristic relationship is as follows: y ^ -〇.2x + 〇.2 At this time, it is preferable that the above-mentioned titanium atom is a polycondensation reaction catalyst derived from the hydrolysis of a titanium halide compound. The above-mentioned polyester (P-4) is made of polyethylene terephthalate only: ° This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -19-585881 A7 _____ B7 V. Description of the invention (17) In addition, another form of the present invention is related to polyester. In the case of injection molding under ° C, the ratio (L / T) of the flow length (L) to the flow thickness (T) is Y, and the above When the solid injection molding of the molded article obtained has a viscosity of X (d 1 / g), and the X-γ maintaining its characteristics of polyester under the relationship shown in Formula (P - 5).

Y2647-500X 該聚酯（P — 5 )例如可按照下述方法而製得： 由鹵化鈦化合物水解而成水解產物（I - m )所構成 縮聚反應觸媒，另由鹵化鈦化合物和鈦以外之其他元素中 至少選擇一種元素之化合物或該化合物之前驅物間之混合 物經水解而成水解產物（I - η )所構成縮聚反應觸媒， 或由 (I )，上述水解產物（I 一 m )或水解產物（I 一 η )所構成縮聚反應觸媒成分，和 (Π )，鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷 、鋅、鍺、銻和磷所構成群中至少選擇一種元素之化合物 所構成輔觸媒成分而成縮聚反應觸媒之存在下，將芳香族 二羧酸或其酯形成性衍生物和脂肪族二元醇或其酯形成性 衍生物進行縮聚反應而製成。 上述鈦以外之其他元素中至少選擇一種元素之化合物 或該化合物之前驅物，其例舉如同前述。 上述輔觸媒成分（Π )以鎂化合物爲較宜，該時聚酯 以鈦原子含量1〜1 0 0 p pm範圍，鎂原子含量在1〜 2 0 0 p pm範圍，上述鈦原子和鎂原子之重量比率（ (請先閱讀背面之注意事項再填寫本頁) 4Y2647-500X The polyester (P-5) can be prepared, for example, according to the following method: a polycondensation reaction catalyst composed of a hydrolyzed product (I-m) of a titanium halide compound, and a titanium halide compound and other than titanium A polycondensation catalyst composed of a hydrolysate (I-η) of a compound of at least one element selected from other elements or a mixture of precursors of the compound by hydrolysis, or (I), the above-mentioned hydrolysate (I-m ) Or hydrolysate (I-η) catalyst components for polycondensation reaction, and (Π), beryllium, magnesium, calcium, rubidium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, germanium, antimony and phosphorus In the presence of a polycondensation reaction catalyst composed of a co-catalyst component composed of at least one element selected from the constituent group, an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic glycol or an ester-forming derivative thereof are derived. The product is made by polycondensation reaction. A compound or a precursor of at least one element selected from the above elements other than titanium is exemplified as described above. The auxiliary catalyst component (Π) is preferably a magnesium compound. At this time, the polyester has a titanium atom content in the range of 1 to 100 p pm and a magnesium atom content in the range of 1 to 2 0 p p pm. The titanium atom and magnesium Atomic weight ratio ((Please read the notes on the back before filling this page) 4

、1T 經濟部智慧財產局員工消費合作社印製 本纸張尺度適用中國國家標準（CNS ) Α4規格（21〇Χ297公釐） -20- 585881 A7 B7 五、發明説明（18 )、 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to Chinese National Standards (CNS) A4 specifications (21 × 297 mm) -20-585881 A7 B7 V. Description of the invention (18)

Tl/Mg)在0 · 0 1以上爲較宜。 聚酯（P — 5 )以聚乙烯對苯二甲酸酯爲宜。 (請先閱讀背面之注意事項再填寫本頁) 本發明之一種形態有關聚酯成型物，有自上述聚酯（ P - 1 )所製得爲其特徵者，聚酯成型物之種類有中空成 型物’薄膜或片狀物，纖維等。 本發明之另一種形態有關聚酯成型物，有自上述聚醋 (P — 4)所製得，其環狀三聚物含量在0 · 6重量％以 下爲其特徵之中空成型物。 又，本發明之其他形態有關聚酯成型物，有自上述聚 酯（P — 5 )所製得爲其特徵之中空成型物用預塑物和中 空成型物。 圖面之簡單說明： 圖1示固態狀鈦化合物之結晶化度之測定方法所用X 光衍射譜。 圖2示測定煙霧、環狀三聚物含量以及乙醛含量等所 使用階梯式矩形成型物之斜視圖。 經濟部智慧財產局員工消費合作社印製 本發明有關聚酯製造用觸媒’使用該觸媒之聚酯製造 方法，由該方法所得聚酯和其用途具體說明如下： 本發明之一種形態有關聚酯製造用觸媒’係由下述之 固態狀鈦化合物（I 一 a )和/或固態狀含鈦化合物（I -b )，必要時，還加上下述輔觸媒成分（π)。Tl / Mg) is preferably at least 0 · 0 1. Polyester (P-5) is preferably polyethylene terephthalate. (Please read the precautions on the back before filling in this page.) One aspect of the present invention relates to polyester moldings, which are characterized by being produced from the above polyester (P-1), and the types of polyester moldings are hollow Molded articles' films or sheets, fibers, etc. Another aspect of the present invention relates to a polyester molded product, which is a hollow molded product prepared from the above-mentioned polyacetate (P-4) and having a cyclic trimer content of 0.6% by weight or less. Further, according to another aspect of the present invention, a polyester molded article includes a preform for a hollow molded article and a hollow molded article produced from the above-mentioned polyester (P-5). Brief description of the drawings: Figure 1 shows the X-ray diffraction spectrum used in the method for measuring the crystallinity of a solid titanium compound. Fig. 2 is a perspective view of a stepped rectangular shaped article used for measuring the content of smoke, cyclic trimer, and acetaldehyde. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the catalyst for polyester manufacturing related to the present invention. The polyester manufacturing method using the catalyst, and the polyester obtained by the method and its use are specifically described below. The catalyst for ester production is composed of the following solid titanium compound (I-a) and / or solid titanium-containing compound (I-b), and if necessary, the following auxiliary catalyst component (π) is added.

固態狀鈦化合物（I 一 a )/固態狀含欽化合物（I 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公楚）_ 〇1 - 585881 A7 _____B7 五、發明説明（19 ) -b ) 本發明之固態狀鈦化合物（I - a )藉由將鹵化鈦化 合物水解後脫水乾燥而製得。 鹵化鈦化合物係分子內至少有一個以上之鈦原子和鹵 素原子間之結合存在的化合物，具體言之，例如四氯化鈦 ’四溴化鈦，四碘化鈦等之四鹵化鈦；三氯鈦等之三鹵化 鈦；二氯化鈦等之二鹵化鈦和一鹵化鈦等。 鹵化鈦化合物之水解方法並無特別限制，例如①，添 加鹵化鈦於水中之方法，②，添加水於鹵化鈦中之方法， ③’水中導入含有鹵化鈦化合物之蒸汽的氣體之方法，④ ’鹵化鈦化合物中導入含有水蒸汽之氣體的方法，⑤，使 含有鹵化鈦化合物之氣體和含有水蒸汽之氣體接觸之方法 等。 本發明中，如上述在水解方法上並無特別限制，但是 任何方法都必須以過剩量之水和鹵化鈦化合物作用，使水 解得以充分進行。當水解不能充分進行，所得水解產物如 含有特公昭5 1 - 1 9 4 7 7號公報中所記載之局部水解 產物時’其縮聚合反應速度有不足之虞。 進行水解反應之溫度通常在1 〇 〇 t以下，尤以在〇 〜7 0 °C範圍爲宜。 另一方面，本發明之固態狀含鈦化合物一 b )係 由鹵化鈦化合物和鈦以外之其他元素中至少選擇一種元素 之化合物或該化合物之前驅物（下文中，或簡稱爲其他元 素之化合物）間之混合物加以水解後，乾燥而製得。換言 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)Solid state titanium compound (I aa) / solid state Chin-containing compound (I This paper size applies the Chinese National Standard (CNS) A4 specification (210X297)) 〇1-585881 A7 _____B7 V. Description of the invention (19) -b ) The solid titanium compound (I-a) of the present invention is prepared by hydrolyzing and dehydrating the titanium halide compound. Titanium halide compounds are compounds in which at least one or more titanium atoms and halogen atoms are combined in the molecule, specifically, for example, titanium tetrahalide, titanium tetrabromide, titanium tetraiodide, and other titanium tetrahalides; trichloride; Titanium trihalides such as titanium; titanium dihalides such as titanium dichloride and titanium monohalides. There are no particular restrictions on the hydrolysis method of titanium halide compounds, for example, ① a method of adding titanium halide to water, ②, a method of adding water to titanium halide, ③ 'a method of introducing a gas containing steam of a titanium halide compound into water, ④' A method of introducing a gas containing water vapor into a titanium halide compound, ⑤ a method of bringing a gas containing a titanium halide compound into contact with a gas containing water vapor, and the like. In the present invention, there is no particular limitation on the hydrolysis method as described above, but any method must act with an excess amount of water and a titanium halide compound to allow the hydrolysis to proceed sufficiently. When the hydrolysis does not proceed sufficiently, if the obtained hydrolysate contains the localized hydrolysate described in Japanese Patent Publication Nos. 5 1 to 197 4 7 ', the polycondensation reaction rate may be insufficient. The temperature at which the hydrolysis reaction is carried out is usually below 1000 t, particularly preferably in the range of 0 to 70 ° C. On the other hand, the solid state titanium-containing compound 1b) of the present invention is a compound selected from at least one element of a titanium halide compound and other elements other than titanium or a precursor of the compound (hereinafter, simply referred to as a compound of other elements) The mixture is then hydrolyzed and dried. In other words, the paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling in this page)

、1T 經濟部智慧財產局員工消費合作社印製 •22- 585881 A7 B7 五、發明説明（2C)) 之，在其他元素之化合物共存下，進行鹵化鈦化合物之水 解’將所產生沈澱物乾燥而得固態狀含鈦化合物（I - b )° 上述其他元素乃係指鈹、鎂、鈣、緦、鋇、銃、釔、 鋼、錯、給、銳、銳、組、絡、銷、鶴、猛、鐵、釘、銘 、铑、鎳、鈀、銅、鋅、硼、鋁、鎵、矽、鍺、錫、銻和 磷（下文中，或將上述元素簡稱爲「其他元素」）所構成 群中至少選擇一種元素之化合物或該化合物之前驅體。上 述其他元素之化合物，例如其氫氧化物等。 上述其他元素之化合物可單獨一種使用，或二種以上 調配使用。 鹵化鈦化合物和其他元素之化合物的混合物所進行水 解方法並無特別限制，例如可採用①溶解或懸濁有其他元 素之化合物之水中，添加鹵化鈦化合物之方法，②水中添 加以鹵化鈦化合物和其他元素之化合物之混合物以方法， ③鹵化鈦化合物和其他元素之化合物之混合物中，添加水 之方法，④，鹵化鈦化合物中，添加溶解或懸濁有其他元 素之化合物之水的方法，⑤，溶解或懸濁有其他元素之化 合物的水中’導入含有鹵化鈦化合物之蒸汽的氣體的方法 ，⑥，水中導入含有鹵化鈦化合物之蒸汽和其他元素之化 合物之蒸汽的氣體的方法，⑦，鹵化鈦化合物和其他元素 之化合物的混合物中導入含有水蒸汽之氣體的方法，⑧， 鹵化鈦化合物中，導入含有水蒸汽和其他元素之化合物的 蒸汽的氣體之方法，⑨，使含有鹵化鈦化合物之氣體和含 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）-23 - (請先閱讀背面之注意事項再填寫本頁) 4 訂 經濟部智慧財產局W工消費合作社印製 585881 A7 B7 五、發明説明（21 ) 有其他元素之化合物之蒸汽的氣體以及含有水蒸汽之氣體 接觸之方法等。 (請先閱讀背面之注意事項再填寫本頁) 水解之際，鹵化鈦化合物中之鈦（T i )和其他元素 之化合物中之其他元素（E )間之莫耳比率（E / T 1 ) 在1/5 0〜5 0/1範圍爲宜。又，進行水解反應之溫 度通常在100t以下，尤以0〜70t範圍爲宜。 鹵化鈦化合物或鹵化鈦化合物和其他元素之化合物之 混合物進行水解之際，由於鹵化鈦化合物之水解而產生之 鹵化氫而液性會呈現酸性。由於該酸性可能導致水解之不 能終結，因此，可添加鹼而進行中和。上述所使用之鹼（ 下文中或稱爲中和用鹼）可舉氨水，氫氧化鈉，氫氧化鉀 ’氫氧化鎂等元素周期表中第1 ，2族元素之氫氧化物， 或碳酸鈉，碳酸氫鈉，碳酸鉀，碳酸氫鉀等元素周期表中 之第1 ，2族元素之碳酸化合物或碳酸氫化合物，尿素， 鹼性有機化合物等。中和終點以p Η 4以上爲宜，又，中 和宜在7 0 °C以下進行。 經濟部智慧財產局員工消費合作社印製 上述水解反應所得鹵化鈦化合物之水解產物或鹵化鈦 化合物和其他元素之化合物之混合物的水解產物，在這階 段乃屬所謂原鈦酸之含水氫氧化物之凝膠或含水複合氫氧 化物凝膠。該含水氫氧化物凝膠或含水複合氫氧化物凝膠 經脫水乾燥而得本發明之固態狀鈦化合物（I - a )或固 態狀含鈦化合物（I - b )。據上述乾燥過程可去除氫氧 基之一部分。 上述乾燥可在常壓或減壓下可在固相狀態或懸濁於高 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -24- 8 5 8 A7 B7 五、發明説明（22 ) 於水之沸點的液相狀態中進行，乾燥溫度並無特別限制， 但以3 0 °C以上，3 5 0 °C以下爲宜。又，乾燥之前，先 將含水氫氧化物凝膠或含水複合氫氧化凝膠加以水洗，乾 燥後將固態狀鈦化合物，固態狀含鈦化合物加以水洗而去 除其水溶性成分亦可行。又，乾燥以快速進行爲宜。 按照上述方法所得固態狀鈦化合物（I - a )和固態 狀含欽化合物（I - b )，其組成分隨所共存之其他元素 之有無或含量，有無水洗，乾燥方法，乾燥程度而有異， 但其氫氧基（〇H)和鈦（T 1 )之莫耳比率（〇H/ T 1 )通常在〇 · 09以上，而4以下，其中以0 . 1〜 3爲較宜，尤以0 · 1〜2爲最佳。氫氧基和鈦之莫耳比 率可藉所附著水分和加熱脫離水分之測定而求之，具體測 定方法如下。 求得固態狀含鈦化合物中之氫氧基含量，首先藉卡爾 -費歇水分測定儀測定附著水分含量。其次，藉熱重量分 析法加熱至6 0 0 t而測定其加熱失重。加熱至6 0 0 °C 時，附著水分會脫離，氫氧基以被考慮以水而脫離。因此 ，由加熱失重減去附著水分量而求得氫氧基含量。固態狀 含鈦化合物中之含鈦量，可利用感應耦合電漿光譜學（ Inductively coupled plasma spectroscopy)方法求得。由上 述含鈦量和氫氧基含量求得〇H/T i比率。 更具體言之，例如調製時使用氨水爲中和劑之固態狀 含鈦化合物，其固態狀含鈦化合物中之含鈦量爲4 6重量 %，附著水分量爲6 · 7 3重量％，加熱到6 0 〇 °C時之 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) .4Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs • 22-585881 A7 B7 V. Description of the Invention (2C)) In the coexistence of compounds of other elements, hydrolyze the titanium halide compound 'to dry the resulting precipitate and The solid state titanium-containing compound (I-b) ° The above other elements refer to beryllium, magnesium, calcium, scandium, barium, scandium, yttrium, steel, wrong, sharp, sharp, group, pin, pin, crane, Consisting of manganese, iron, nails, inscriptions, rhodium, nickel, palladium, copper, zinc, boron, aluminum, gallium, silicon, germanium, tin, antimony, and phosphorus (hereinafter, the above elements are simply referred to as "other elements") A compound of at least one element or a precursor of the compound is selected from the group. Compounds of the other elements mentioned above, for example, hydroxides thereof. The compounds of the other elements mentioned above can be used singly or in combination of two or more. There are no particular restrictions on the method of hydrolysis of a mixture of a titanium halide compound and a compound of other elements. For example, ① a method of adding a titanium halide compound to water in which a compound of other elements is dissolved or suspended, ② a titanium halide compound and A method of adding a mixture of other element compounds, ③ a method of adding water to a mixture of a titanium halide compound and a compound of other elements, ④ a method of adding water that dissolves or suspends a compound containing other elements to a titanium halide compound, ⑤ ， Method of introducing gas containing steam of titanium halide compound into or dissolving in water with compounds of other elements, ⑥ Method of introducing gas containing steam of titanium halide compound and steam of compounds of other elements into water, ⑦, halogenation A method of introducing a gas containing water vapor into a mixture of a titanium compound and a compound of other elements, ⑧, a method of introducing a gas containing water vapor and a vapor containing a compound of other elements into a titanium halide compound, ⑨, making a compound containing a titanium halide compound Gas and paper with appropriate size Use Chinese National Standard (CNS) A4 specification (210X 297 mm) -23-(Please read the notes on the back before filling out this page) 4 Order printed by the Ministry of Economic Affairs, Intellectual Property Bureau, W Industrial Consumer Cooperative, 585881 A7 B7 V. Invention Explanation (21) The method of contacting the gas of vapor containing compounds of other elements and the gas containing water vapor. (Please read the notes on the back before filling this page.) Mole ratio (E / T 1) between titanium (T i) in titanium halide compounds and other elements (E) in other halogenated compounds during hydrolysis. The range is preferably from 1/5 0 to 5 0/1. The temperature at which the hydrolysis reaction is carried out is usually 100 t or less, particularly preferably in the range of 0 to 70 t. When a titanium halide compound or a mixture of a titanium halide compound and a compound of other elements is hydrolyzed, the hydrogen halide generated by the hydrolysis of the titanium halide compound will be acidic. Since this acidity may cause the hydrolysis to fail, neutralization may be performed by adding a base. The alkali used above (hereinafter also referred to as a base for neutralization) may be ammonia water, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and other elements of the periodic table of the Group 1, 2, or sodium carbonate, or sodium carbonate , Sodium bicarbonate, potassium carbonate, potassium bicarbonate and other elements of the Periodic Table of the Group 1, 2, carbonic acid compounds or hydrogen carbonates, urea, basic organic compounds, etc. The end point of neutralization is preferably above p 以上 4, and neutralization should be performed below 70 ° C. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the hydrolysate of the titanium halide compound obtained from the above hydrolysis reaction or the hydrolyzate of the mixture of the titanium halide compound and other element compounds. At this stage, it is the so-called hydrous hydroxide of orthotitanic acid. Gel or aqueous composite hydroxide gel. The aqueous hydroxide gel or the aqueous composite hydroxide gel is dehydrated to obtain the solid titanium compound (I-a) or the solid titanium-containing compound (I-b) of the present invention. According to the above-mentioned drying process, a part of the hydroxyl group can be removed. The above drying can be in the solid phase state or suspended under normal pressure or reduced pressure. It can be suspended in high paper size. Applicable to China National Standard (CNS) A4 (210X297 mm) -24- 8 5 8 A7 B7 V. Description of the invention (22) It is carried out in the liquid phase state of the boiling point of water, and the drying temperature is not particularly limited, but it is preferably 30 ° C or more and 350 ° C or less. Before drying, the water-containing hydroxide gel or the water-containing composite hydroxide gel is washed with water. After drying, the solid titanium compound and the solid titanium-containing compound are washed with water to remove the water-soluble component. It is preferable that the drying is performed quickly. The composition of the solid titanium compound (I-a) and the solid chitin-containing compound (I-b) obtained according to the above method varies with the presence or absence of other elements, the presence or absence of washing, the drying method, and the degree of drying. However, the molar ratio (OH / T1) of its hydroxyl group (OH) and titanium (T1) is usually above 0.99, and below 4; among them, 0.1 ~ 3 is preferable, especially 0 · 1 to 2 is the best. The molar ratios of the hydroxyl group and titanium can be determined by the measurement of the attached water and the heat release moisture. The specific measurement method is as follows. To determine the hydroxyl group content in the solid titanium-containing compound, first, the Karl-Fisher moisture meter was used to determine the moisture content of the adhesion. Next, the weight loss was measured by heating to 600 t by thermogravimetric analysis. When heated to 600 ° C, the attached moisture will be detached, and the hydroxyl group will be detached with water. Therefore, the amount of hydroxyl groups was determined by subtracting the amount of attached water from the weight loss on heating. The titanium content of the solid titanium-containing compound can be determined by the method of inductively coupled plasma spectroscopy. The OH / T i ratio was determined from the titanium content and the hydroxyl group content. More specifically, for example, a solid state titanium-containing compound using ammonia as a neutralizing agent during preparation, the titanium content in the solid state titanium-containing compound is 46% by weight, and the amount of attached water is 6.33% by weight. Heating The paper size up to 600 ° C applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) (Please read the precautions on the back before filling this page). 4

、1T 經濟部智慧財產局Β(工消費合作社印製 -25- 8 5 8 A7 --—-----___ -———-- 五、發明説明（23 ) 加熱失重爲9 · 67重量％，含氮量爲1 · 3重量％，含 (請先閱讀背面之注意事項再填寫本頁) 氯羹爲1 4 P P m之〇Η / 丁 1比率可按照下述方法計算 之°又，含氮量可藉微量總含氮量分析設備（化學發光法 )測定，含氯量可藉層析分析法求得。 固態狀含氮化合物1 〇 0 g中之鈦的莫耳量按照下列 方法計算之。 46-4 7.88 = 0.9607 (含鈦量） （鈦原子量） 又，固態狀含鈦化合物中之氮和氯分別以氨，氯化氫 而脫離，所以加熱脫離水量（重量％ )可按照下列方法求 得之。 9.67 — (1.3x(17/14) — (0.0014x(36.5/35.5) = 8.090 6〇〇°C 含氮量氨換算含氯量 氯化氫換算 加熱失重 經濟部智慧財產局8工消費合作社印製 由上述什算結.果和附者水分量之測定値，按以下方法 求得氫氧基來源之加熱脫離水分量（重量％ )。 8.090-6.73 = 1.360 據此，1 0 0 g之固態狀含氮化合物中所含氫氧基之 莫耳量可按照下列方法求得之。 (1 · 360/18)x2 = 0 · 1511 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 一 -26- 8 5 8 A7 _________B7 五、發明説明（24 ) 由上述結果’可求得固態狀含鈦化合物中之含鈦量和 氫氧基含量之莫耳比率（〇H/T i ) (請先閱讀背面之注意事項再填寫本頁) 〇· 1511+0 ·96〇 7 二 0.157 上述固態狀鈦化合物（I 一 a )和固態狀含鈦化合物 (1〜b )在縮聚合反應進行之溫度下，例如在約2 8 〇 °C下也有氫氧基殘存。 固態狀欽化合物（I 一 a )和固態狀含鈦化合物（I 一 b)之〇h/T i比率在上述範圍，並且在約28〇Χ： 下氫氧基還殘存之事實，顯示固態狀鈦化合物（I 一 a ) 和固態狀含鈦化合物（I - b )和特開昭 52 — 572 91號公報或特公昭47 — 26597號公 報所言及之原鈦酸（以ΗιΤ i〇4表示。鈦和氫氧基之莫 耳比率爲1 : 4 )在本質上不同，同時和特開昭 5 0 - 1 5 6 5 9 5號公報等做爲聚酯製造用觸媒使用之 氧化鈦在本質上也不相同。、 1T Intellectual Property Bureau of the Ministry of Economy Β (printed by Industrial and Consumer Cooperatives -25- 8 5 8 A7 --------------- ---------) V. Description of the invention (23) Weight loss during heating is 9.67 weight %, Nitrogen content is 1.3% by weight, including (please read the precautions on the back before filling out this page). Chlorine is 1 4 PP m of 〇Η / but 1 ratio can be calculated according to the following method. The nitrogen content can be measured by a trace total nitrogen content analysis device (chemiluminescence method), and the chlorine content can be obtained by chromatographic analysis. The molar content of titanium in 100 g of solid nitrogen-containing compound according to the following method Calculate it. 46-4 7.88 = 0.9607 (titanium content) (titanium atomic weight) In addition, the nitrogen and chlorine in the solid titanium-containing compound are separated by ammonia and hydrogen chloride, so the amount of water to be removed by heating (% by weight) can be as follows Find it. 9.67 — (1.3x (17/14) — (0.0014x (36.5 / 35.5) = 8.090 600 ° C nitrogen content ammonia conversion chlorine content hydrogen chloride conversion heating weightlessness intellectual property bureau of the Ministry of Economic Affairs 8 labor consumption The cooperative prints the moisture content of the above-mentioned calculation results, fruits, and appendixes, and calculates the source of the hydroxyl group by the following method: The amount of moisture desorbed by heat (% by weight). 8.090-6.73 = 1.360 Based on this, the molar amount of hydroxyl groups contained in 100 g of a solid nitrogen-containing compound can be obtained by the following method. (1 · 360 / 18) x2 = 0 · 1511 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 1-26- 8 5 8 A7 _________B7 V. Description of the invention (24) From the above results, a solid state can be obtained Molar ratio of titanium content and hydroxyl group content in titanium-containing compounds (〇H / T i) (Please read the precautions on the back before filling this page) 〇 1511 + 0 · 96〇7 2 0.157 The above solid The titanium compound (I a a) and the solid titanium-containing compound (1 to b) also have hydroxyl groups remaining at a temperature at which the condensation polymerization reaction proceeds, for example, at about 2800 ° C. The solid state Chin compound (I a a) The solid-state titanium-containing compound (I-b) has an OH / T i ratio in the above range, and at about 280 ×: the fact that the hydroxyl group still remains, shows the solid-state titanium compound (I-a) And solid state titanium-containing compounds (I-b) and Japanese Patent Laid-Open No. 52-572 91 or Japanese Patent Laid-Open No. 47-26597 And orthotitanic acid (represented by ΤΤΤ〇4. The molar ratio of titanium to hydroxyl group is 1: 4) is essentially different, and it is also made with JP-A-Sho 5 0-1 5 6 5 9 5 The titanium oxides used for polyester manufacturing catalysts are also fundamentally different.

又’本發明有關之固態狀含鈦化合物（1 一 b )以該 化合物中之鈦（T i )和其他元素（e )之莫耳比率（E 經濟部智慧財4¾員工消費合作社印製 /Ti)在 1/50 〜50/1 ，其中以 1/40 〜40 /1爲較且’尤以1/ 3 0〜3 0/ 1爲最佳。 本發明有關之固態狀鈦化合物（I 一 a )和固態狀含 鈦化合物（I 一 b)，其含氯量通常在〇〜1 0000 ppm，其中以〇〜l〇〇PPm爲較宜。 上述固態狀鈦化合物（I - a )或固態狀含鈦化合物 (I - b )’必要時倂用下述輔觸媒化合物所構成之輔觸 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) -27· 585881 A7 B7__ 五、發明説明（25 ) 媒成分（Π )。 (請先閲讀背面之注意事項再填寫本頁) 輔觸媒化合物 輔觸媒化合物乃係由鈹、鎂、鈣、緦、鋇、硼、鋁、 鎵、錳、鈷、鋅、鍺、銻和磷所構成群中至少選擇一種元 素之化合物。 由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷、鋅、 鍺、銻和磷所構成群中至少選擇一種元素之化合物，例如 該元素之乙酸鹽等脂肪酸鹽，該元素之碳酸鹽，硫酸鹽， 硝酸鹽，氯化物等鹵化物，該元素之乙醯丙酮配位基鹽， 該元素之氧化物等，其中以乙酸鹽或碳酸鹽爲較宜。 又’磷化合物可舉元素周期表中第1族，第2族，周 期表上第4周期之遷移金屬，鉻，給和鋁中至少選擇一種 之金屬之磷酸鹽，亞磷酸鹽。 本發明中所使用輔觸媒化合物之更具體例舉如下。 鋁化合物有乙酸鋁等脂肪酸鋁鹽，碳酸鋁，氯化鋁， 鋁之乙醛丙酮配位基鹽等，其中以乙酸鋁或碳酸鋁爲較宜 〇 經濟部智慈財產局員工消費合作社印製 鋇化合物有乙酸鋇等脂肪酸鋇鹽，碳酸鋇，氯化鋇， 鋇之乙醯丙酮配位基鹽等，其中以乙酸鋇或碳酸鋇爲較宜 〇 鈷化合物有乙酸鈷等脂肪酸鈷鹽，碳酸鈷，氯化鈷， 鈷之乙醯丙酮配位基鹽等，其中以乙酸鈷或碳酸鈷爲較宜 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -28- 585881 A7 B7 ^-------------- 真、發明説明（26 ) 鎂化合物有乙酸鎂等脂肪酸鎂鹽，碳酸鎂，氯化鎂， 鎂之乙醯丙酮配位基鹽等，其中以乙酸鎂或碳酸鎂爲較宜 ’ 宜 錳較 化爲 氯錳 ’ 酸 錳碳 酸或 碳錳 ’ 酸 鹽乙 錳以 酸中 肪其 脂， 等等 錳鹽 醯基 乙位 有配 物酮 合丙 化醯 錳乙 之 錳 等等 緦鹽 酸基 乙位 有配 物酮 合丙 化醯 緦乙 之 緦 脂 ， 宜 緦較 化爲 氯總 ’ 酸 緦碳 酸和 碳緦 , 酸 鹽乙 緦以 酸中 肪其 (請先閲讀背面之注意事項再填寫本頁) 鋅化合物有乙酸鋅等之脂肪酸鋅鹽，碳酸鋅，氯化鋅 ，鋅之乙醯丙酮配位基鹽等，其中以乙酸鋅或碳酸鋅爲較 宣。 鍺化合物有二氧化鍺，乙酸鍺等。 銻化合物有二氧化銻，乙酸銻等。 經濟部智慧財產局員工消費合作社印製 磷化合物中之磷酸鹽有磷酸鋰，磷酸二氫鋰，磷酸氫 二鋰，磷酸鈉，磷酸二氫鈉，磷酸氫二鈉，磷酸鉀，磷酸 二氫鉀，磷酸氫二鉀，磷酸緦，磷酸二氫緦，磷酸氫二緦 ，磷酸鉻，磷酸鋇，磷酸鋁，磷酸鋅等。其中尤以磷酸鈉 ，磷酸二氫鈉，磷酸氫二鈉，磷酸鉀，磷酸二氫鉀，磷酸 氫二鉀爲較宜採用。 又，磷化合物中之亞磷酸鹽有鹼金屬，鹼土金屬，周 期表第四周期之遷移金屬，鉻，飴和鋁中至少選擇一種之 金屬之亞磷酸鹽，更具體言之，可使用亞磷酸鋰，亞磷酸 鈉，亞磷酸鉀，亞磷酸緦，亞磷酸鉻，亞磷酸鋇，亞磷酸 本紙張尺度適用中國國家標準（CNS ) A4規格（21GX 297公襲） -29- 585881 A7 B7 五、發明説明（27) 鋁’亞磷酸鋅等。其中以使用亞磷酸鈉，亞磷酸鉀爲較宜 〇 (請先閲讀背面之注意事項再填寫本頁) 輔觸媒化合物中，以碳酸鎂，乙酸鎂等鎂化合物；碳 酸鈣’乙酸鈣等鈣化合物；氯化鋅，乙酸鋅等鋅化合物爲 較佳。 上述輔觸媒化合物可一種單獨使用，或二種以上調配 做爲輔觸媒成分使用。 上述輔觸媒成分（Π )之使用，以上述固態狀鈦化合 物（I 一 a )中之鈦和輔觸媒成分（π)中之金屬原子之 莫耳比率〔（Π ) / ( I - a )〕，或上述固態狀含鈦化 合物（I 一 b )中之鈦和其他元素以及輔觸媒成分（π ) 中之金屬原子之莫耳比率〔（Π)/(Ι — b)〕在1/ 50〜50/1 ，其中以1/40〜40/1爲較宜，最 好在1/ 3 0〜3 0/1範圍。又，使用磷酸鹽或亞磷酸 鹽等磷化物時，以磷化合物中所含金屬原子換算之。 經濟部智慧財產局員工消費合作社印製 使用上述聚酯製造用觸媒製造聚酯之方法如後述過程 進行，縮聚合反應時使用固態狀鈦化合物一 a )或固 態狀含鈦化合物（I - b )，低縮聚物中之芳香族二羧酸 單位計，以金屬原子換算，使用〇·001〜〇·2莫耳 %，其中以使用◦· 002〜0 · 1莫耳％爲宜。 固態狀鈦化合物（I - a )或固態狀含鈦化合物（I 一 b )之外，再倂用輔觸媒成分（π)時，輔觸媒成分（ Π )之用量以低縮聚物中之芳香族二羧酸單位計，金屬原 子換算使用0·001〜0·5莫耳％，其中以使用 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -30- 585881 A7 經濟部智慧財產局員工消費合作社印製Also 'The solid titanium-containing compound (1-b) of the present invention is represented by the molar ratio of titanium (T i) and other elements (e) in the compound (E Ministry of Economic Affairs Intellectual Property 4¾ printed by employee consumer cooperatives / Ti ) In the range of 1/50 to 50/1, of which 1/40 to 40/1 is preferred, and 1/3 0 to 3 0/1 is the best. The solid titanium compound (I-a) and the solid titanium-containing compound (I-b) according to the present invention usually have a chlorine content of 0 to 10,000 ppm, of which 0 to 100 PPm is preferred. The above-mentioned solid titanium compound (I-a) or solid titanium-containing compound (I-b) 'is used when necessary. The auxiliary catalysts composed of the following auxiliary catalyst compounds are applicable to the Chinese National Standard (CNS) A4 specifications ( 210X297 mm) -27 · 585881 A7 B7__ 5. Description of the invention (25) Medium component (Π). (Please read the notes on the back before filling out this page) Co-catalyst compounds Co-catalyst compounds are made of beryllium, magnesium, calcium, rubidium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, germanium, antimony and A compound of at least one element is selected from the group consisting of phosphorus. A compound consisting of at least one element selected from the group consisting of beryllium, magnesium, calcium, rubidium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, germanium, antimony, and phosphorus, such as fatty acid salts such as acetate of the element, the Halides such as carbonates, sulfates, nitrates, chlorides of the elements, acetoacetone complex salts of the elements, oxides of the elements, etc. Among them, acetates or carbonates are preferred. The phosphorus compound may be a phosphate or phosphite of at least one metal selected from the group consisting of metals of group 1, group 2, and period 4 of the periodic table in the periodic table. More specific examples of the auxiliary catalyst compound used in the present invention are as follows. Aluminum compounds include aluminum salts of fatty acids such as aluminum acetate, aluminum carbonate, aluminum chloride, and acetaldehyde acetone complex salts of aluminum. Among them, aluminum acetate or aluminum carbonate is more suitable. Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs. Barium compounds include barium salts of fatty acids such as barium acetate, barium carbonate, barium chloride, and acetoacetone complex salts of barium. Among them, barium acetate or barium carbonate is preferred. Cobalt compounds include cobalt salts of fatty acids such as cobalt acetate, carbonic acid. Cobalt, cobalt chloride, acetylacetonate complex salt of cobalt, etc. Among them, cobalt acetate or cobalt carbonate is more suitable. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -28- 585881 A7 B7 ^ -------------- Truth and description of the invention (26) Magnesium compounds include magnesium salts of fatty acids such as magnesium acetate, magnesium carbonate, magnesium chloride, and acetoacetone ligand salts of magnesium, etc., among which Magnesium acetate or magnesium carbonate is more suitable, 'manganese is better than chloromanganese', manganese carbonate, carbonic acid or carbon manganese, and the salt is ethyl manganese, which is fat in the acid, and so on.醯 Manganese, ethyl, manganese, etc. Fatty acid esters should be converted to total chlorine, acid, carbonic acid, and carbon dioxide, and the acid salt should be fatty acid (please read the precautions on the back before filling this page). The zinc compound is zinc acetate. And other fatty acid zinc salts, zinc carbonate, zinc chloride, zinc acetoacetone complex salts, etc., among which zinc acetate or zinc carbonate is more pronounced. Germanium compounds include germanium dioxide, germanium acetate, and the like. Antimony compounds include antimony dioxide and antimony acetate. The phosphates in the phosphorus compounds printed by the employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are lithium phosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium phosphate, and potassium dihydrogen phosphate. , Dipotassium hydrogen phosphate, osmium phosphate, osmium dihydrogen phosphate, diammonium hydrogen phosphate, chromium phosphate, barium phosphate, aluminum phosphate, zinc phosphate and the like. Among them, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate are more suitable. In addition, the phosphite in the phosphorus compound is an alkali metal, an alkaline earth metal, a migrating metal in the fourth period of the periodic table, and at least one metal selected from chromium, rhenium, and aluminum. More specifically, phosphorous acid may be used. Lithium, Sodium Phosphite, Potassium Phosphite, Rhenium Phosphite, Chromium Phosphite, Barium Phosphite, Phosphorous Phosphate This paper is applicable to Chinese National Standard (CNS) A4 (21GX 297) -29- 585881 A7 B7 V. Description of the invention (27) Aluminum 'zinc phosphite and the like. Among them, it is more suitable to use sodium phosphite and potassium phosphite. (Please read the precautions on the back before filling this page.) Among the auxiliary catalyst compounds, magnesium compounds such as magnesium carbonate and magnesium acetate; calcium carbonate, calcium acetate and other calcium Compounds; zinc compounds such as zinc chloride and zinc acetate are preferred. The above-mentioned auxiliary catalyst compounds can be used singly or in combination of two or more as auxiliary catalyst ingredients. The use of the auxiliary catalyst component (Π) is based on the molar ratio of titanium in the solid titanium compound (Ia) to the metal atom in the auxiliary catalyst component (π) [(Π) / (I-a )], Or the Mohr ratio [(Π) / (Ι — b)] of titanium and other elements in the solid state titanium-containing compound (I-b) and the metal atom in the auxiliary catalyst component (π) is 1 / 50 ~ 50/1, among which 1/40 ~ 40/1 is more suitable, and it is preferably in the range of 1/3 0 ~ 3 0/1. When a phosphide such as a phosphate or a phosphite is used, it is converted into a metal atom contained in the phosphorus compound. The method of manufacturing polyester using the above polyester manufacturing catalyst by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is carried out as described later, and a solid titanium compound (a) or a solid titanium-containing compound (I-b) ), Based on the aromatic dicarboxylic acid units in the low polycondensate, in terms of metal atoms, 0.001 to 0.2 mol% is used, and 002 to 0.1 mol% is preferably used. In addition to the solid titanium compound (I-a) or the solid titanium-containing compound (I-b), when the auxiliary catalyst component (π) is used again, the amount of the auxiliary catalyst component (Π) is equal to that in the low polycondensate Aromatic dicarboxylic acid units, metal atom conversion using 0 · 001 ~ 0 · 5 mol%, of which the Chinese national standard (CNS) A4 specification (210X297 mm) is applied at the paper size -30- 585881 A7 Ministry of Economic Affairs Printed by the Intellectual Property Bureau Staff Consumer Cooperative

B7五、發明説明（28 ) 0.002〜0.3莫耳％量爲宜。 上述由固態狀鈦化合物（I - a )，固態狀含鈦化合 物（I - b )以及必要時再加上輔觸媒成分（Π )所構成 之聚酯製造用觸媒，在縮聚合反應之際存在即可。因此， 聚酯之添加可在原料泥漿調製步驟，酯化步驟，液相縮聚 合反應步驟等之任意步驟中進行。又，觸媒可全量一次添 加，或分爲數次添加均可行。又，倂用輔觸媒成分（Π ) 時，可以和固態狀鈦化合物（I - a )或固態狀含鈦化合 物（I - b )同一步驟中添加，或分開在不同步驟中添加 皆可。 由上述聚酯製造用觸媒所得聚酯可經熔融成型爲瓶等 中空成型物，片狀物，薄膜，纖維等使用，其中以提供瓶 用途爲較宜。 上述聚酯製造用觸媒較之已往做爲縮聚合反應觸媒使 用之鍺化合物，銻化合物得以高觸媒活性而製造聚酯。又 使用本發明之聚酯製造用觸媒製造聚酯時，較之使用銻化 合物爲縮聚合反應觸媒時，可得透明性，色相更優異，乙 醛含量更少之聚酯。 本發明之其他形態有關聚酯製造用觸媒，由下述之固 態狀鈦化合物（I 一 c )和輔觸媒成分（Π )所構成，或 由下述之固態狀含鈦化合物（I - d )和必要時再倂用輔 觸媒成分（Π)而構成。 固態狀鈦化合物（I - c )/固態狀含鈦化合物（I (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -31 - 經濟部智慧財產局員工消費合作社印製 585881 A7 B7 五、發明説明（29 ) 〜d ) 本發明之固態狀鈦化合物（I - c )由水解鹵化鈦化 合物後，再脫水乾燥而製得。 上述鹵化鈦化合物可舉前述相同之鹵化鈦化合物。 鹵化鈦化合物之水解方法並無特別限制，例如前述調 製固態狀鈦化合物（I 一 a )之際所使用①至⑤項之方法 皆可採用。 本發明中，如上述在水解方法上並無特別限制，但任 何方法中，以使用過剩量之水和鹵化鈦化合物作用，使7]C 解充分進行爲宜。進行水解反應之溫度，通常在1 〇 〇 t 以下，特別是在0〜7 0 °C範圍下進行爲宜。 上述固態狀鈦化合物（I - c )可和上述由輔觸媒化 合物所構成輔觸媒成分（Π )倂用之。 另一方面，固態狀含鈦化合物（I 一 d )係由幽化鈦 化合物和上述其他元素之化合物之混合物，進行水解係脫 水乾燥而製得。換言之，在其他元素之化合物之共存下， 進行鹵化鈦化合物之水解，所生成沈澱物進行固液相分離 而得固態狀含鈦化合物（I 一 d )。 鹵化鈦化合物和其他元素之化合物之混合物之水解方 法並無特別限制，例如可採用上述之固態狀含鈦化合物（ I 一 d )調製之際所利用①至⑨項之方法等。 水解之際，鹵化鈦化合物中之鈦（T 1 )和其他元素 之化合物中之其他元素（E)之莫耳比率（E/T丄 在1/5 0〜5 0/1範圍。又，水解反應溫度通常在 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ' ---- (請先閱讀背面之注意事項再填寫本頁) 4 、1Τ -32- 585881 A7 B7 五、發明説明（3〇 ) 1〇0t：以下，其中以0〜70 t：範圍爲較宜。 鹵化鈦化合物或鹵化鈦化合物和其他元素之化合物之 混合物，在水解之際，由鹵化鈦化合物之水解時所產生鹵 化氫而液相會呈現酸性。由該酸性而可能水解無法終結， 因此，如前述添加中和用鹼進行中和亦可行。中和之終點 以p Η 4以上爲宜，又，中和宜在7 0 °C以下進行。 上述水解反應所得鹵化鈦化合物之水解產物或鹵化欽 化合物和其他元素之化合物之混合物之水解產物（含水氫 氧化物之凝膠或含水複合氫氧化物之凝膠）經脫水乾燥而 得固態狀鈦化合物（I 一 c )或固態狀含鈦化合物（I 一 d )。 上述乾燥在常壓或減壓下，固相狀態或高於水之沸點 的液相中懸濁狀態下進行，乾燥溫度並無特別限制，但以 3 0 °C以上而3 5 0 °C以下爲較宜。又，乾燥前，將含水 氫氧化物凝膠或含水複合氫氧化物凝膠加以水洗，或乾燥 後，將固態狀鈦化合物，固態狀含鈦化合物加以水洗，而 去除水溶性成分亦可。又，乾燥以快速進行爲較宜。 按照上述方法所得固態狀鈦化合物（I - c )和固態 狀含鈦化合物（I - d )，其組成分隨所共存之其他元素 之有無，或含量，有無水洗，乾燥方法，乾燥程度而有異 ，但其氫氧基（OH)和鈦（丁 i )之莫耳比率（〇h/ 丁 i )通常在0至4以下，其中以〇 · 〇〇 1〜3爲較宜 ，尤以在0 · 0 1〜2之範圍爲最佳。氫氧基和鈦之莫耳 比率’具體而言，可按照前述方法求得。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 0! (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 •33- 585881 A7 B7 經濟部智慧財產局工消費合作社印製 五 、發明説明 ( 31 ) 1 | 又 ， 固 態 狀 鈦 化 合物 ( I 一 C ) 和 固 態 狀 含 鈦 化 合 物 1 I ( I — d ) 在 進 行 縮 聚合 反 應之溫 度 例 如 約 2 8 0 Cc 下 1 1 I ， 也 有 氫 氧 基 殘 存 〇 1 I 請 1 I 又 固 態 狀 含 鈦 化合 物 (I - d ) 以 該 化 合 物 中 之 鈦 先 閱 1 I T 讀 1 ( i ) 和 其 他 元 素 (Ε ) 之莫耳 比 率 ( E / 丁 1 ) 通 常 背 ιέ 1 I 在 1 / 5 〇 5 〇 / 1， 其 中以1 / 4 〇 4 0 / 1 爲 較 之 意 1 1 I 宜 尤 以 1 / 3 0 3 0 , / 1爲最佳（ 事 項 1 1 固 態 狀 鈦 化 合 物 (I — c )和 固 態 狀 含 鈦 化 合 物 ( I 再 填 寫 本 4 — d ) 其 含 氯 量 通 常在 0 〜1 0 〇 〇 0 P P m 其 中 以 頁 1 I 〇 1 〇 〇 P P m爲較宜 〇 1 •1 上 述 固 態 狀 鈦 化 合物 ( I - C ) 和 上 述 輔 觸 媒 成 分 ( 1 I Π ) 倂 用 而 上 述 固 態狀 含 鈦化合 物 ( I 一 d ) 在 必 要 時 1 訂 可 和 上 述 輔 觸: 媒; 成: 分 (Π ; )倂用之。 > 1 1 上 述 輔 觸 媒 成 分 (Π ) 之使用 以 上 述 固 態 狀 鈦 化 合 1 I 物 ( I — C ) 中 之 鈦 和輔 觸 媒成分 ( Π ) 中 之 金 屬 原 子 之 1 1 I 耳 比 率 [ ( Π ) / (I — c )〕 y 或 上 述 固 態 狀 含 鈦 化 ( m 合 物 ( I — d ) 中 之 鈦和 其 他元素 以 及 輔 觸 媒 成 分 ( Π ) 1 中 之 金 屬 原 子 之 耳 比率 [ (Π ) / ( I — d ) ] 在 1 / ! 1 5 0 5 0 / 1 其 中以 1 /40 4 0 / 1 用 量 爲 較 宜 1 I 尤 以 在 1 / 3 0 3 0 / 1範圍 用 量 使 用 爲 最 佳 〇 又 1 1 | 使 用 磷 酸 鹽 或 亞 磷 酸 鹽等 磷 化合物 時 以 磷 化 合 物 中 所 含 1 1 金 屬 原 子 換 算 之 〇 又 ，使 用 鎂化合 物 爲 輔 Mtm 觸 媒 成 分 ( Π ) 1 1 時 上 述 固 態 狀 鈦 化 合物 ( I 一 c ) 中 之 鈦 和 鎂 化 合 物 中 1 I 之 鎂 原 子 之 重 量 比 率 〔Μ g / ( I 一 C ) ] 又 上 述 固 1 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -34 - 585881 A7 經濟部智慧財產局員工消費合作社印製 _ __B7五、發明説明（32 ) 態狀鈦化合物（I - d )中之鈦和其他元素以及鎂化合物 中之鎂原子之重量比率〔Mg/ ( I - d)〕通常在 0 . 01以上，其中以0 . 06〜10爲較宜，尤以 〇·06〜5之範圍量使用爲最佳。在該範圍下使用鎂化 合物時，所得聚酯具有優異之透明性。 使用上述聚酯製造用觸媒而製造聚酯，可按照後述方 法進行，縮聚合反應中，固態狀鈦化合物（I - c )或固 態狀含鈦化合物（I - d )之用量，以低縮聚物中之芳香 族二羧酸單位計，金屬原子換算，通常使用0·001〜 0 · 2莫耳％，其中以使用0 · 002〜0 · 1莫耳％爲 較宜。 固態狀鈦化合物（I - c ) 一起使用之輔觸媒成分（ π )，或必要時和固態狀含鈦化合物（I - d )倂用之輔 觸媒成分（π )，以低縮聚物中之芳香族二羧酸單位計， 金屬原子換算，通常使用0·001〜0·5莫耳％，其 中以使用0·002〜0.3莫耳％量爲較宜。 使用上述聚酯製造用觸媒所製成之聚酯，例如聚乙烯 對苯二甲酸酯具有優異之色相，特別是透明性優異，而乙 醛含量很少。 上述聚酯製造用觸媒所製得聚酯，各做爲各種成型物 之原料使用，例如熔融成型爲瓶等中空成型物，片狀物， 薄膜，纖維等使用，其中以提供瓶用途爲較宜。 由上述聚酯，例如由聚乙烯對苯二甲酸酯成型爲瓶， 片狀物，薄膜，纖維等之方法，可採用已往周知之方法。 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -35- 585881 A7 B7 五、發明説明（33) (請先閱讀背面之注意事項再填寫本頁) 上述聚醋製造用觸媒和已往做爲縮聚合反應觸媒使用 之鍺化合物’銻化合物比較，可以較高觸媒活性而製造聚 酯。又，使用本聚酯製造用觸媒製造聚酯時，較之使用銻 化合物做爲縮聚合反應觸媒時，可得透明性，色相優異， 乙醛含量較少之聚酯。更進而使用本聚酯製造用觸媒所得 聚乙烯對苯二甲酸酯以及其成型物，也具有優異之透明性 和色相，其乙醛含量也較少。 又，本發明之其他形態有關之聚酯製造用觸媒，乃由 下述固態狀鈦化合物（I 一 e )，固態狀鈦化合物（I 一 f )，固態狀含鈦化合物（I 一 g )或固態狀含鈦化合物 (I 一 h ) ’必要時，再加上下述輔觸媒成分（Π)所構 成。 固態狀鈦化合物（I — e ) ， （ I — f )，固態狀含 鈦化合物（I — g ) ，（ I _ h ) 經濟部智慧財產局g(工消費合作社印製 本發明之固態狀鈦化合物（I - e )乃係由鹵化鈦化 合物和水接觸，使含鹵化鈦化合物水解所得鹵化鈦化合物 之水解產物之酸性溶液，以鹼變成鹼性，再用酸調整爲 p Η 2〜6，所生成之沈澱物加以脫水乾燥而製成。固態 狀鈦化合物（I - f )係將鹵化鈦化合物和水接觸，使含 鹵化鈦化合物水解所得鹵化鈦化合物之水解產物之酸性溶 液，直接用鹼調整爲p Η 2〜6，將所生成之沈澱物加以 脫水乾燥而製得。 調製固態狀鈦化合物（I - e )和固態狀鈦化合物（ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）· 36 - 585881 A7 _____B7 五、發明説明（34 ) 1 - ί )所使用之鹵化鈦化合物如同前述之鹵化鈦化合物 〇 (請先閱讀背面之注意事項再填寫本頁) 調製固態狀鈦化合物（I - e )和固態狀鈦化合物（ 1 - ί )之任意情形，水解鹵化鈦化合物之方法皆無特別 限制’例如上述調製固態狀鈦化合物（1 一 a )之際，所 使用①至⑤項之方法均可採用。 本發明中’水解方法如上述並無特別限制，但任何方 法下’皆使用過剩量之水和鹵化鈦化合物作用，乃爲使水 解充分進行上所必要條件。進行水解反應溫度通常在 1 0 0 C以下’特別以〇〜7 0°C範圍爲較宜。 按照上述方法進行鹵化鈦化合物之水解，可得含有鹵 化鈦化合物之水解產物之酸性溶液。該酸性溶液通常示 Ρ Η 1程度之酸性。 經濟部智慧財產局g(工消費合作社印製 §周製固態狀欽化合物（I - e )時，上述含有水解產 物之酸性溶液，用鹼調整爲ρ Η 9〜1 2，其中調整爲 ΡΗ9〜1 1爲較宜，然後用酸調整爲ΡΗ2〜6 ，其中 調整爲ΡΗ3〜6爲較宜。該時溫度通常在5 0°C以下， 其中確以4 0 °C以下爲較宜。按照上述調整爲ρ Η 2〜6 時可使沈澱物產生。 上述使用之鹼，例如有氣，氫氧化鈉，氫氧化鉀，碳 酸鈉，碳酸鉀等，其中以氨和氫氧化鈉爲較宜。又，上述 使用之酸類，例如可舉乙酸，硝酸等，其中以乙酸爲較宜 〇 將上述含有水解產物之酸性溶液一旦變成鹼性之後， 本紙張尺度適用中國國家標準（CNS)Α4規格（210x297公羡） -37- 585881 Α7 Β7 五、發明説明（35 ) 再變成酸性而使沈澱物產生時，可將後述固液相分離後之 脫水步驟縮短時間。又，所得固態狀鈦化合物（I 一 e ) 中，來自鹼之氮，鈉，鉀等也較少殘存，可得縮聚合反應 活性優異，能製得品質優異之聚酯的聚酯製造用觸媒。 調製固態狀鈦化合物（I - f )時，上述含有水解產 物之酸性溶液，用鹼調整爲ρ Η 2〜6，其中以調整爲 ρ Η 3〜6爲較宜。該時溫度通常在5 0 t：以下，特別以 4 0°C以下爲較宜。按照上述調整爲pH2〜6時，會有 沈澱物產生。 上述使用之鹼如同調製固態狀鈦化合物（I — e )時 所使用者，其中以採用氨，氫氧化鈉爲較宜。 按照上述方法將含有水解產物之酸性溶液，調整爲 ρ Η 2〜6 ，使沈澱物產生時，可縮短固液相分離後之脫 水步驟時間。又，所得固態狀鈦化合物（I 一 f )中，來 源於鹼之氮，鈉，鉀等之殘存減少，可得具有縮聚合反應 活性優異，能製造品質優異之聚酯用觸媒。 調製固態狀鈦化合物（I - e )和固態狀鈦化合物（ I 一 ί )之任意情形下，將上述酸性溶液調整爲ρ Η 2〜 6 ’就會有沈澱物產生，但該沈澱物在該階段下，乃係所 謂原鈦酸之含水氫氧化物之凝膠。該含水氫氧化物凝膠經 脫水乾燥而得本發明有關之固態狀鈦化合物（I 一 e )和 固態狀鈦化合物（I - f )。又，經脫水乾燥使含水氫氧 化物凝膠所含氫氧基之一部分去除。 按照上述方法，將酸性溶液調整爲ρ Η 2〜6，可使 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ----------- (請先閲讀背面之注意事項再填寫本頁) 、-?口 經濟部智慧財產局員工消費合作社印製 585881 A7 B7 五、發明説明（36 ) 沈澱物產生，將該沈澱物進行固液相分離，再行乾燥而得 固態狀鈦化合物（I 一 e )或固態狀鈦化合物（I - ί ) (請先閱讀背面之注意事項再填寫本頁) 〇 乾燥可在常壓或減壓下，固相狀態或懸濁於高於水之 沸點的液相狀態下進行，乾燥溫度雖然無特別限制，通常 在3 〇°C以上而3 5 0°C以下爲宜。又，乾燥前，將含水 氫氧化物凝膠加以水洗，或乾燥後，將固態狀鈦化合物（ I 一 e )和固態狀鈦化合物（I 一 f )加以水洗而去除水 溶性成分亦無妨。又，乾燥宜快速進行。 經濟部智慧財產局員工消費合作社印製 固態狀含鈦化合物（I 一 g )係將鹵化鈦化合物和上 述其他元素之化合物之混合物以水接觸，將水解鹵化鈦化 合物所得含有其水解產物之酸性溶液，用鹼變成鹼性後， 再以酸調整爲P Η 2〜6 ，所產生沈澱物加以脫水乾燥而 製成，固態狀含鈦化合物（I - h )係將鹵化鈦化合物和 上述鈦以外之其他元素中至少選擇一種元素之化合物或該 化合物之前驅物之混合物，以水接觸，將鹵化鈦化合物水 解所得含有鹵化鈦化合物之水解產物之酸性溶液，直接用 鹼調整爲P Η 2〜6 ，將所產生沈澱物進行脫水乾燥而製 得。 調製固態狀含鈦化合物（I - g )和固態狀含鈦化合 物（I - h )所用之鹵化鈦化合物，可舉上述相同之鹵化 鈦化合物。 其他元素之化合物，可一種單獨使用，或二種以上調 配使用。 I紙張尺度適用中國國家標準(CNS ) A4規格（210X297公釐） 585881 A7 B7__ 五、發明説明（37 ) (請先閲讀背面之注意事項再填寫本頁) 調製固態狀含鈦化合物（I - g )和固態狀含鈦化合 物（I - h )之任意情形下，鹵化欽化合物和其他元素之 化合物的混合物之水解方法並無特別限制，例如調製上述 固態狀含鈦化合物（I - b )之際所採用①至⑨項之方法 均可使用。 本發明中，如上述其水解方法雖無特別限制，但任何 情形下，皆必要以過剩量之水跟鹵化鈦化合物和其他元素 之化合物之混合物作用而使水解反應充分進行。 水解之際，鹵化鈦化合物中之鈦（T i )和其他元素 之化合物中之其他元素（E)之莫耳比率（E/T i )以 1/5 0〜5 0/1範圍爲較宜。又，進行水解之溫度通 常在1 00 t：以下，其中以〇〜70 °C範圍爲較宜。 按照上述將鹵化鈦化合物和其他元素之化合物之混合 物，加以水解，可得含有鹵化鈦化合物之水解產物和其他 元素之化合物的酸性溶液。該酸性溶液之p Η値通常爲 Ρ Η 1程度。 經濟部智慧財產局員工消費合作社印製 調製固態狀含鈦化合物（I - g ).時，將含有上述水 解產物和其他元素之化合物之酸性溶液，以鹼調整爲ρ Η 9〜12 ，其中以調整爲ΡΗ9〜11之鹼性爲較宜，然 後用酸調整爲ρΗ2〜6 ，其中調整爲ρΗ3〜6爲較宜 。該時之溫度通常在5 0 °C以下，其中尤以4 0 °C以下爲 宜。按照上述調整爲pH 2〜6，可使沈澱物產生。 前述調製固態狀鈦化合物（I - e )所使用相同鹼類 可利用之，其中以氨，氫氧化鈉爲較宜。又，上述使用之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -40- 585881 A7 B7 五、發明説明（38 ) 酸’也可採用前述調製固態狀欽化合物（1 一 e )所使用 相同酸類，其中以乙酸爲較宜。 按照上述將含有水解產物和其他元素之化合物之酸性 溶液一旦變成鹼性，再改成酸性使之產生沈澱物時，可縮 短固液相分離後之脫水步驟之時間。又’所得固態狀含鈦 化合物（I 一 g )中’來源於鹼之氮、鈉、鉀等之殘存量 也變少，可得縮聚合反應活性優異，能製得品質優異之聚 酯用聚酯製造用觸媒。 調製固態狀含鈦化合物（I - h )時’將上述含有水 解產物和其他元素之化合物之酸性溶液，用鹼調整爲P H 2〜6 ，其中調整爲ΡΗ3〜6爲較宜。該時之溫度通常 在5 0 t以下，特別以4 0 °C以下爲宜。按照上述調整爲 p Η 2〜6可使沈澱物產生。 上述所使用之鹼，可舉前述調製固態狀鈦化合物（I - e )所使用相同之鹼類，其中以氨，氫氧化鈉爲較宜。 按照上述方法，將含有水解產物和其他元素之化合物 之酸性溶液調整爲p Η 2〜6而使沈澱物產生時，可以縮 短固液相分離後之脫水步驟所需時間。又，所得固態狀含 鈦化合物（I 一 h )中之來源於鹼之氮、鈉、鉀之殘存量 也減少，可得縮聚合反應活性優異，能製成品質優異之聚 酯用觸媒。 調製固態狀含鈦化合物（I - g )和固態狀含鈦化合 物（I - h )之任意情形中，藉由調整上述酸性溶液爲 p Η 2〜6而能使沈澱物產生，但該沈澱物在該階段下係 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本貢) tr 經濟部智慧財產局員工消費合作社印製 -41 - 585881 A7 B7__ 五、發明説明（39 ) (請先閱讀背面之注意事項再填寫本頁) 所謂原鈦酸之含有含水氫氧化物之含水複合氫氧化物凝膠 。該含水複合氫氧化物凝膠經脫水乾燥而得本發明有關之 固態狀含鈦化合物（I 一 g )和固態狀含鈦化合物（I 一 h )。又，藉上述脫水乾燥而含水複合氫氧化物凝膠所含 有之一部分氫氧基被除去。 上述乾燥可在常壓或減壓下，可在固相狀態或懸濁於 高於水之沸點的液相狀態下進行，乾燥溫度並無特別限制 ’以3 0 °C以上而3 5 0 °C以下爲宜。又，乾燥前，將含 水複合氫氧化物凝膠加以水洗，乾燥後，將固態狀含欽化 合物（I 一 g )和固態狀含鈦化合物（I 一 h )加以水洗 ’而去除水溶性成分亦可行。又，乾燥宜快速進行。 按照上述所得固態狀鈦化合物（I 一 e )，固態狀欽 化合物（I 一 f )，固態狀含鈦化合物（I 一 g )和固態 狀含鈦化合物（I - h )，其組成分隨所共存其他元素之 有無或量之不同，有無水洗，乾燥方法，乾燥程度而異， 但氫氧基（0H)和鈦（T i )之莫耳比率（〇H/T丄 )通常以0 · 09以上而4以下爲宜，其中以〇 · 1〜3 經濟部智慧財產局員工消費合作社印製 爲較宜，尤以〇 · 1〜2爲最佳。氫氧基和鈦之莫耳比率 ’可按照上述方法藉測定附著水分和加熱脫離水分而求得 〇 又’固態狀欽化合物（I 一 e )，固態狀鈦化合物（ 1 一：f ) ’固態狀含鈦化合物（I 一 g )和固態狀含鈦化 合物（I - h )在進行縮聚合反應之溫度下，例如約 2 8 0°C下，尙有氫氧基殘存。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -42、 585881 A7 B7__ 五、發明説明（40 ) (請先閱讀背面之注意事項再填寫本頁〕 固態狀含鈦化合物（I 一 g )和固態狀含鈦化合物（ 工一h)以該化合物中之鈦（丁 1 )和其他元素（E)之 莫耳比率（E/Ti )在1/50〜50/1爲宜’其中 以1/40〜40/1爲較宜，尤以1/30〜30/1 爲最佳。 固態狀鈦化合物（I 一 e )，固態狀鈦化合物（I 一 f )，固態狀含鈦化合物（I 一 g )和固態狀含鈦化合物 (I 一 h)，其含氯量通常在0〜lOOOOppm，其 中以〇〜1OOppm較宜。 必要時，和上述固態狀鈦化合物（I - e )，固態狀 鈦化合物（I 一 f )，固態狀含鈦化合物（I 一 g )或固 態狀含鈦化合物（I 一 h )倂用之輔觸媒成分（Π )，可 採用前述輔觸媒成分相同者，其中以碳酸鎂，乙酸鎂等鎂 化合物；碳酸鈣，乙酸鈣等鈣化合物；氯化鋅，乙酸鋅等 鋅化合物爲宜。輔觸媒化合物可一種單獨使用，或二種以 上調配做爲輔觸媒成分使用。 經濟部智慧財產局員工消費合作社印製 上述輔觸媒成分（Π )之用量，以上述固態狀鈦化合 物（I 一 e )或固態狀鈦化合物（I 一 f )中之鈦和輔觸 媒成分（Π)中之金屬原子之莫耳比率〔（Π)/(ι 一 e )或（Π ) / ( ]； 一 f )〕，或上述固態狀含鈦化合物 (I - g )或固態狀含鈦化合物（I 一 h )中之鈦和其他 元素以及輔觸媒成分（Π)中之金屬原子之莫耳比率〔（ n)//(I 〜g)或（Π)/(Ι - h)〕在 1/50 〜 50/1爲宜’其中以1/4〇〜40/1爲較佳，尤以 $紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ；297公釐） -43- 585881 A7 B7 五、發明説明（41 ) (請先閱讀背面之注意事項再填寫本頁) 1/ 3 0〜3 0/1之範圍用量爲最佳。又，使用磷酸鹽 或亞碟酸鹽等碟化合物時，以碟化合物中所含金屬原子換 算之。又，使用鎂化合物爲輔觸媒成分（Π )時，上述固 態狀鈦化合物（I 一 e )或（I — f )中之鈦和鎂化合物 中之鎂原子之重量比率〔Mg / ( I - e)或（；[一 f ) 〕’或上述固態狀含鈦化合物（I - g )或固態狀含鈦化 合物（I - h )中之鈦和其他元素以及鎂化合物中之鎂原 子之重量比率〔Mg/(I - g)或（I 一 h)〕在 0 · 01以上，其中以0 · 06〜10爲較宜，尤以 0 · 06〜5之範圍量使用爲最佳。在上述範圍使用鎂化 合物時，可得透明性優異之聚酯。 使用上述聚酯製造用觸媒製造聚酯之方法如後述，在 縮聚合反應中，將固態狀鈦化合物（I - e )，固態狀鈦 化合物（I — ί )，固態狀含鈦化合物（I 一 g )或固態 狀含鈦化合物（I 一 h )，對低縮聚物中之芳香族二羧酸 單位計算，以金屬原子換算使用0·001〜0.2莫耳 %，其中以使用〇·〇〇2〜0·1莫耳％爲更佳。 經濟部智慧財產局員工消費合作社印製 固態狀鈦化合物（I 一 e )，固態狀鈦化合物（I — f )，固態狀含鈦化合物（I 一 g )或固態狀含鈦化合物 (I 一 h)之外，再加以使用輔觸媒成分（Π)時，輔觸 媒成分（Π )之用量，對低縮聚物中之芳香族二羧酸單位 計，以金屬原子換算，使用0·001〜〇·5莫耳％爲 宜，其中使用〇 · 002〜0 · 3莫耳％爲更佳。 上述由固態狀鈦化合物（I - e )，固態狀鈦化合物 -44· 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公羞） 585881 A7 B7 五、發明説明（42 ) (請先閱讀背面之注意事項再填寫本頁) (ί 一 f )，固態狀含鈦化合物（I 一 g )和固態狀含鈦 化合物（I - h )中選擇一種之欽化合物，和必要時再力口 以輔觸媒成分（Π )而構成之觸媒，祗要在縮聚合反應時 存在即可。因此，該觸媒之添加可在原料泥漿調製步驟， 酯化步驟，液相縮聚合反應步驟等之任意步驟中進行。又 ’可將觸媒總量一次添加，或分爲數次添加皆可行。又， 倂用輔觸媒成分（Π )時，可在和添加固態狀鈦化合物（ I 一 e )，固態狀鈦化合物（I 一 f )，固態狀含鈦化合 物（I 一 g )或固態狀含鈦化合物（I 一 h )相同步驟添 加，或另外不同步驟添加亦可行。 上述聚酯製造用觸媒，特別是由固態狀鈦化合物（I 一 e ) ， （ I 一 ί ) ’固態狀含鈦化合物（I — g )或固 態狀含鈦化合物（I 一 h )和輔觸媒成分（Π )所構成， 且輔觸媒成分（Π )係鎂化合物之觸媒，最適於聚乙烯對 苯二甲酸酯之製造用觸媒。這種固態狀鈦化合物（I 一 e )，固態狀鈦化合物（I 一 ί )，固態狀含鈦化合物（I - g )或固態狀含駄化合物（I 一 h )和鎂化合物所構成 經濟部智慧財產局員工消費合作社印製 觸媒用以製造聚乙烯對苯二甲酸酯時，例如原料可使用對 苯二甲酸或其酯形成性衍生物以及乙二醇或其酯形成性衍 生物，必要時再加上對苯二甲酸以外之芳香族二羧酸和/ 或乙二醇以外之脂肪族二元醇，按照後述方法酯化，液相 縮聚合反應，需要時再進行固相縮聚合反應。 該時，對苯二甲酸或其酯形成性衍生物之使用量，對 芳香族二羧酸1 0 0莫耳％計，使用8 0莫耳％以上，最 -45- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 585881 A7 B7__ 五、發明説明（43 ) 好使用9 0莫耳％以上，乙二醇或其酯形成性衍生物之使 用量。對脂肪族二元醇1 〇 0莫耳％計，使用8 0莫耳％ ’以使用9 0莫耳％以上爲最佳。 -- (請先閱讀背面之注意事項再填寫本頁) 按照上述方法所製得之聚乙烯對苯二甲酸酯，其含欽 量在1〜20〇ppm，特別以在1〜l〇〇PPm範圍 爲宜，含鎂量在1〜2 Ο Ο ρ ρηι，特別以在1〜1 〇 〇 P Pm範圍爲宜。又，該聚乙烯對苯二甲酸酯中所含鈦和 鎂之重量比率（Mg/Ti)在0 . 01以上，其中在 〇· 06〜10爲宜，尤以在0 · 06〜5範圍爲最佳。 又’該聚乙烯對苯二甲酸酯之含氯量在0〜1 0 0 0 p pm，其中以在〇〜1 〇 〇 p pm範圍爲宜。 上述聚乙烯對苯二甲酸酯具有優異之色相，其透明性 特別優異，乙醛含量也少，尤其適用於製瓶用途。 由上述聚酯製造用觸媒所得聚酯可提供各種成型體之 原料用途，例如熔融成型爲瓶等中空成型物，片狀物，薄 膜，纖維等使用，但以提供製瓶用途爲宜。 經濟部智慧財產局員工消費合作社印製 由上述聚酯製造用觸媒所製得聚酯，例如聚乙烯對苯 二甲酸酯，其製成瓶，片狀物，薄膜，纖維等之成型方法 可採用已往周知之方法。 上述聚酯製造用觸媒，較之已往做爲縮聚合反應觸媒 使用之鍺化合物，銻化合物，得以更高觸媒活性而製造聚 酯。又，和使用銻化合物爲縮聚合反應觸媒時比較’可得 透明性，色相優異，乙醛含量較少之聚酯。 本發明之另一形態有關之聚酯製造用觸媒’可由下述 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）-46 · 585881 經濟部智慧財產局員工消費合作社印製 A7 _B7 ____ 五、發明説明（44 ) 固態狀鈦化合物（I - 1 )和必要時加以輔觸媒成分（π )所構成。 固態狀鈦化合物（I 一 i ) 本發明之固態狀鈦化合物（I - i )係由氫氧化鈦化 合物脫水乾燥而製成。氫氧化鈦化合物例如可由水解鈦化 合物而製得。 水解所使用鈦化合物，例如鹵化鈦化合物，烷氧基鈦 化合物等。 上述鹵化鈦化合物可舉前述相同之鹵化鈦化合物，烷 氧基鈦化合物之例舉有丁氧基鈦，四異丙氧基鈦等。 本發明中之鈦化合物使用鹵化鈦化合物乃係本發明之 較宜途徑之一種。鹵化鈦化合物之水解方法具體說明如下 ’另外烷氧基鈦化合物之水解也可以按照相同方法進行。 鹵化鈦化合物之水解方法並無特別限制，例如前述調 製固態狀鈦化合物（I - a )之際所採用①至⑤項之方法 均可使用。 如上述，水解方法雖然沒有特別限制，但是任何方法 中’皆必要以過剩量之水和鹵化纟太化合物作用，方能期得 水解之充分進行。 進行水解反應之溫度通常在6 0 °C以下，其中尤以〇 〜5 0 C軸圍爲佳。在上述軔圍溫度進丫了水解反應時，有 獲得結晶化度低之固態狀欽化合物之傾向。 鹵化鈦化合物在水解之際，如前述可有其他元素之化 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29?公釐）_ ^7 Φ _| (請先閱讀背面之注意事項再填寫本頁) 訂 585881 A7 B7 五、發明説明（45 ) 合物共存。該其他元素之化合物，可一種單獨或 調配使用。 (請先閱讀背面之注意事項再填寫本頁) 水解反應之際，鹵化鈦化合物中之鈦（丁 1 )和其他 元素之化合物中之其他元素（E)之莫耳比率（E/丁 χ )在1/5 0〜5 0/1車E圍爲宜。又，進彳了水解反脾、之 溫度通常在6 Ot：以下，其中以0〜5 之範圍爲較宜 。在上述溫度範圍進行水解時，有獲得結晶化度低之固態 狀鈦化合物之傾向。 鹵化欽化合物在水解之際’由於鹵化欽化合物之水解 而產生鹵化氫，致使液性呈現酸性。該酸性可能使水解反 應不能終結之情形產生，因此，如同前述可利用中和用驗 加以中和。中和之終點在P Η 4以上爲宜，又，該中和宜 在6 0 °C以下進行，其中以〇〜5 0 °C範圍下進行爲更佳 。在上述範圍溫度下進行時，有獲得結晶化度低之固態狀 欽化合物之傾向。 上述水解反應所得含鈦之化合物，或含鈦和其他元素 之化合物’在該階段下爲所謂原鈦酸之含水氫氧化物凝膠 0 經濟部智慧財產局員工消費合作社印製 本發明中，該含水氫氧化物凝膠經脫水乾燥而成固態 狀之水解產物（即固態狀鈦化合物）。據該乾燥過程可除 去一部分之氫氧基。 上述水解產物之乾燥可在常壓或減壓下，或在固相狀 態或懸濁於高過水之沸點之液相狀態下進行，乾燥溫度並 無特別限制，在3 0 °C以上而3 5 0 °c以下，其中以3 0 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ 297公釐）-48 - 585881 A7 B7 五、發明説明（46) 〜2 0 0 t：範圍爲較宜。在上述範圍溫度下進行水解產物 之乾燥時，有獲結晶化度低之固態狀鈦化合物之傾向。 ----------- (請先閱讀背面之注意事項再填寫本頁) 又，乾燥前’將含水氫氧化物凝膠加以水洗，或乾燥 後，將固態狀含鈦化合物加以水洗，而去除水溶性成分亦 可行。又，乾燥宜快速進行。 按照上述方法所得之固態狀鈦化合物（I - i )據 2 (9 (衍射角度）在1 8〜3 5 °範圍之X光衍射譜所計算 之結晶化度爲5 0 %以下，其中以4 5 %以下爲較宜，最 好在4 0 %以下或非晶質化合物。結晶化度在上述範圍內 之固態狀鈦化合物，做爲聚酯製造用之縮聚合反應觸媒具 有優異活性。 固態狀鈦化合物（I - 1 )之結晶化度，例如可按照 下述方法測定之。圖1示固態狀鈦化合物之結晶化度之測 定方法所用X光衍射譜。 測定試料之X光衍射譜（圖1 ( A ))以及非晶質之 固態狀鈦化合物之X光衍射譜（圖1 ( B ))。基線定在 1 8 °〜3 5 °，以非晶質之固態狀鈦化合物之X光衍射譜之 2 0 = 2 8 · 5 °之位置（不妨礙結晶高峰之位置）爲基準 經濟部智慧財產局員工消費合作社印製 ’對試料之X光衍射譜能重疊狀在強度方向縮小而抄錄（ 圖 1 ( C ))。 由按照上述方法合成之X光衍射譜，求得衍射角在 1 8 °〜3 5 °範圍之試料之X光衍射譜（除去背景）之面積 (I ◦)和非晶質之固態狀鈦化合物之X光衍射譜（除去背 景）之面積（Ia)，以（IQ— ia)/(lQ)xl〇〇 -49· 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 585881 A7 B7 五、發明説明（47) 之値做爲結晶化度（％)。 固態狀鈦化合物（I 一 1 )之組成分隨所共存之其他 元素之有無或含量，有無水洗，乾燥方法，乾_胃g胃_ 然有異，但其氫氧基（〇H)和鈦（T i )之莫耳比率（ 〇 H / T 1 )，通常在0 . 09以上而4以下，其中以 0 · 1〜3爲較宜，尤其在0 · 1〜2範圓時，就縮聚合 活性之觀點而言最理想。氫氧基和鈦之莫耳比$，司·胃測j 定附著水分和加熱脫離之水分而求得。氫氧基和鈦之莫耳; 比率，具體言之，可依照上述方法求得。 又，當固態狀鈦化合物（I - i )含有其他元素時， 該化合物中之鈦（T i )和其他元素（E )之莫耳比率（ E/丁 i )在1/50〜50/1範圍，其中以1/4〇 〜4 0/1爲較宜，尤以1/3 0〜3 0/, 1爲最佳。 固態狀駄化合物（I - i )之含氯量通常在〇〜 1〇〇〇〇卩？1!1，其中以〇〜1〇〇口0111爲較宜。 該固態狀鈦化合物（I - i )在可行縮聚合反應之溫 度下，例如約在2 8 0°C下，仍有氫氧基殘存。 上述固態狀鈦化合物（I _ i )，必要時可和輔觸媒 成分（Π )倂用。必要時所倂用之輔觸媒成分（Π )，可 舉前述輔觸媒成分相同者，其中以碳酸鎂，乙酸鎂等鎂化 合物；碳酸鈣，乙酸鈣等鈣化合物；氯化鋅，乙酸鋅等鋅 化合物爲較宜。輔觸媒化合物可一種單獨或二種以上調配 做爲輔觸媒成分使用。 上述輔觸媒成分（Π )之用量，以上述固態狀鈦化合 ---------— (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財/I局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -50- ^5881 A7 S'—------- 五、發明説明（48) (請先閲讀背面之注意事項再填寫本頁) 物（1 一 1 )中之欽（當固態狀鈦化合物（I 一 1 )含有 其他元素時’包括欽和其他元素在內）和輔觸媒成分（π )中之金屬原子之莫耳比率〔（Π)/(Ι - i)〕在1 /5〇〜50/1 ’其中以1/4〇〜4〇/；[爲較宜， 尤以1/3 0〜3 0/1範圍量使用爲最佳。又，使用憐 酸鹽或亞磷酸鹽等磷化合物時，以磷化合物所含金屬原子 換算之。 使用上述聚酯製造用觸媒製造聚酯之方法，按照後述 方法進行，縮聚合反應中，固態狀鈦化合物（I - i )之 用量，以低縮聚物中之芳香族二羧酸單位計，金屬原子換 算’在0·001〜〇.2莫耳％，其中以使用 〇.002〜0.1莫耳％爲較宜。 固態狀鈦化合物（I - i )之外，再加用輔觸媒成分 (Π )時，輔觸媒成分（π )之用量，以低縮聚物中之芳 香族二羧酸單位計，金屬原子換算，在0 . 0 〇 1〜 〇 . 5莫耳％，其中以使用0 · 002〜0 · 3莫耳％爲 較宜。 經濟部智慧財產局g(工消費合作社印製 上述固態狀鈦化合物（I - i )以及必要時再加用之 輔觸媒成分（Π )所構成之觸媒，祗要在縮聚合反應時存 在即可。因此，觸媒之添加可在原料泥漿調製步驟，酯化 步驟，液相縮聚合反應步驟等之任意步驟中進行。又，將 觸媒一次全量添加或分批爲數次添加均可。又，倂用輔觸 媒成分（Π )時，可在和固態狀鈦化合物（I 一 i )相同 步驟中添加，也可以另外在不同步驟中添加。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -51 - A7 B7 五、發明説明（49) (請先閱讀背面之注意事項再填寫本頁) 由上述聚酯製造用觸媒所製得聚酯，最好是聚乙烯對 苯二甲酸酯，而可熔融成型爲瓶等中空成型物，片狀物’ 薄'膜’纖維等使用，其中以提供瓶之用途爲較宜。 上述之聚酯製造用觸媒，較之已往使用爲縮聚合反應 觸媒用途之鍺化合物，銻化合物，可藉更高觸媒活性而製 ^聚酯。又，和使用銻化合物做爲縮聚合反應觸媒比較， 可製得透明性，色相優異，乙醛含量少之聚酯。 又，本發明之另一形態有關.之聚酯製造用觸媒，乃係 由（A - 1 )水解鈦化合物而成水解產物（〗一 j )，或 鈦化合物和鈦以外之其他元素中至少選擇一種元素之化合 物或該化合物之前驅體之混合物加以水解而成水解產物（ 1 一 k )(下文中，上述水解產物或稱爲「含鈦水解產物 (A - 1 )」，和 (B )鹼性化合物，以及 (C )脂肪族二元醇之混合物加熱而得泥漿所構成。 水解產物（I — j ) ，（ I — k ) 經濟部智慈財產局員工消費合作社印製 水解產物（I - j )可由水解鈦化合物而得，水解產 物（I - k )係由鈦化合物和上述其他元素之化合物之混 合物加以水解而製得。 上述水解所用之鈦化合物，可使用如同前述之烷氧基 鈦，鹵化鈦化合物等。 使用鹵化鈦化合物做爲鈦化合物，乃係本發明之較佳 形態之途徑之一。以下就使用鹵化鈦化合物做爲鈦化合物 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -52- 585881 A7 B7 五、發明説明（5〇 ) 時之含鈦水解產物之調製方法具體說明之。使用烷氧基欽 之水解產物之調製也可以按照同樣方法進行。 鹵化鈦化合物之水解方法並無特別限制’例如前述調 製固態狀鈦化合物（I 一 a )之際，所使用①至⑤項之方 法均可採用。 ^ 上述水解方法雖無特別限制，但任何方法中，必須使 用過剩量之水和鹵化鈦化合物作用有利於水解反應之充分 進行。進行水解反應之溫度通常在1 0 0 t以下，尤以0 〜7 0 °C範圍爲較宜。 含鈦水解產物（A — 1 )可爲鹵化鈦化合物和上述其 他元素之化合物之混合物行水解而成水解產物。換言之， 該水解產物可在其他元素之化合物之共存下，水解鹵化鈦 化合物而製得。其他元素之化合物可單獨一種或二種以上 調配使用。 鹵化鈦化合物和其他元素之化合物之混合物所行水解 方法並無特別限制，例如上述調製固態狀鈦化合物（I -b )之際所使用①至⑨項之方法均可採用。 水解之際，鹵化鈦化合物中之鈦（丁 i )和其他元素 之化合物中之其他元素（E)之莫耳比率（e/t i )在 1/5 0〜5 0 / 1範圍爲宜。又’進行水解反應之溫度 通常在1 0 0°C以下，其中以0〜7 範圍爲較宜。 鹵化鈦化合物或鹵化鈦化合物和其他元素之化合物之 混合物在水解之際，由於鹵化鈦化合物之水解所產生鹵化 氫會造成液性呈現酸性。該酸性會使水解不能終結。因此 本紙張尺度適用中國國家標準（CNS) A4規格（210x 297公楚） (請先閱讀背面之注意事項再填寫本頁) it 口 經濟部智慧財產局g(工消費合作社印製 585881 A7 __B7 _ _ _ 五、發明説明（51 ) ，可添加上述之中和用鹼加以中和。中和之終點在p H 4 以上爲宜，又，中和宜在7 0 °C以上溫度進行。 上述水解所得水解產物（即含水氫氧化物凝膠或含水 複合氫氧化物凝膠）可直接做爲縮聚合反應觸媒使用’但 以經脫水乾燥成爲固態狀之水解產物（即，固態狀含鈦化 合物（I 一 k))爲較宜。 上述水解產物之乾燥可在常壓或減壓下，在固相狀態 或懸濁於高過水之沸點的液相狀態下進行，乾燥溫度並無 特別限制，但在3 0 °C以上而3 5 0 °C以下爲宜。又，乾 燥前，可將含水氫氧化物凝膠或含水複合氫氧化物凝膠加 以水洗，或乾燥後，將固態狀含鈦化合物（I - k )加以 水洗而去除水溶性成分亦可。又，乾燥宜快速進行。 按照上述方法所得固態狀含鈦化合物（I - k )，其 組成分隨所共存之其他元素之有無或量，有無水洗，乾燥 方法，乾燥程度而異，但從縮聚合反應活性之觀點，通常 以氫氧基（0H)和鈦（T 1 )之莫耳比率（〇H/T i )在Ο · 09以上而4以下，其中以Ο · 1〜3爲較宜， 尤以在0 · 1〜2之範圍爲最佳。氫氧基和鈦之莫耳比率 ’具體言之，可按照上述方法求得。 該固態狀含鈦化合物（I - k )在進行縮聚合反應之 溫度下，例如約2 8 0 °C下也有氫氧基殘存。 又，固態狀含鈦化合物（I - k )含有其他元素時， 該化合物中之鈦（T i )和其他元素（E )之莫耳比率（ E/T i )通常在1/50〜50/1 ，其中以1/40 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） (請先閱讀背面之注意事項再填寫本頁) .祕衣_ 訂 經濟部智態財產局員工消費合作社印製 -54- 585881 Α7 Β7 五、發明説明（52) 〜4 0/1爲較宜，尤以1/3 0〜3 0/1爲最佳。 上述含水氫氧化物凝膠，含水複合氫氧化物凝膠，固 態狀含鈦化合物（I - k )等之含鈦水解產物（A - 1 ) 通常其含氯量在0〜1 0 0 0 0 p pm，其中以〇〜 l〇〇ppm爲較宜。 鹼性化合物（B) 鹼性化合物（B )乃係在水溶液中顯示鹼性之化合物 ，具體言之，例如氫氧化四乙基銨，氫氧化四甲基銨，氨 水，氫氧化鈉，氫氧化鉀，N —乙基嗎啉，N —甲基嗎啉 等，其中以氫氧化四乙基銨爲較宜。 脂肪族二元醇（C ) 脂肪族二元醇（C)之具體例舉有乙二醇，1 ，3 — 丙二醇，丙二醇，1 ，4 一 丁二醇，新戊二醇，1 ，6- 己二醇，1 ，12 —十二烷二醇等，其中以使用乙二醇爲 較佳。 本發明有關之聚酯製造用觸媒係將上述含鈦水解產物 (A - 1 )和鹼性化合物（B )以及脂肪族二元醇（C ) 所構成之混合物加熱成爲泥漿而得。 上述混合液中，含有0 · 0 5〜3 0重量％之含鈦水 解產物（A - 1 )，其中以含有0 · 1〜2 0重量％爲較 宜，最好係含有0 · 5〜1 5重量％ ;鹼性化合物含有 0 · 5〜50重量％，其中1〜40重量％爲較宜，尤以 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ：297公釐） 0|丨 (請先閱讀背面之注意事項存填寫本萸) 訂 經濟部智慧財產局員工消費合作社印製 585881 A7 _____B7_ 五、發明説明（53 ) 2〜3 0重量％之比率爲最佳。又，殘餘爲脂肪族二元醇 〇 含鈦水解產物（A - 1 )之含有比率在0 · 0 5重量 %以上時，脂肪族二元醇（C )之添加量可以減少，而聚 合反應速度會加速。又，含鈦水解產物之含有比率在3 0 重量％以下時，加熱時之著色情形減少，因此，藉此所聚 合而得之聚酯之色相也變爲良好。 又，鹼性化合物（B )之含有比率在0 · 5重量％以 上時，會提升觸媒活性，鹼性化合物之含有比率低於5 0 重量％時，加熱時之著色會減少。 上述混合物之加熱溫度通常在1 0 0〜3 0 0°C，其 中以120〜250 °C爲較宜，尤以140〜200 °C爲 最佳，加熱時間在5分鐘〜1 0小時，其中以3 0分鐘〜 8小時爲較宜。 使用上述聚酯製造用觸媒製造聚酯之方法，可按照後 述方法進行，該聚酯製造用觸媒之使用比率，對芳香族二 羧酸和脂肪族二元醇之混合物重量計，以該觸媒中之金屬 重量換算，通常在0·0005〜0.2重量％，其中以 0·001〜0·05重量％範圍爲較宜。 聚酯製造用觸媒可以在酯化反應步驟中添加在聚合反 應容器中，也可以在縮聚合反應步驟之第一階段添加在反 應容器中。 本發明，上述聚酯製造用觸媒之外，尙可加上上述輔 觸媒化合物爲輔觸媒成分使用。輔觸媒成分以碳酸鎂，乙 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）· 56 - (請先閱讀背面之注意事項再填寫本頁}B7 V. Description of the invention (28) 0. 002 ~ 0. An amount of 3 mole% is appropriate. The above-mentioned catalyst for polyester production, which is composed of a solid titanium compound (I-a), a solid titanium-containing compound (I-b) and, if necessary, an auxiliary catalyst component (Π), undergoes polycondensation reaction. Just exist. Therefore, the addition of the polyester can be performed in any of the raw material slurry preparation step, the esterification step, and the liquid phase polycondensation reaction step. The catalyst can be added all at once or divided into several times. When the auxiliary catalyst component (Π) is used, it may be added in the same step as the solid titanium compound (I-a) or the solid titanium-containing compound (I-b), or may be added separately in different steps. The polyester obtained from the above-mentioned catalyst for polyester production can be melt-molded into a hollow molded article such as a bottle, a sheet, a film, a fiber, and the like, and among them, a bottle application is preferred. As compared with the germanium compound which has been used as a polycondensation reaction catalyst in the above-mentioned polyester manufacturing catalyst, the antimony compound can produce polyester with high catalyst activity. Furthermore, when polyester is produced by using the polyester manufacturing catalyst of the present invention, it is possible to obtain a polyester having better transparency, better hue, and lower acetaldehyde content than when using an antimony compound as a condensation polymerization reaction catalyst. The catalyst for polyester production according to another aspect of the present invention is composed of the following solid titanium compound (I-c) and auxiliary catalyst component (Π), or the following solid titanium-containing compound (I- d) and if necessary, the auxiliary catalyst component (Π) is used. Solid Titanium Compound (I-c) / Solid Titanium Compound (I (Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210X 297 mm) -31 -Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 585881 A7 B7 V. Description of the invention (29) ~ d) The solid titanium compound (I-c) of the present invention is prepared by hydrolyzing the titanium halide compound and then dehydrating and drying it. The titanium halide compound may be the same titanium halide compound as described above. The method for hydrolyzing the titanium halide compound is not particularly limited. For example, the methods ① to ⑤ used in the above-mentioned preparation of the solid titanium compound (Ia) can be used. In the present invention, there is no particular limitation on the hydrolysis method as described above, but in any method, it is preferable to use an excessive amount of water and a titanium halide compound to sufficiently perform the 7] C decomposition. The temperature at which the hydrolysis reaction is carried out is usually below 1000 t, particularly preferably in the range of 0 to 70 ° C. The solid titanium compound (I-c) can be used in combination with the auxiliary catalyst component (Π) composed of the auxiliary catalyst compound. On the other hand, the solid titanium-containing compound (I-d) is obtained by hydrolyzing and dehydrating a mixture of a titaniumized compound and a compound of the other elements described above. In other words, in the coexistence of compounds of other elements, hydrolysis of the titanium halide compound is performed, and the resulting precipitate is subjected to solid-liquid phase separation to obtain a solid titanium-containing compound (I-d). The method for hydrolyzing a mixture of a titanium halide compound and a compound of other elements is not particularly limited. For example, the methods ① to ⑨ used in the preparation of the solid titanium-containing compound (I-d) described above can be used. At the time of hydrolysis, the molar ratio of titanium (T 1) in the titanium halide compound and other elements (E) in other element compounds (E / T 丄 is in the range of 1/5 0 to 5 0/1. Also, hydrolysis The reaction temperature usually applies the Chinese National Standard (CNS) A4 specification (210X297 mm) at this paper scale. '---- (Please read the precautions on the back before filling this page) 4 、 1Τ -32- 585881 A7 B7 V 、 Description of the invention (30) 100t: The following, in which the range of 0 ~ 70t: is more suitable. The titanium halide compound or the mixture of the titanium halide compound and other element compounds is hydrolyzed by the hydrolysis of the titanium halide compound. When the hydrogen halide is generated, the liquid phase will be acidic. Due to the acidity, hydrolysis may not be terminated. Therefore, neutralization with a base as described above is also possible. The end point of neutralization is preferably p Η 4 or more. Neutralization should be carried out below 70 ° C. Hydrolysate of the titanium halide compound obtained by the above hydrolysis reaction or hydrolyzate of a mixture of a halide compound and other element compounds (a hydrous hydroxide gel or a hydrous composite hydroxide) gel) Dehydration and drying to obtain a solid titanium compound (I-c) or a solid titanium-containing compound (I-d). The above drying is suspended in a solid phase or a liquid phase above the boiling point of water under normal pressure or reduced pressure. The drying temperature is not particularly limited, but it is more suitable to be above 30 ° C and below 350 ° C. In addition, before drying, the aqueous hydroxide gel or the aqueous composite hydroxide gel is applied. After washing with water or drying, the solid titanium compound and the solid titanium-containing compound are washed with water to remove water-soluble components. It is also preferable to perform drying quickly. The solid titanium compound (I-c ) And solid titanium-containing compounds (I-d), the composition of which depends on the presence or absence of other elements, or the content, the presence or absence of washing, drying methods, and the degree of drying vary, but its hydroxyl (OH) and titanium The molar ratio (0h / buti) of (ding i) is usually 0 to 4 or less, among which 0.001 to 3 is more preferable, and the range of 0 to 0 1 to 2 is most preferable. The molar ratio of the hydroxyl group to the titanium group is specifically determined by the method described above. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 0! (Please read the precautions on the back before filling out this page) Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives • 33-585881 A7 B7 Printed by the Industrial and Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (31) 1 | Also, the solid state titanium compound (I-C) and the solid state titanium-containing compound 1 I (I — d) are at the temperature at which the polycondensation reaction proceeds. For example, about 1 8 I under 2 8 Cc, there are also hydroxyl groups remaining. 0 I I please 1 I solid state titanium-containing compound (I-d). Titanium in the compound first read 1 IT read 1 (i) and others The Mohr ratio (E / Ding 1) of the element (E) is usually referred to as 1 I at 1/5 〇 05 〇 / 1, where 1/4 〇 4 0/1 is better than 1 1 I should be especially 1 / 3 0 3 0, / 1 is the best (Matter 1 1 solid titanium compound (I — c) and solid titanium-containing compound (I refill this 4 — d) Its chlorine content is usually 0 ~ 1 0 0 0 0 0 0 PP m Among which 1 1 0 0 0 0 0 0 m 2 is more suitable 0 1 • 1 The solid titanium compound (1- C) and the above-mentioned auxiliary catalyst component (1 I Π), and the above-mentioned solid titanium-containing compound (I-d) may be used with the above-mentioned auxiliary catalysts: medium; component: (II;) if necessary. . > 1 1 The use of the above-mentioned auxiliary catalyst component (Π) is based on the above-mentioned solid titanium compound 1 I compound (I-C) titanium and the metal atom in the auxiliary catalyst component (Π) 1 1 I ear ratio [ (Π) / (I — c)] y or the above-mentioned solid state titanium-containing (m-complex (I-d)) titanium and other elements and the metal atomic ratio of the auxiliary catalyst component (Π) 1 [ (Π) / (I — d)] in 1 /! 1 5 0 5 0/1 Among which 1/40 4 0/1 is more suitable 1 I especially in the range of 1/3 0 3 0/1 It is the best. 1 1 | When using phosphorus compounds such as phosphate or phosphite, the conversion is based on 1 1 metal atoms contained in the phosphorus compound, and when a magnesium compound is used as the auxiliary Mtm catalyst component (Π) 1 1 Weight ratio of titanium atom in solid titanium compound (I-c) to magnesium compound in 1 I [Mg / (I-C)] The above solid 1 1 1 National Standard (CNS) A4 Specification (210X297 mm) -34-585881 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _ __B7 V. Description of the Invention (32) Titanium and titanium in the state titanium compound (I-d) The weight ratio of other elements and magnesium atoms in the magnesium compound [Mg / (I-d)] is usually 0.  01 or more, with 0 as the value.  06 to 10 is preferable, and the amount in the range of 06 to 5 is most preferable. When a magnesium compound is used within this range, the obtained polyester has excellent transparency. The polyester can be produced by using the polyester manufacturing catalyst described above. The polycondensation reaction uses a solid state titanium compound (I-c) or a solid state titanium-containing compound (I-d) to reduce polycondensation. The aromatic dicarboxylic acid unit in the content is generally converted into a metal atom in the range of 0.001 to 0.2 mol%, and it is preferable to use 0. 002 to 0.1 mol%. Co-catalyst component (π) used together with solid titanium compound (I-c), or co-catalyst component (π) used with solid titanium-containing compound (I-d) if necessary, in low polycondensate The aromatic dicarboxylic acid units, metal atom conversion, usually use 0 · 001 ~ 0 · 5 mole%, of which 0 · 002 ~ 0. An amount of 3 mole% is preferred. Polyesters such as polyethylene terephthalate produced using the polyester manufacturing catalysts described above have excellent hue, particularly excellent transparency, and have a low acetaldehyde content. The polyesters produced by the aforementioned polyester manufacturing catalysts are each used as raw materials for various moldings, such as melt molding into hollow moldings such as bottles, sheets, films, fibers, etc. should. As the method for forming a bottle, a sheet, a film, a fiber, or the like from the polyester, for example, polyethylene terephthalate, a conventionally known method can be used. (Please read the precautions on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) -35- 585881 A7 B7 V. Description of the invention (33) (Please read the back Please fill in this page again for the matters needing attention) Compared with the germanium compound 'antimony compound' which has been used as a polycondensation reaction catalyst, the above polyester production catalyst can produce polyester with higher catalyst activity. In addition, when polyester is produced by using the catalyst for polyester production, a polyester having superior transparency and hue, and less acetaldehyde content can be obtained compared with the case where an antimony compound is used as a condensation polymerization reaction catalyst. Furthermore, the polyethylene terephthalate obtained by using the polyester manufacturing catalyst and its molded article have excellent transparency and hue, and have a low acetaldehyde content. In addition, the catalyst for polyester production according to another aspect of the present invention is composed of the following solid titanium compound (I-e), solid titanium compound (I-f), and solid titanium-containing compound (I-g). Or a solid titanium-containing compound (I-h) ', if necessary, it is composed of the following auxiliary catalyst component (Π). Solid state titanium compound (I-e), (I-f), solid state titanium-containing compound (I-g), (I_h) Intellectual Property Bureau of the Ministry of Economic Affairs g (industrial and consumer cooperatives printed the solid titanium of the present invention Compound (I-e) is an acidic solution of a hydrolysate of a titanium halide compound obtained by hydrolyzing a titanium halide compound by contacting water with a titanium halide compound and water. The base is made alkaline, and then adjusted to p Η 2 ~ 6 with an acid. The resulting precipitate is made by dehydration and drying. The solid titanium compound (I-f) is an acidic solution of the hydrolysate of the titanium halide compound obtained by contacting the titanium halide compound with water and hydrolyzing the titanium halide compound, and directly using an alkali. It is adjusted to p Η 2 ~ 6, and the resulting precipitate is dehydrated and dried to obtain a solid titanium compound (I-e) and a solid titanium compound (This paper size applies Chinese National Standard (CNS) A4 specifications ( 210X297 mm) · 36-585881 A7 _____B7 V. Explanation of the invention (34) 1-ί) The titanium halide compound used is the same as the titanium halide compound described above. (Please read the precautions on the back before filling in this Page) In any case of preparing the solid titanium compound (I-e) and the solid titanium compound (1-ί), the method of hydrolyzing the titanium halide compound is not particularly limited. For example, in the case of the above-mentioned preparation of the solid titanium compound (1-a) The methods of items ① to ⑤ can be used. In the present invention, the method of hydrolysis is not particularly limited as described above, but in any method, an excess amount of water and a titanium halide compound are used to make the hydrolysis fully proceed. The necessary conditions. The temperature of the hydrolysis reaction is usually below 100 ° C, especially in the range of 0 ~ 70 ° C. The hydrolysis of the titanium halide compound according to the above method can obtain the acidity of the hydrolyzate containing the titanium halide compound. Solution. This acidic solution usually shows a degree of acidity of pH 时. When the Intellectual Property Bureau of the Ministry of Economic Affairs g (printed by the Industrial and Consumer Cooperative § weekly solid solid compounds (I-e)), the above-mentioned acidic solution containing the hydrolysate, use an alkali It is adjusted to ρ Η 9 ~ 1 2, which is preferably adjusted to ρ 9 ~ 1 1, and then adjusted with acid to ρ 2 to 6, where adjusted to ρ 3 ~ 6 is more appropriate. At this time, the temperature is usually at Below 50 ° C, it is more suitable to be below 40 ° C. When adjusted to ρ Η 2 ~ 6 according to the above, the precipitate can be generated. The alkali used above is, for example, gas, sodium hydroxide, potassium hydroxide , Sodium carbonate, potassium carbonate, etc., among which ammonia and sodium hydroxide are more suitable. In addition, the above-mentioned acids, such as acetic acid, nitric acid, etc., among which acetic acid is more suitable. After it becomes alkaline, the paper size applies the Chinese National Standard (CNS) A4 (210x297) -37- 585881 Α7 Β7 V. Description of the invention (35) When it becomes acidic again to cause precipitation, the solid and liquid described below can be used. The dehydration step after phase separation shortens the time. In addition, in the obtained solid titanium compound (I-e), nitrogen, sodium, potassium, and the like derived from the base are also relatively small, and a polycondensation reaction having excellent polycondensation activity and a polyester having excellent quality can be obtained. Media. When preparing a solid titanium compound (I-f), the above-mentioned acidic solution containing a hydrolyzed product is adjusted to ρ 〜 2 to 6 with a base, and ρ Η 3 to 6 is more preferable. At this time, the temperature is usually 50 ° C or less, and preferably 40 ° C or less. When the pH is adjusted to 2 to 6 as described above, a precipitate may be generated. The bases used above are the same as those used when preparing solid titanium compounds (I-e). Among them, ammonia and sodium hydroxide are preferred. According to the above method, the acidic solution containing the hydrolysate is adjusted to ρ Η 2 ~ 6, so that when the precipitate is generated, the dehydration step time after the solid-liquid phase separation can be shortened. Further, in the obtained solid titanium compound (I-f), residuals of nitrogen, sodium, potassium, etc. derived from the alkali are reduced, and a polyester catalyst having excellent polycondensation reaction activity and excellent quality can be obtained. In any case where a solid titanium compound (I-e) and a solid titanium compound (I ί) are prepared, if the above acidic solution is adjusted to ρ Η 2 ~ 6 ', a precipitate will be generated, but the precipitate is In this stage, it is a so-called hydrous hydroxide gel of orthotitanic acid. The aqueous hydroxide gel is dehydrated and dried to obtain the solid titanium compound (I-e) and the solid titanium compound (I-f) according to the present invention. In addition, a part of the hydroxyl groups contained in the aqueous hydroxide gel is removed by dehydration and drying. According to the above method, adjust the acid solution to ρ Η 2 ~ 6, so that the paper size can be applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) ----------- (Please read the back first (Notes on this page, please fill out this page),-585881 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (36) The precipitate is generated, and the precipitate is separated into solid and liquid phases, and then dried. Obtain a solid titanium compound (I-e) or a solid titanium compound (I-ί) (please read the precautions on the back before filling this page) 〇 Drying can be in the solid state or suspended under normal or reduced pressure It is carried out in a liquid phase state higher than the boiling point of water, and although the drying temperature is not particularly limited, it is usually preferably above 30 ° C and below 350 ° C. Before drying, the aqueous hydroxide gel is washed with water, or after drying, the solid titanium compound (I-e) and the solid titanium compound (I-f) are washed with water to remove water-soluble components. Also, drying should be performed quickly. The solid state titanium-containing compound (I-g) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is a mixture of a titanium halide compound and a compound of the other elements mentioned above with water, and an acidic solution containing a hydrolysate obtained by hydrolyzing the titanium halide compound After the alkali becomes alkaline, the acid is adjusted to PΗ 2 ~ 6, and the resulting precipitate is dehydrated and dried to make it. The solid titanium-containing compound (I-h) is a titanium halide compound and other than the above titanium. At least one of the other elements is selected from the compound of the element or a mixture of the precursors of the compound. The acidic solution containing the hydrolysate of the titanium halide compound obtained by hydrolyzing the titanium halide compound by contacting with water is directly adjusted to P Η 2 ~ 6 with an alkali. The resulting precipitate is prepared by dehydration and drying. As the titanium halide compound used for preparing the solid state titanium-containing compound (I-g) and the solid state titanium-containing compound (I-h), the same titanium halide compounds as mentioned above can be mentioned. Compounds of other elements can be used alone or in combination of two or more. I paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 585881 A7 B7__ V. Description of the invention (37) (Please read the notes on the back before filling this page) Modulation of solid titanium-containing compounds (I-g ) And solid titanium-containing compound (I-h), there is no particular limitation on the method of hydrolyzing a mixture of a halogenated compound and compounds of other elements. For example, when preparing the solid titanium-containing compound (I-b) All the methods ① to 均可 can be used. In the present invention, although the hydrolysis method is not particularly limited as described above, in any case, it is necessary to use an excess amount of water with a mixture of a titanium halide compound and a compound of other elements to sufficiently proceed the hydrolysis reaction. During hydrolysis, the molar ratio (E / T i) of titanium (T i) in the titanium halide compound and other elements (E) in other element compounds is preferably in the range of 1/5 0 to 5 0/1. . In addition, the temperature at which hydrolysis is performed is usually 100 t: or less, and a range of 0 to 70 ° C is preferable. An acidic solution containing a hydrolyzate of a titanium halide compound and a compound of other elements can be obtained by hydrolyzing a mixture of a titanium halide compound and a compound of other elements as described above. The p Η 値 of this acidic solution is usually about Η Η. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Modulated solid titanium-containing compounds (I-g). At this time, the acidic solution containing the above-mentioned hydrolysate and other element compounds is adjusted to ρ Η 9 ~ 12 with a base, among which the basicity is adjusted to ρ 9 ~ 11, and then adjusted to ρ Η 2 ~ 6 with an acid, where It is more appropriate to adjust it to ρΗ3 ~ 6. The temperature at this time is usually below 50 ° C, especially below 40 ° C. By adjusting the pH to 2 to 6 as described above, a precipitate can be generated. The same bases used for the aforementioned preparation of the solid titanium compound (I-e) can be used. Among them, ammonia and sodium hydroxide are preferred. In addition, the size of the paper used above applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -40-585881 A7 B7 V. Description of the invention (38) The acid can also be used to prepare the solid state compound (1- e) The same acids are used, with acetic acid being preferred. Once the acidic solution containing the hydrolysate and other element compounds is made alkaline as described above, and then changed to acidic to produce a precipitate, the time for the dehydration step after solid-liquid phase separation can be shortened. In addition, in the obtained solid titanium-containing compound (I-g), the residual amount of nitrogen, sodium, potassium, etc. derived from the base also becomes smaller, and the polycondensation reaction is excellent, and a polyester for high quality polyester can be obtained. Catalyst for ester production. When preparing a solid state titanium-containing compound (I-h) ', the above-mentioned acidic solution of the compound containing the hydrolysate and other elements is adjusted to pH 2 to 6 with a base, and more preferably adjusted to pH 3 to 6. The temperature at this time is usually below 50 t, especially below 40 ° C. According to the above adjustment, p Η 2 to 6 can cause precipitation. The bases used above may be the same bases used for the preparation of the solid titanium compound (I-e). Among them, ammonia and sodium hydroxide are preferred. When the acidic solution containing a hydrolysate and a compound of other elements is adjusted to p Η 2 to 6 according to the method described above to produce a precipitate, the time required for the dehydration step after solid-liquid phase separation can be shortened. In addition, the residual amount of nitrogen, sodium, and potassium derived from the base in the obtained solid titanium-containing compound (I-h) is also reduced, and a polyester catalyst with excellent polycondensation reaction activity and excellent quality can be obtained. In any case where a solid state titanium-containing compound (I-g) and a solid state titanium-containing compound (I-h) are prepared, a precipitate can be generated by adjusting the acidic solution to p Η 2 to 6, but the precipitate At this stage, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this tribute) tr Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -41-585881 A7 B7__ 5. Description of the invention (39) (Please read the precautions on the back before filling this page) So-called orthotitanic acid-containing water-containing composite hydroxide gel containing water-containing hydroxide. The aqueous composite hydroxide gel is dehydrated and dried to obtain the solid titanium-containing compound (I-g) and the solid titanium-containing compound (I-h) related to the present invention. Furthermore, a part of the hydroxyl groups contained in the aqueous composite hydroxide gel is removed by the above-mentioned dehydration and drying. The above drying can be performed under normal pressure or reduced pressure, in a solid phase state or suspended in a liquid phase state higher than the boiling point of water, and the drying temperature is not particularly limited. C is preferred. Before drying, the water-containing composite hydroxide gel is washed with water. After drying, the solid-state compound (I-g) and the solid-state titanium-containing compound (I-h) are washed with water to remove water-soluble components. feasible. Also, drying should be performed quickly. According to the solid titanium compound (I-e), solid Chin compound (I-f), solid titanium-containing compound (I-g), and solid titanium-containing compound (I-h) obtained according to the above, the composition is as follows The presence or absence of other elements differs in amount or amount, with or without water washing, drying method, and degree of drying, but the molar ratio (OH / T 丄) of the hydroxyl group (0H) and titanium (Ti) is usually 0. 09 Above and below 4 are preferable, among which, it is more suitable to print it from 0.1 to 3 of the Intellectual Property Bureau's Consumer Cooperatives, especially from 0.1 to 2. The molar ratio of hydroxyl group to titanium can be obtained by measuring the attached water and heating and removing the water according to the method described above, and the solid titanium compound (I-e) and the solid titanium compound (1-a: f) can be obtained in the solid state. At the temperature at which the titanium-containing compound (I-g) and the solid titanium-containing compound (I-h) undergo condensation polymerization reaction, for example, at about 280 ° C, hydroxyl groups remain. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -42, 585881 A7 B7__ V. Description of the invention (40) (Please read the precautions on the back before filling this page) Solid titanium-containing compounds ( Ig) and solid titanium-containing compound (Gongyih), the molar ratio (E / Ti) of titanium (but 1) and other elements (E) in the compound is preferably 1/50 ~ 50/1 'Among them, 1/40 ~ 40/1 is more suitable, especially 1/30 ~ 30/1. The solid titanium compound (I-e), the solid titanium compound (I-f), The titanium compound (I-g) and the solid titanium-containing compound (I-h) have a chlorine content of usually 0 to 1000 ppm, and preferably 0 to 100 ppm. When necessary, the solid titanium compound (I-e) ), Solid state titanium compound (I-f), solid state titanium-containing compound (I-g) or solid state titanium-containing compound (I-h) as auxiliary catalyst component (Π), the aforementioned auxiliary catalyst can be used Those with the same composition include magnesium compounds such as magnesium carbonate and magnesium acetate; calcium compounds such as calcium carbonate and calcium acetate; zincation such as zinc chloride and zinc acetate The auxiliary catalyst compounds can be used alone, or two or more can be used as auxiliary catalyst ingredients. The amount of the above auxiliary catalyst ingredients (Π) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs should be based on the above solid state. Molar ratio of titanium in the titanium compound (I-e) or solid titanium compound (I-f) and the metal atom in the auxiliary catalyst component (Π) [(Π) / (ι-e) or (Π ) / (]; A f)], or the titanium and other elements in the solid state titanium-containing compound (I-g) or the solid state titanium-containing compound (I-h) and the metal in the auxiliary catalyst component (Π) Mole ratio of atom [(n) // (I ~ g) or (Π) / (Ι-h)] is preferably 1/50 to 50/1 ', of which 1/40 to 40/1 is more suitable Good, especially the $ paper standard is applicable to the Chinese National Standard (CNS) A4 specification (21〇 ×; 297 mm) -43- 585881 A7 B7 V. Description of the invention (41) (Please read the precautions on the back before filling this page ) The best dosage is in the range of 1/3 0 to 3 0/1. In addition, when a dish compound such as phosphate or citrate is used, it is converted by the metal atom contained in the dish compound. When a magnesium compound is used as the auxiliary catalyst component (Π), the weight ratio of the titanium in the solid titanium compound (I-e) or (I-f) to the magnesium atom in the magnesium compound [Mg / (I-e ) Or (; [一 f)] 'or the weight ratio of titanium and other elements in the solid state titanium-containing compound (I-g) or the solid state titanium-containing compound (I-h) and the magnesium atom in the magnesium compound [ Mg / (I-g) or (I-h)] is greater than or equal to 0. 01, of which 0. 06 to 10 is preferable, and an amount in the range of 0. 06 to 5 is most preferable. When a magnesium compound is used within the above range, a polyester having excellent transparency can be obtained. The method for producing polyester using the above polyester production catalyst is described later. In the polycondensation reaction, a solid state titanium compound (I-e), a solid state titanium compound (I-ί), and a solid state titanium-containing compound (I A g) or solid state titanium-containing compound (I a h), calculated for the aromatic dicarboxylic acid units in the low polycondensate, using a metal atom conversion of 0 · 001 ~ 0. 2 mole%, of which the use of 0.002 ~ 0.1 mole% is more preferred. Printed in solid state titanium compound (I-e), solid state titanium compound (I-f), solid state titanium-containing compound (I-g) or solid state titanium-containing compound (I-h) ) In addition, when the auxiliary catalyst component (Π) is used, the amount of the auxiliary catalyst component (Π) is converted to the metal atom of the aromatic dicarboxylic acid unit in the low polycondensate, using 0 · 001 ~ 0.5 mole% is preferred, and 0.002 to 0.3 mole% is more preferred. The above-mentioned solid titanium compound (I-e), solid titanium compound-44 · This paper size is applicable to Chinese National Standard (CNS) A4 specification (210x297), 585881 A7 B7 V. Description of the invention (42) (Please read first Note on the back page, please fill in this page) (ί 一 f), choose one of the solid titanium-containing compounds (I-g) and solid titanium-containing compounds (I-h), and if necessary, try again. The catalyst composed of the auxiliary catalyst component (Π) may be present during the condensation polymerization reaction. Therefore, the addition of the catalyst can be performed in any step such as a raw material slurry preparation step, an esterification step, a liquid phase condensation polymerization step, and the like. It is also possible to add the total amount of catalyst at one time, or divide it into several times. In addition, when the auxiliary catalyst component (Π) is used, a solid state titanium compound (I-e), a solid state titanium compound (I-f), a solid state titanium-containing compound (I-g), or a solid state may be added. Titanium-containing compound (I-h) can be added in the same step, or added in different steps. The above-mentioned catalysts for polyester production are particularly composed of a solid titanium compound (I-e), (I-ί) 'a solid titanium-containing compound (I-g) or a solid titanium-containing compound (I-h) and an auxiliary A catalyst composed of a catalyst component (Π), and the auxiliary catalyst component (Π) is a magnesium compound catalyst, which is most suitable for a catalyst for manufacturing polyethylene terephthalate. This solid state titanium compound (I-e), solid state titanium compound (I-ί), solid state titanium-containing compound (I-g) or solid state thorium-containing compound (I-h) and magnesium compound constitute the Ministry of Economic Affairs. When the Intellectual Property Bureau employee consumer cooperative prints a catalyst to manufacture polyethylene terephthalate, for example, the raw materials can be terephthalic acid or its ester-forming derivative and ethylene glycol or its ester-forming derivative. If necessary, an aromatic dicarboxylic acid other than terephthalic acid and / or an aliphatic diol other than ethylene glycol is added, and esterified according to the method described below, and the liquid phase condensation polymerization reaction is performed, and the solid phase condensation polymerization is performed when necessary. reaction. At this time, the amount of terephthalic acid or its ester-forming derivative is 100 mol% of aromatic dicarboxylic acid, and more than 80 mol% is used. The most -45- Standard (CNS) A4 specification (210X297 mm) 585881 A7 B7__ V. Description of the invention (43) It is good to use more than 90 mole% of ethylene glycol or its ester-forming derivative. For 100 mol% of aliphatic diol, it is best to use 80 mol% and more than 90 mol%. -(Please read the precautions on the back before filling this page) The polyethylene terephthalate prepared according to the above method has a content of 1 to 20 ppm, especially 1 to 100. The range of PPm is suitable, and the magnesium content is in the range of 1 ~ 2 0 0 ρ ρ η, especially in the range of 1 ~ 100P Pm. Moreover, the weight ratio (Mg / Ti) of titanium and magnesium contained in the polyethylene terephthalate is 0.  01 or more, among which 0. 06 to 10 is preferable, and the most preferable range is 0. 06 to 5. In addition, the chlorine content of the polyethylene terephthalate is in the range of 0 to 1 0 0 p pm, and preferably in the range of 0 to 1 0 0 p pm. The above polyethylene terephthalate has excellent hue, is particularly excellent in transparency, and has a low acetaldehyde content, and is particularly suitable for bottle making applications. The polyester obtained from the above-mentioned catalyst for polyester production can be used as a raw material for various molded articles, for example, melt-molded into hollow molded articles such as bottles, sheets, films, fibers, etc., but it is preferable to provide bottle-making applications. Printing method for polyester, such as polyethylene terephthalate, produced by the above-mentioned polyester manufacturing catalysts by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. A method known in the past may be used. Compared with the germanium compound and antimony compound that have been used as polycondensation reaction catalysts, the polyester manufacturing catalysts described above can be used to produce polyesters with higher catalytic activity. Further, compared with the case where an antimony compound is used as a polycondensation catalyst, it is possible to obtain a polyester having transparency, excellent hue, and low acetaldehyde content. The catalyst for polyester manufacturing related to another form of the present invention can be printed on the following paper size to the Chinese National Standard (CNS) A4 specification (210X297 mm) -46 · 585881 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs _B7 ____ 5. Description of the invention (44) It is composed of solid titanium compound (I-1) and auxiliary catalyst component (π) if necessary. Solid state titanium compound (I-i) The solid state titanium compound (I-i) of the present invention is prepared by dehydrating and drying a titanium hydroxide compound. The titanium hydroxide compound can be produced, for example, by hydrolyzing a titanium compound. The titanium compound used for the hydrolysis is, for example, a titanium halide compound, a titanium alkoxide compound, and the like. Examples of the titanium halide compound include the same titanium halide compounds as described above, and examples of the titanium alkoxide compound include titanium butoxide, titanium tetraisopropoxide, and the like. The use of a titanium halide compound as the titanium compound in the present invention is one of the more preferable ways of the present invention. The method for hydrolyzing the titanium halide compound is specifically explained as follows. 'In addition, the hydrolysis of the titanium alkoxide compound can also be carried out in the same manner. The method for hydrolyzing the titanium halide compound is not particularly limited. For example, the methods ① to ⑤ used in the above-mentioned preparation of the solid titanium compound (I-a) may be used. As described above, although the hydrolysis method is not particularly limited, in any method, it is necessary to use an excessive amount of water and a halogenated halogen compound in order to achieve sufficient hydrolysis. The temperature for carrying out the hydrolysis reaction is usually below 60 ° C, and among them, the axis range of 0 to 50 C is preferred. When the hydrolysis reaction proceeds at the above-mentioned range of temperature, there is a tendency to obtain a solid compound having a low degree of crystallinity. When the titanium halide compound is hydrolyzed, other elements may be used as described above. The paper size applies the Chinese National Standard (CNS) A4 (210X29? Mm) _ 7 Φ _ | (Please read the precautions on the back before filling This page) Order 585881 A7 B7 V. Description of invention (45) Coexistence of compounds. These other element compounds can be used alone or in combination. (Please read the precautions on the back before filling in this page) Mole ratio (E / 丁 χ) of titanium (but 1) in titanium halide compounds and other elements (E) in other element compounds during the hydrolysis reaction It is advisable to drive around E from 1/5 0 to 5 0/1. In addition, the temperature of the hydrolysis-resistant spleen is usually 6 Ot: or less, and a range of 0 to 5 is preferable. When hydrolysis is performed in the above temperature range, there is a tendency to obtain a solid titanium compound having a low degree of crystallinity. When the halogenated chitin compound is hydrolyzed, hydrogen halide is generated due to the hydrolysis of the halogenated chitin compound, causing the liquidity to be acidic. This acidity may cause a situation in which the hydrolysis reaction cannot be terminated, and therefore, it can be neutralized by using a neutralization test as described above. The end point of neutralization is preferably above P Η 4, and the neutralization is preferably performed at 60 ° C or less, and it is more preferable to perform at a temperature of 0 to 50 ° C. When carried out at a temperature in the above range, there is a tendency to obtain a solid compound having a low degree of crystallinity. The titanium-containing compound obtained from the above-mentioned hydrolysis reaction, or a compound containing titanium and other elements, is at this stage an aqueous hydroxide gel called so-called orthotitanic acid. The hydrous hydroxide gel is dehydrated to form a solid hydrolysate (ie, a solid titanium compound). According to this drying process, a part of the hydroxyl groups can be removed. The above-mentioned hydrolysate can be dried under normal pressure or reduced pressure, or in a solid phase state or suspended in a liquid phase state with a high boiling point over water. The drying temperature is not particularly limited, and the temperature is above 30 ° C and 3 Below 50 ° C, in which 30 paper sizes are applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -48-585881 A7 B7 V. Description of the invention (46) ~ 2 0 0 t: The range is more than should. When the hydrolysate is dried at a temperature in the above range, a solid titanium compound having a low degree of crystallinity tends to be obtained. ----------- (Please read the precautions on the back before filling in this page) Also, before drying, 'wash the hydroxide hydroxide gel with water, or after drying, apply the solid titanium-containing compound. Wash with water and remove water-soluble components. Also, drying should be performed quickly. The solid state titanium compound (I-i) obtained according to the above method has a crystallinity of 50% or less calculated from an X-ray diffraction spectrum of 2 (9 (diffraction angle) in the range of 18 to 3 5 °, in which 4 is 5% or less is preferred, preferably 40% or less, or an amorphous compound. A solid titanium compound having a degree of crystallinity within the above range has excellent activity as a polycondensation catalyst for polyester production. Solid state The crystallinity of the titanium compound (I-1) can be measured, for example, as follows. Fig. 1 shows the X-ray diffraction spectrum used for the method for measuring the crystallinity of the solid titanium compound. Figure 1 (A)) and the X-ray diffraction spectrum of the amorphous solid titanium compound (Figure 1 (B)). The baseline is set at 18 ° ~ 3 5 °. The position of 2 0 = 2 8 · 5 ° of the light diffraction spectrum (the position that does not hinder the crystallization peak) is the benchmark printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives. Transcript (Figure 1 (C)). From the X-ray diffraction spectrum synthesized according to the above method, The area (I ◦) of the X-ray diffraction spectrum (with the background removed) and the area of the X-ray diffraction spectrum (with the background removed) of the amorphous solid titanium compound were obtained with diffraction angles ranging from 18 ° to 3 5 ° ( Ia), take (IQ-ia) / (lQ) x100-49 · This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 585881 A7 B7 V. Invention Note (47) Degree of crystallization (%). The composition of the solid titanium compound (I-1) depends on the presence or absence of other coexisting elements, the presence or absence of washing, and the drying method. The dry_stomach and stomach_ are different, but their hydrogen and oxygen Molar ratio (〇H / T 1) of titanium (〇H) and titanium (Ti), usually at 0.  09 or more and 4 or less, among which 0 · 1 to 3 is preferable, and in the range of 0 · 1 to 2 circles, it is most preferable from the viewpoint of polycondensation activity. The molar ratios of hydroxyl and titanium are determined by determining the amount of water attached and the water removed by heating. The molar ratio of hydroxide and titanium; specifically, can be obtained according to the method described above. When the solid titanium compound (I-i) contains other elements, the molar ratio (E / buti) of titanium (T i) and other elements (E) in the compound is 1/50 to 50/1. The range is preferably 1/40 ~ 4 0/1, especially 1/3 0 ~ 3 0 /, 1 is the best. The chloride content of the solid amidine compound (I-i) is usually between 0 and 100,000. 1! 1, among which 0 to 100 port 0111 is more suitable. The solid titanium compound (I-i) still has hydroxyl groups remaining at a temperature at which a polycondensation reaction is possible, for example, at about 280 ° C. The above-mentioned solid titanium compound (I_i) can be used with the auxiliary catalyst component (Π) if necessary. The auxiliary catalyst component (Π) used when necessary can be the same as the aforementioned auxiliary catalyst component, among which are magnesium compounds such as magnesium carbonate and magnesium acetate; calcium compounds such as calcium carbonate and calcium acetate; zinc chloride and zinc acetate Other zinc compounds are preferred. The auxiliary catalyst compound can be used alone or in combination of two or more as the auxiliary catalyst component. The amount of the above auxiliary catalyst component (Π) is based on the above solid titanium compound ---------— (Please read the precautions on the back before filling this page) Order the smart money of the Ministry of Economic Affairs / I Bureau staff consumption The paper size printed by the cooperative applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -50- ^ 5881 A7 S '—------- 5. Description of the invention (48) (Please read the note on the back first Please fill in this page for further information) Chin in the substance (1-1) (when the solid titanium compound (I-1) contains other elements' including Chin and other elements) and the metal in the auxiliary catalyst component (π) Mole ratio [(Π) / (Ι-i)] of the atom is in the range of 1/5/5 ~ 50/1 ', among which 1/40 ~ 4〇 /; [is more suitable, especially 1/3 0 ~ 3 0/1 range is best used. When a phosphorus compound such as a phosphonate or a phosphite is used, it is converted into a metal atom contained in the phosphorus compound. The method for producing polyester using the above-mentioned catalyst for polyester production is carried out according to the method described later. The amount of solid titanium compound (I-i) in the polycondensation reaction is based on the aromatic dicarboxylic acid units in the low polycondensate. Metal atom conversion 'is in the range of 0.001 ~ 〇. 2 mole%, of which 〇. 002 ~ 0. 1 mole% is more suitable. In addition to the solid titanium compound (I-i), when the auxiliary catalyst component (Π) is added, the amount of the auxiliary catalyst component (π) is based on the aromatic dicarboxylic acid unit in the low polycondensate, and the metal atom Conversion in 0.  0 〇 1 ~ 〇.  5 mol%, of which 0.002 to 0.3 mol% is more suitable. The catalyst composed of the Intellectual Property Bureau of the Ministry of Economic Affairs (the industrial and consumer cooperatives printed the above solid titanium compound (I-i) and the auxiliary catalyst component (Π) added if necessary, should exist during the condensation polymerization reaction That is why, the catalyst can be added in any of the raw material slurry preparation step, the esterification step, the liquid phase condensation polymerization step, etc. Also, the catalyst can be added all at once or in batches. In addition, when the auxiliary catalyst component (Π) is used, it can be added in the same step as the solid titanium compound (I-i), or it can be added in different steps. This paper size applies the Chinese National Standard (CNS) A4 Specifications (210X297mm) -51-A7 B7 V. Description of the Invention (49) (Please read the precautions on the back before filling this page) Polyester made from the above polyester manufacturing catalyst, preferably poly Ethylene terephthalate, can be melt-molded into hollow moldings such as bottles, sheets of 'thin' film 'fibers, etc., among which the use of providing bottles is more suitable. The aforementioned polyester manufacturing catalyst, Condensation polymerization compared to previous uses The germanium compounds and antimony compounds used as media can be made into polyester with higher catalytic activity. In addition, compared with the use of antimony compounds as condensation polymerization catalysts, it can be made transparent, has excellent hue, and has low acetaldehyde content. The polyester. Also, another aspect of the present invention. The polyester manufacturing catalyst is a hydrolysate ([a] j) obtained by hydrolyzing a titanium compound (A-1), or a compound selected from at least one element of the titanium compound and other elements other than titanium or a precursor of the compound Hydrolysate (1-k) (hereinafter referred to as "titanium-containing hydrolysate (A-1)", and (B) basic compound, and (C) aliphatic The mixture of glycols is heated to obtain a slurry. Hydrolysate (I — j), (I — k) The hydrolysate (I-j) printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs can be obtained by hydrolyzing titanium compounds, The hydrolysate (I-k) is prepared by hydrolyzing a mixture of a titanium compound and a compound of the other elements mentioned above. As the titanium compound used for the above hydrolysis, the aforementioned titanium alkoxide, titanium halide compound, etc. can be used. Titanium halide As a titanium compound, the compound is one of the preferred forms of the present invention. The following uses a titanium halide compound as a titanium compound. This paper applies the Chinese National Standard (CNS) A4 standard. (210X297 mm) -52- 585881 A7 B7 5. The method of preparing the titanium-containing hydrolysate at the time of the invention description (50) is specifically explained. The preparation of the hydrolysate using alkoxyqin can also be performed in the same way. Halogenation There is no particular limitation on the hydrolysis method of the titanium compound. For example, in the case of preparing the solid titanium compound (Ia), the methods ① to ⑤ may be used. ^ Although the above hydrolysis method is not particularly limited, any method may be used. The excess amount of water and titanium halide compound must be used to facilitate the full progress of the hydrolysis reaction. The temperature of the hydrolysis reaction is usually below 100 t, especially in the range of 0 ~ 70 ° C. Titanium-containing hydrolysis products (A -1) may be a hydrolysate obtained by hydrolyzing a mixture of a titanium halide compound and a compound of the other elements mentioned above. In other words, the hydrolysate may be obtained by hydrolyzing the titanium halide compound in the coexistence of compounds of other elements. Other elements The compound can be used singly or in combination of two or more. Hydrolysis method of a mixture of a titanium halide compound and a compound of other elements There is no particular limitation. For example, the methods ① to ⑨ used in the preparation of the solid titanium compound (I -b) described above can be used. During hydrolysis, the titanium (butyl) and other compounds in the halogenated titanium compound are used. The molar ratio (e / ti) of the other elements (E) is preferably in the range of 1/5 0 to 50 0/1. The temperature of the hydrolysis reaction is usually below 100 ° C, in which 0 to The range of 7 is more suitable. When the titanium halide compound or a mixture of titanium halide compound and other element compounds is hydrolyzed, the hydrogen halide generated by the hydrolysis of the titanium halide compound will cause the liquid to show acidity. This acidity will prevent the hydrolysis from ending. Therefore, this paper size applies the Chinese National Standard (CNS) A4 specification (210x 297 cm) (Please read the precautions on the back before filling this page) it Intellectual Property Bureau of the Ministry of Economy g (printed by the Industrial and Consumer Cooperatives 585881 A7 __B7 _ _ _ 5. Description of the invention (51), the above neutralization can be added and neutralized with a base. The end point of neutralization is preferably above p H 4, and neutralization should be performed at a temperature above 70 ° C. The above hydrolysis The obtained hydrolysate (that is, an aqueous hydroxide gel or an aqueous composite hydroxide gel) can be directly used as a condensation polymerization reaction catalyst, but is hydrolyzed into a solid state by dehydration and drying (that is, a solid state titanium-containing compound). (I-k)) is more suitable. The above-mentioned hydrolysate may be dried under normal pressure or reduced pressure, in a solid phase state or suspended in a liquid phase state with a high boiling point of water, and the drying temperature is not particularly limited. , But above 30 ° C and below 350 ° C is preferred. Before drying, the hydrous hydroxide gel or hydrous composite hydroxide gel can be washed with water, or after drying, the solid The titanium compound (I-k) is washed with water and It is also possible to remove the water-soluble components. In addition, drying should be performed quickly. The solid titanium-containing compound (I-k) obtained according to the method described above, its composition depends on the presence or absence of other elements, the presence or absence of washing, the drying method, and drying The degree varies, but from the standpoint of polycondensation reaction activity, the molar ratio (OH / T i) of the hydroxyl group (0H) and titanium (T 1) is usually 0. 09 or more and 4 or less. · 1 to 3 is preferable, and the range of 0 to 1 to 2 is more preferable. The molar ratio of the hydroxyl group and the titanium is specifically determined according to the above method. The solid titanium-containing compound ( I-k) Hydroxyl groups remain at the temperature at which the polycondensation reaction proceeds, for example, at about 280 ° C. When the solid titanium-containing compound (I-k) contains other elements, the titanium ( The Mohr ratio (E / T i) of T) and other elements (E) is usually 1/50 ~ 50/1, of which the Chinese national standard (CNS) A4 specification (210X29 * 7) is applied at 1/40 of this paper size. (Mm) (Please read the notes on the back before filling out this page). Secret clothing_ Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives -54- 585881 Α7 Β7 V. Description of the invention (52) ~ 4 0/1 is more suitable, especially 1/3 0 ~ 3 0/1 good. The above-mentioned aqueous hydroxide gel, aqueous composite hydroxide gel, solid titanium-containing compound (I-k) and other titanium-containing hydrolysates (A-1) usually have a chlorine content of 0 to 1 0 0 0 0 p pm, in which 0 to 100 ppm is more suitable. Basic compound (B) Basic compound (B) is a compound that shows basicity in an aqueous solution, specifically, for example, tetraethylammonium hydroxide, tetramethylammonium hydroxide, ammonia water, sodium hydroxide, and hydroxide Potassium, N-ethylmorpholine, N-methylmorpholine, etc. Among them, tetraethylammonium hydroxide is more suitable. Aliphatic Glycol (C) Specific examples of the aliphatic diol (C) include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-monobutylene glycol, neopentyl glycol, 1,6- Hexanediol, 1,12-dodecanediol and the like, among which ethylene glycol is preferred. The catalyst for polyester production according to the present invention is obtained by heating a mixture of the titanium-containing hydrolysate (A-1), the basic compound (B), and the aliphatic diol (C) to form a slurry. The above-mentioned mixed solution contains 0. 05 to 30% by weight of a titanium-containing hydrolysate (A-1). Among them, it is preferable to contain 0. 1 to 20% by weight, and it is preferable to contain 0. 5 to 1 5% by weight; basic compounds contain 0.5 to 50% by weight, of which 1 to 40% by weight is more appropriate, especially the Chinese national standard (CNS) A4 specification (210 ×: 297 mm) applicable to this paper scale 0 | 丨(Please read the notes on the back and fill in this card first) Order 585881 A7 _____B7_ printed by the Intellectual Property Bureau's Consumer Cooperatives of the Ministry of Economic Affairs 5. Description of the invention (53) The ratio of 2 to 30% by weight is the best. In addition, when the content of the aliphatic diol is 0 and the content of the titanium-containing hydrolysate (A-1) is 0.5% by weight or more, the amount of the aliphatic diol (C) can be reduced, and the polymerization reaction rate can be reduced. Will speed up. In addition, when the content ratio of the titanium-containing hydrolysate is 30% by weight or less, the coloring situation during heating is reduced, and therefore, the hue of the polyester obtained by the polymerization becomes good. In addition, when the content ratio of the basic compound (B) is 0.5% by weight or more, the catalyst activity is enhanced. When the content ratio of the basic compound is less than 50% by weight, the coloring during heating is reduced. The heating temperature of the above mixture is usually 100 ~ 300 ° C, of which 120 ~ 250 ° C is more suitable, especially 140 ~ 200 ° C, and the heating time is 5 minutes ~ 10 hours, of which 30 minutes to 8 hours is more appropriate. The method for producing polyester by using the above-mentioned catalyst for polyester production can be carried out according to the method described later. The ratio of the use of the catalyst for polyester production is based on the weight of the mixture of aromatic dicarboxylic acid and aliphatic diol. Conversion of metal weight in catalyst, usually between 0 · 0005 ~ 0. 2% by weight, with a range of 0.001 to 0.05% by weight being preferred. The polyester manufacturing catalyst may be added to the polymerization reaction container in the esterification reaction step, or may be added to the reaction container in the first stage of the polycondensation reaction step. In the present invention, in addition to the above-mentioned catalysts for polyester production, the above-mentioned auxiliary catalyst compounds can be used as auxiliary catalyst components. The auxiliary catalyst component is magnesium carbonate. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm). 56-(Please read the precautions on the back before filling this page}

、1T 經濟部智慧財產局員工消費合作社印製 585881 A7 B7 五、發明説明（54) 酸鎂之鎂化合物；碳酸鈣，乙酸鈣等之鈣化合物；氯化鋅 ’乙酸鋅等之鋅化合物爲較宜。輔觸媒化合物可單獨一種 或二種以上調配使用。 上述輔觸媒成分之用量，以上述聚酯製造用觸媒中之 鈦（含有其他元素時，鈦和其他元素）（T i )和輔觸媒 成分中之金屬原子（M)之莫耳比率〔（M)/(Ti) 在1/50〜50/1範圍，其中以1/40〜40/1 爲較宜，尤以1/ 3 0〜3 0/1範圍之用量爲最佳。又 ，使用磷酸鹽或亞磷酸鹽等磷化合物時，以磷化合物中所 含金屬原子換算之。 輔觸媒成分可在酯化反應步驟中添加到聚合反應容器 中，也可以在液相縮聚合反應步驟之第一階段添加在反應 容器中。又，在酯化反應步驟中添加輔觸媒成分時，也可 以和上述聚酯製造用觸媒同時添加，更可以分開添加。 使用上述聚酯製造用觸媒時，可以在短時間內獲得具 備所期待固有粘度之聚酯。 本發明之再一種形態有關之聚酯製造用觸媒乃係由 (A - 2 )鹵化欽化合物水解而成水解產物（I 一 m )或鹵化鈦化合物和鈦以外之其他元素中至少選擇一種元 素之化合物或該化合物之前驅物之混合物經水解而成水解 產物（I — η )(下文中，或稱上述水解產物爲「含鈦水 解產物（Α - 2」）’和 (D )含敍、錢、銘、總、棚、銘、錄、猛、銘和辞 中至少選擇一種元素之碟酸金屬鹽所構成’或 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）· 57 · -- (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T 585881 A7 B7 V. Description of the invention (54) Magnesium compounds of magnesium acid; Calcium compounds of calcium carbonate, calcium acetate, etc .; should. The auxiliary catalyst compounds can be used alone or in combination of two or more. The amount of the above-mentioned auxiliary catalyst component is the molar ratio of the titanium (including other elements, titanium and other elements) (T i) and the metal atom (M) in the auxiliary catalyst component in the polyester manufacturing catalyst. [(M) / (Ti) is in the range of 1/50 ~ 50/1, of which 1/40 ~ 40/1 is more suitable, and the dosage in the range of 1/3 0 ~ 3 0/1 is the best. When a phosphorus compound such as phosphate or phosphite is used, it is converted into a metal atom contained in the phosphorus compound. The auxiliary catalyst component may be added to the polymerization reaction vessel in the esterification reaction step, or may be added to the reaction vessel in the first stage of the liquid phase condensation polymerization reaction step. When the auxiliary catalyst component is added in the esterification reaction step, the auxiliary catalyst component may be added at the same time as the polyester production catalyst, or may be added separately. When the polyester manufacturing catalyst is used, a polyester having a desired inherent viscosity can be obtained in a short time. The catalyst for polyester production according to another aspect of the present invention is a product obtained by hydrolysis of (A-2) halogenated ammonium compound (I -m) or at least one element selected from titanium halide compound and other elements other than titanium. The compound or a mixture of the precursors of the compound is hydrolyzed to form a hydrolysate (I — η) (hereinafter, the above-mentioned hydrolysate is referred to as "titanium-containing hydrolysate (A-2") 'and (D) containing Qian, Ming, General, Shed, Ming, Lu, Meng, Ming, and at least one element selected from the group consisting of acid metal salts of discs or this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) · 57 ·-(Please read the notes on the back before filling this page)

、1T 經濟部智慧財產局g(工消費合作社印製 585881 A7 B7 i、發明説明（55 ) (A - 2 )由鹵化鈦化合物水解而成水解產物（I 一 m )或鹵化欽化合物和欽以外之其他元素中至少選擇一種 $素之化合物或該化合物之前驅物之混合物經水解而成水 解產物（I — η )，和 (Ε )含鈹、鎂、鈣、緦、硼、鋁、鎵、錳、鈷和鋅 中至少選擇一種元素之金屬化合物，以及 (F )由磷酸和磷酸酯中至少選擇一種之磷化合物， 和 (G )脂肪族二元醇之混合物加熱而得泥漿所構成。 水解產物（I 一 m ) ，（ I 一 η ) 水解產物（I - m )可由水解鹵化鈦化合物而製得， 水解產物（I - m )可由鹵化鈦化合物和上述其他元素之 化合物之混合物添加經水解而製成。 調製含鈦水解產物（A - 2 )所使用之鹵化鈦化合物 如同前述鹵化鈦化合物相同種類者。 鹵化鈦化合物之水解方法並無特別限制，例如前述調 製固態狀鈦化合物（I - a )之際所使用①至⑤項之方法 皆可採用。 如上述水解方法雖無特別限制，但是任何方法中必須 使用過剩量之水和鹵化鈦化合物作用以使水解反應得充分 進行。進行水解反應之溫度通常在1 0 0 °C以下，其中以 0〜7 0°C範圍爲較宜。 含鈦水解產物（A - 2 )可爲鹵化鈦化合物和上述其 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-58 - (請先閎讀背面之注意事項再填寫本頁j 、-tv1T Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperatives 585881 A7 B7 i) Description of the invention (55) (A-2) Hydrolyzed product (I-m) produced by hydrolysis of titanium halide compounds At least one of the other elements is selected from a compound or a mixture of precursors of the compound to be hydrolyzed (I-η), and (E) containing beryllium, magnesium, calcium, scandium, boron, aluminum, gallium, A metal compound of at least one element selected from the group consisting of manganese, cobalt, and zinc, and (F) a slurry obtained by heating a mixture of a phosphorus compound selected from at least one of phosphoric acid and a phosphate ester, and (G) an aliphatic diol. Hydrolysis The product (I-m), (I-η), the hydrolysate (I-m) can be prepared by hydrolyzing the titanium halide compound, and the hydrolysate (I-m) can be hydrolyzed by adding a mixture of the titanium halide compound and the above-mentioned other element compounds The titanium halide compound used to prepare the titanium-containing hydrolysate (A-2) is the same type as the aforementioned titanium halide compound. The method for hydrolyzing the titanium halide compound is not particularly limited, for example, the aforementioned adjustment The solid titanium compound (I-a) can be used in any of the methods ① to ⑤. Although the above-mentioned hydrolysis method is not particularly limited, in any method, an excess amount of water and a titanium halide compound must be used to effect hydrolysis. The reaction proceeds sufficiently. The temperature at which the hydrolysis reaction is carried out is usually below 100 ° C, and a range of 0 to 70 ° C is preferred. The titanium-containing hydrolysate (A-2) may be a titanium halide compound and the above-mentioned essence. Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -58-(Please read the precautions on the back before filling in this page j, -tv

I 經濟部智慧財產局員工消費合作社印製 585881 A7 B7_ 五、發明説明（5 ) 他元素之化合物之混合物行水解而成水解產物。換言之， 該水解產物可在其他元素之化合物共存下’將鹵化鈦化合 物水解而得。其他元素之化合物可單獨一種或二種以上調 配使用。 鹵化鈦化合物和其他元素之化合物之混合物行水解之 方法並無特別限制’例如上述調製固知狀欽化合物（I -b )之際所使用①至⑨項之方法均可採用。 水解之際，鹵化鈦化合物中之鈦（丁 i )和其他元素 之化合物中之其他元素（E)之莫耳比率（E/Ti)， 在1/5 0〜5 0/1範圍爲宜。又，進行水解反應之溫 度通常在1 0 0°C以下，其中以0〜7 0°C範圍爲較宜。 鹵化鈦化合物或鹵化鈦化合物和其他元素之化合物之 混合物行水解之際，由鹵化鈦化合物之水解所產生鹵化氫 以致液性呈現酸性。該酸性會使水解不能終結，因此，可 添加上述中和用鹼加以中和。中和之終點在P Η 4以上爲 宜，又，中和宜在7 0 °C以下進行。 上述水解所得水解產物（含水氫氧化物凝膠或含水複 合氫氧化物凝膠）雖然可直接提供縮聚合反應觸媒使用， 但以脫水乾燥成固態狀之水解產物（即，固態狀含鈦化合 物（A—2))而使用爲宜。 水解產物之乾燥可在常壓或減壓下，在固相狀態或懸 濁於高於水之沸點的液相狀態下進行，乾燥溫度並無特別 限制，以3 0 °C以上而3 5 0 °C以下爲宜。又，乾燥之前 ，將含水氫氧化物凝膠或含水複合氫氧化物凝膠加以水洗 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）.59. ---------罐II (請先閱讀背面之注意事項再填寫本頁)I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 585881 A7 B7_ V. Description of the invention (5) A mixture of compounds of other elements is hydrolyzed to form a hydrolysate. In other words, the hydrolysate can be obtained by hydrolyzing a titanium halide compound in the presence of compounds of other elements. Compounds of other elements can be used alone or in combination. The method for hydrolyzing a mixture of a titanium halide compound and a compound of another element is not particularly limited. For example, the methods ① to 所 used in the above-mentioned preparation of the compound (I -b) may be used. During the hydrolysis, the molar ratio (E / Ti) of titanium (butyl i) in the titanium halide compound and other elements (E) in other element compounds is preferably in the range of 1/5 0 to 5 0/1. In addition, the temperature at which the hydrolysis reaction is performed is usually 100 ° C or lower, and a range of 0 to 70 ° C is preferable. When the titanium halide compound or a mixture of a titanium halide compound and a compound of other elements is hydrolyzed, the hydrogen halide generated by the hydrolysis of the titanium halide compound makes the liquidity acidic. This acidity prevents the hydrolysis from ending. Therefore, the above-mentioned neutralization may be added to neutralize it. The end point of neutralization is preferably above P Η 4, and neutralization is preferably performed below 70 ° C. Although the hydrolysis product (aqueous hydroxide gel or aqueous composite hydroxide gel) obtained by the above hydrolysis can be directly used as a condensation polymerization catalyst, it is dehydrated and dried to form a solid state hydrolysate (ie, a solid state titanium-containing compound) (A-2)). The drying of the hydrolysate can be carried out under normal pressure or reduced pressure, in a solid phase state or suspended in a liquid phase state higher than the boiling point of water. The drying temperature is not particularly limited, and the temperature is above 30 ° C and 3 5 0 ° C is preferred. In addition, before drying, the aqueous hydroxide gel or aqueous composite hydroxide gel is washed with water. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm). 59. -------- -Tank II (Please read the notes on the back before filling this page)

、1T 經濟部智慧財產局8工消費合作社印製 585881 A7 B7 五、發明説明（57 ) ，或乾燥後，將固態狀含鈦化合物（A - 2 )加以水洗而 除去水溶性成分均可。又，乾燥宜快速進行。 (請先閱讀背面之注意事項再填寫本頁) 按照上述方法所得固態狀含欽化合物（A - 2 )，其 組成物分隨所共存之其他元素之有無或量，有無水洗，乾 燥方法，乾燥程度而異，但就縮聚合反應活性之觀點而言 ，以氫氧基（〇H)和鈦（T i )之莫耳比率（〇h/Printed by 8T Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs, 1T 585881 A7 B7 5. Description of the invention (57), or after drying, the solid titanium-containing compound (A-2) can be washed with water to remove water-soluble components. Also, drying should be performed quickly. (Please read the notes on the back before filling this page.) The solid-state compound (A-2) obtained according to the above method, its composition is determined by the presence or absence of other coexisting elements, the amount of washing, the drying method, and drying. The degree varies, but from the standpoint of polycondensation reaction activity, the molar ratio (OH / OH) of titanium (Ti) to titanium (Ti)

Ti )通常在0 · 09以上而4以下，其中以〇 · 1〜3 爲較宜，尤以0 · 1〜2範圍爲最佳。氫氧基和鈦之莫耳 比率，具體言之，可按照前述方法求得之。 該固態狀含鈦化合物（A - 2 )在進行縮聚合反應之 溫度下，例如約在2 8 0 °C下，仍有氫氧基殘存。 又，當固態狀含鈦化合物（A — 2 )含有其他元素時 ，該化合物中之鈦（T 1 )和其他元素（e )之莫耳比率 (E/Ti)，通常在1/50〜5〇/1範圍，其中以 1/40〜40/1爲較宜，尤以在1/30〜30/1 爲最佳。 上述含水氫氧化物凝膠，含水複合氫氧化凝膠，固態 狀含鈦化合物（A - 2 )等之含鈦水解產物，其含氯量通 經濟部智慧財產局員工消費合作社印製 常在0〜1 OOOOppm，以〇〜1 〇〇ppm爲較宜 〇 磷酸金屬鹽（D ) 磷酸金屬鹽（D )係含有鈹、鎂、鈣、緦、硼、鋁、 鎵、錳、鈷和鋅中至少選擇一種元素之化合物。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -60- 585881 A7 B7 五、發明説明（58) 磷酸金屬鹽（D )之具體例舉有例如磷酸氫鎂，二磷 酸二鎂’亞磷酸鎂等之磷酸鎂鹽； 磷酸氫齡’磷酸二氫鈣，磷酸三鈣等之磷酸鈣鹽； 磷酸氫緦等之磷酸緦鹽； 磷酸鋁等之磷酸鋁鹽； 磷酸二氫猛’磷酸錳等之磷酸錳鹽， 磷酸銘等之磷酸銘鹽； 磷酸鋅等之磷酸鋅鹽等，其中以磷酸鎂鹽爲較宜，尤 以磷酸氫鎂，二磷酸三鎂爲最佳。 使用上述聚酯製造用觸媒製造聚酯之方法，可按照後 述方法進行’縮聚合反應中，上述含鈦水解產物（A - 2 )之用量’對於低縮聚物中之芳香族二羧酸之莫耳量（芳 香族二羧酸換算），以含鈦水解產物（A - 2 )中之金屬 Z原子換算，通常在〇·〇〇〇5〜〇·2莫耳％，其中 以0·001〜〇·〇5莫耳％範圍爲宜，又，磷酸金屬 鹽（D )之使用比率以磷原子換算，通常在〇 . 〇〇1〜 〇·200莫耳％，其中以〇·002〜〇·050莫耳 %之範圍爲較宜。含鈦水解產物（A - 2 )和磷酸金屬鹽 (D )之使用量在上述範圍時，具有優異之聚合活性，所 得聚酯之乙醛含量較少。 又’本發明說明書中，乙醛含量乃按照下述方法測定 而決定之。即，將2 g之試料冷卻粉碎，恢復室溫後，採 取1 g放入容器中，加入2 cc之內部標準液於該容器中， 並加以密閉，繼之，在1 2 0 °C之烘乾箱中萃取1小時之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) itTi) is usually 0. 09 or more and 4 or less. Among them, 0. 1 to 3 is more preferable, and 0. 1 to 2 is more preferable. The molar ratio of the hydroxyl group to titanium, specifically, can be obtained by the aforementioned method. The solid titanium-containing compound (A-2) still has hydroxyl groups remaining at a temperature at which the condensation polymerization reaction proceeds, for example, at about 280 ° C. When the solid titanium-containing compound (A-2) contains other elements, the molar ratio (E / Ti) of titanium (T 1) and other elements (e) in the compound is usually 1/50 to 5 〇 / 1 range, among which 1/40 ~ 40/1 is more suitable, especially 1/30 ~ 30/1 is the best. The above-mentioned water-containing hydroxide gel, water-containing composite hydroxide gel, and solid-state titanium-containing compounds (A-2) and other titanium-containing hydrolysates, whose chlorine content is printed at 0 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. ~ 1 OOOOppm, preferably 0 ~ 100ppm. Metal phosphate (D) Phosphate (D) contains at least one of beryllium, magnesium, calcium, thallium, boron, aluminum, gallium, manganese, cobalt and zinc. Select a compound of one element. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -60-585881 A7 B7 V. Description of the invention (58) Specific examples of metal phosphate (D) include, for example, magnesium hydrogen phosphate, dimagnesium diphosphate 'Magnesium phosphates such as magnesium phosphite; Hydrogen phosphate age' Calcium phosphates such as calcium dihydrogen phosphate, tricalcium phosphate; phosphonium salts such as ammonium hydrogen phosphate; aluminum phosphates such as aluminum phosphate; dihydrogen phosphate Manganese phosphate salts such as manganese phosphate, phosphate salts such as phosphate phosphate; zinc phosphate salts such as zinc phosphate, etc. Among them, magnesium phosphate is more suitable, especially magnesium hydrogen phosphate and trimagnesium diphosphate. The method for producing polyester by using the above-mentioned catalyst for polyester production can be carried out according to the method described later, "the amount of the above-mentioned titanium-containing hydrolysate (A-2) in the polycondensation reaction" for the aromatic dicarboxylic acid in the low polycondensate. Molar amount (in terms of aromatic dicarboxylic acid), converted to the metal Z atom in the titanium-containing hydrolysate (A-2), usually in the range of 0.005 to 0.2 mol%, in which 0.001 A range of ~ 0.005 mole% is suitable. In addition, the use ratio of the metal phosphate (D) is converted into phosphorus atoms, and is usually in the range of 0.002 ~ 200mol%, in which 0.002 ~ 〇 · The range of 050 mol% is more suitable. When the amount of the titanium-containing hydrolysate (A-2) and the metal phosphate (D) is in the above range, it has excellent polymerization activity, and the resulting polyester has less acetaldehyde content. In the present specification, the acetaldehyde content is determined by measuring in the following manner. That is, 2 g of the sample is cooled and crushed, and after returning to room temperature, 1 g of the sample is put into a container, and 2 cc of the internal standard solution is added to the container, and then sealed, and then dried at 120 ° C. The paper size for 1 hour extraction in the dry box is applicable to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page) it

、1T 經濟部智慧財產局W工消費合作社印製 -61 - 585881 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（59 ) 後，冰冷，使用島津製作所製造之G C - 6 A型儀器測定 其5// 1之上澄液而定量。 上述含鈦水解產物（A - 2 )可在酯化反應步驟中添 加到反應容器中，也可以在縮聚合反應步驟之第一階段添 加到反應容器中。上述磷酸金屬鹽（D )可在酯化反應步 驟中添加到反應容器中，也可在縮聚合反應步驟之第一階 段添加到反應容器中。又，磷酸金屬鹽（D )也可以和含 鈦水解產物（A - 2 )同時添加，或分別添加均行。 金屬化合物（E ) 本發明中所使用金屬化合物（E )乃含鈹、鎂、耗、 緦、硼、鋁、鎵、錳、鈷和鋅中至少選擇一種元素之化合 物。 上述金屬化合物（E )之具體例舉有，例如乙酸鎂， 碳酸鎂，氫氧化鎂等之鎂化合物； 氫氧化鈣，乙酸鈣，碳酸鈣等之鈣化合物； 乙酸緦，碳酸緦等之緦化合物； 乙酸鋁，氫氧化鋁，碳酸鋁等之鋁化合物； 乙酸錳等之錳化合物； 乙酸鈷等之鈷化合物； 乙酸鋅等之鋅化合物等，其中以鎂化合物爲較宜，特 別以乙酸鎂，碳酸鎂爲最佳。 磷化合物（F ) 本紙張尺度適用中國國家標準( CNS ) A4規格（210X297公釐） '~~ (請先閱讀背面之注意事項再填寫本頁) -62- Μ)剛 Α7 ___Β7 五、發明説明（60) 本發明中所用之磷化合物（F )，具體言之，例如磷 酉欠和二甲基磷酸醋，三乙基隣酸酷，三正丁基磷酸酯，三 辛基磷酸酯，三苯基磷酸酯，三甲苯酚磷酸酯等之磷酸酯 類’其中以磷酸’三甲基磷酸酯爲較宜。 脂肪族二元醇（G ) 本發明中所使用之脂肪族二元醇（G )，具體言之， 例如乙二醇’ 1 ，3 -丙二醇，丙二醇，1 ，4 — 丁二醇 ’新戊二醇，1 ，6 -己二醇，十二烷基二醇等，其中以 &二醇爲較宜。 本發明有關之聚酯製造用觸媒，尙有由上述含鈦水解 產物（A - 2 )，金屬化合物（E )，磷化合物（F )和 脂肪族二元醇（G )之混合物經加熱而成泥漿者。 上述混合液中，含鈦水解產物（A - 2 )以鈦原子換 算計通常在0 · 1〜30重量％，其中以〇 · 2〜20重 量％爲較宜，最好在0 · 3〜1 0重量％範圍之含量比率 存在，金屬化合物（E)以金屬換算計，通常在〇 · 1〜 3〇重量％，其中以〇·2〜20重量％爲較宜，尤以 〇 · 3〜1 0重量％之含量比率存在爲最佳，磷化合物（ F)以磷原子換算計，通常在0.1〜30重量％，其中 以0·2〜20重量％爲較宜，尤以0·3〜10重量％ 之含量比率存在爲最佳。又，其餘爲脂肪族二元醇（C ) 。又，就聚合活性之觀點而言，使用相同重量之含鈦水解 產物（A — 2)和金屬化合物（E)爲宜。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------Φ —丨 (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慈財產局員工消費合作社印製 -63 - 585881 Α7 Β7 五、發明説明（61 ) 上述混合物之加熱，使溶解在脂肪族二元醇中之金屬 化合物（E )之至少一部分，和溶解在脂肪族二元醇中之 磷化合物（F )之至少一部分發生反應爲目的，金屬化合 物（E)和磷化合物（F)之含量比率在30重量％以下 時’就對於脂肪族二元醇之溶解性而言較宜。 上述混合物之加熱溫度，雖然視所使用脂肪族二元醇 之沸點而異，通常在50〜200 °C，其中以80〜 1 9 〇 °C爲較宜，最好在1 〇 〇 .〜1 9 0 t範圍，加熱時 間通常在3分鐘至5小時，其中以3 0分鐘至4小時爲較 宜’尤以1至4小時爲最佳。 加熱溫度在5 0 °C以上時，溶解在脂肪族二元醇中之 金屬化合物（E )和溶解在脂肪族二元醇中之磷化合物（ E )容易反應，加熱溫度在2 0 0°C以下時，脂肪族二元 醇不容易產生脫水反應等副作用。 使用上述聚酯製造用觸媒製造聚酯，可按照後述方法 進行’縮聚合反應中，該泥漿狀之聚酯製造用觸媒之使用 比率’對於對苯二甲酸和乙二醇之混合物重量計，以該觸 媒中之（由來於含鈦水解產物（A - 2 ))金屬重量計， 通常在0 · 0005〜0 · 2重量％，其中以0 · 001 〜〇 · 005重量％之範圍爲較宜。 上述泥漿狀之聚酯製造用觸媒可在酯化反應步驟中添 加到聚合反應容器中，也可在縮聚合反應步驟之第1階段 添加到反應容器中。 本發明中，由上述含鈦水解產物（A — 2 )和磷酸金 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ 297公麓) --------II (請先閱讀背面之注意事項再填寫本頁)、 1T Printed by the Wisdom Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-61-585881 Printed by the Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. After the description of the invention (59), it is cold and the GC-6 type A manufactured by Shimadzu Corporation is used. The instrument measures its 5 // 1 1 clear solution to quantify. The above-mentioned titanium-containing hydrolysate (A-2) may be added to the reaction vessel in the esterification reaction step, or may be added to the reaction vessel in the first stage of the polycondensation reaction step. The above-mentioned metal phosphate (D) may be added to the reaction vessel in the esterification reaction step, or may be added to the reaction vessel in the first stage of the polycondensation reaction step. The metal phosphate (D) may be added simultaneously with the titanium-containing hydrolysate (A-2), or may be added separately. Metal compound (E) The metal compound (E) used in the present invention is a compound containing at least one element selected from the group consisting of beryllium, magnesium, energy, thorium, boron, aluminum, gallium, manganese, cobalt, and zinc. Specific examples of the above-mentioned metal compound (E) include, for example, magnesium compounds such as magnesium acetate, magnesium carbonate, and magnesium hydroxide; calcium compounds such as calcium hydroxide, calcium acetate, and calcium carbonate; europium compounds such as europium acetate and europium carbonate Aluminum compounds such as aluminum acetate, aluminum hydroxide, aluminum carbonate, etc .; manganese compounds such as manganese acetate; cobalt compounds such as cobalt acetate; zinc compounds such as zinc acetate, etc. Among them, magnesium compounds are preferred, especially magnesium acetate, Magnesium carbonate is the best. Phosphorus compounds (F) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) '~~ (Please read the precautions on the back before filling this page) -62- Μ) Gang A7 ___ Β7 V. Description of the invention (60) Phosphorus compounds (F) used in the present invention, specifically, for example, phosphonium and dimethyl phosphate, triethyl orthophosphate, tri-n-butyl phosphate, trioctyl phosphate, tris Among phosphate esters such as phenyl phosphate and tricresol phosphate, trimethyl phosphate is preferred. Aliphatic Glycol (G) The aliphatic diol (G) used in the present invention, specifically, for example, ethylene glycol '1,3-propanediol, propylene glycol, 1,4-butanediol' neopentyl Diol, 1,6-hexanediol, dodecyl glycol and the like are preferred among them. The catalyst for polyester production according to the present invention comprises a mixture of the above-mentioned titanium-containing hydrolysate (A-2), metal compound (E), phosphorus compound (F) and aliphatic diol (G) by heating. Into the mud. In the above-mentioned mixed solution, the titanium-containing hydrolysate (A-2) is usually 0.1 to 30% by weight in terms of titanium atom conversion, and 0.2 to 20% by weight is preferable, and it is preferably 0.3 to 1 A content ratio in the range of 0% by weight exists. The metal compound (E) is generally in the range of 0.1 to 30% by weight in terms of metal conversion, of which 0.2 to 20% by weight is preferable, and 0.3 to 1% is particularly preferable. A content ratio of 0% by weight is optimal. The phosphorus compound (F) is 0.1 to 30% by weight in terms of phosphorus atom conversion, and 0.2 to 20% by weight is preferable, particularly 0.3 to 10%. The content ratio of weight% is preferably present. The rest is an aliphatic diol (C). From the standpoint of polymerization activity, it is preferable to use the same weight of the titanium-containing hydrolysate (A-2) and the metal compound (E). This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) --------- Φ — 丨 (Please read the precautions on the back before filling this page) Order the staff of the Intellectual Property Office of the Ministry of Economic Affairs Printed by Consumer Cooperatives -63-585881 Α7 B7 5. Description of the invention (61) The above mixture is heated to dissolve at least a part of the metal compound (E) in the aliphatic diol, and to dissolve in the aliphatic diol For the purpose of reacting at least a part of the phosphorus compound (F), when the content ratio of the metal compound (E) and the phosphorus compound (F) is 30% by weight or less, it is more suitable for the solubility of the aliphatic diol. Although the heating temperature of the above mixture varies depending on the boiling point of the aliphatic diol used, it is usually 50 ~ 200 ° C, among which 80 ~ 190 ° C is more preferable, and the best temperature is 100% ~ 1. In the 90 ton range, the heating time is usually from 3 minutes to 5 hours, with 30 minutes to 4 hours being more preferred, and 1 to 4 hours being the best. When the heating temperature is above 50 ° C, the metal compound (E) dissolved in the aliphatic diol and the phosphorus compound (E) dissolved in the aliphatic diol are easily reacted, and the heating temperature is 200 ° C In the following cases, aliphatic diols are less likely to cause side effects such as dehydration reactions. The polyester can be produced by using the polyester production catalyst described above. The ratio of the slurry-like polyester production catalyst used in the polycondensation reaction during the polycondensation reaction is described below based on the weight of the terephthalic acid and ethylene glycol mixture. Based on the weight of the metal in the catalyst (derived from the titanium-containing hydrolysate (A-2)), it is usually from 0. 0005 to 0. 2% by weight, and the range is from 0. 001 to 0.005% by weight. More appropriate. The slurry-like polyester production catalyst may be added to the polymerization reaction vessel in the esterification reaction step, or may be added to the reaction vessel in the first stage of the condensation polymerization reaction step. In the present invention, the size of the titanium-containing hydrolysate (A-2) and gold phosphate paper are applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 male feet) -------- II (please read the back first) (Notes to fill out this page)

、1T 經濟部智慧財產局員工消費合作社印製 -64 - 585881 A7 B7 五、發明説明（62 ) (請先閱讀背面之注意事項存填寫本頁) 屬鹽（D)所構成聚酯製造用觸媒，或上述泥漿狀之聚醋 製造用觸媒之外，尙可倂用以上述輔觸媒化合物爲輔觸媒 成分。上述輔觸媒化合物以使用碳酸鎂，乙酸鎂等鎂化合 物；碳酸鈣，乙酸鈣等鈣化合物；氯化鋅，乙酸鋅等之鋅 化合物爲宜。上述輔觸媒化合物可一種單獨或二種以上調 配使用。 上述輔觸媒成分之使用量，以上述聚酯製造用觸媒中 之鈦（含有其他元素時，鈦和其他元素）（T i )和輔觸 媒成分中之金屬原子（M)之莫耳比率〔（M) / (丁 i )〕計，通常在1/50〜50/1 ，其中以1/40〜 4 0/1爲較宜，尤以1/3 0〜3 0/1範圍之用量使 用爲最佳。 輔觸媒成分可在酯化反應步驟中添加到反應容器中， 也可在液相縮聚合反應步驟之第一階段添加到反應容器中 。又，尙在酯化反應步驟中添加輔觸媒成分時，可以和上 述聚酯製造用觸媒同時添加，也可以分別添加。 本發明有關之聚酯製造用觸媒，可藉高聚合活性而製 造乙醛含量少之聚酯。 經濟部智慧財產局員工消費合作社印製 其次，就使用上述聚酯製造用觸媒之聚酯之製造方法 說明如下。 聚酯之製造方法 使用上述聚酯製造用觸媒之聚酯之製造方法’乃係在 上述任意之聚酯製造用觸媒之存在下，將芳香族二羧酸或 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） -65- 8 8 5 8 5 A7 _______ B7 五、發明説明（63 ) 其酯形成性衍生物和脂肪族二元醇或其酯形成性衍生物加 以縮聚合而製成聚酯。以下舉其一例說明之。 (使用原料） 本發明有關聚酯之製造方法，使用芳香族二羧酸或其 酷形成性衍生物和脂肪族二元醇或其酯形成性衍生物爲原 料而製造。 上述芳香族二羧酸之例舉有對苯二甲酸，磷苯二甲酸 ’間苯二甲酸’萘二甲酸，二苯基二羧酸，二苯氧基乙烷 一殘酸等之芳香族二殘酸。 上述脂肪族二元醇之例舉有乙二醇，1 ，3 -丙二醇 ’丙二醇，1 ，4 一 丁二醇’新戊二醇，1 ，6 —己二醇 ’十二烷二醇等之脂肪族二元醇。 又’本發明中和芳香族二殘酸一起，也可以使用己二 酸’癸一酸，壬二酸，癸烷二羧酸等脂肪族二元醇，環己 ^一殘酸等之脂環族一殘酸等爲原料，另外，和脂肪族二 元醇一起’也可倂用環己烷二甲醇等脂環族二元醇。雙酣 ，氫S比，2 ，2 -雙（4 一 B —羥基乙氧基苯基）丙烷類 。1 ，3 —雙（2 -羥基乙氧基）苯，1 ，4〜雙（2一 經基乙氧基）苯等之芳香族二元醇爲原料。 又’本發明中’也可使用均苯三甲酸，三裡甲基乙院 ’三羥甲基丙烷，戊四醇等多官能性化合物爲原料。 (酯化反應步驟） 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 585881 A7 B7 五、發明説明（64 ) 首先，製造聚酯之際，先使芳香族二羧酸或其酯形成 性衍生物和脂肪族二元醇或其酯形成性衍生物進行酯化反 應。 具體言之’調製含有芳香族二羧酸或其酯形成性衍生 物和脂肪族二元醇或其酯形成性衍生物之泥漿。 上述泥漿中，對於芳香族二羧酸或其酯形成性衍生物 i莫耳計，通常含有1 · 005〜1 · 4莫耳之脂肪族二 元醇或其酯形成性衍生物，其中以含有1 · 〇 1〜1 . 3 莫耳爲較宜，尤以含有1 . 0 3〜1 · 3旲耳爲最佳。該 泥漿在酯化反應步驟中連續供料使用。 上述酯化反應最好以能將兩個以上之酯化反應基加以 串聯結合之裝置，在乙二醇之迴流條件下，把反應中所產 生之水利用精餾塔排除反應系外而進行。 上述酯化反應步驟通常以多階段而實施，第一階段之 酯化反應通常在2 4 0〜2 7 0°C之反應溫度下，其中以 245〜265 T：爲較宜，反應壓力通常在0 . 2〜3 kg/cm2G下，其中以〇 · 5〜2kg/crrfG之條件 下爲較宜，又，最終階段之酯化反應通常在2 5 〇〜 2 8 0°C之反應溫度下，其中以2 5 5〜2 7 5°C爲較宜 ，反應壓力通常爲0〜1 · 5kg/cmG，其中以q〜 1 · 3kg/cm2G之條件下進行爲較宜。 上述各階段中之酯化反應率並無特別限制，但以各階 段中之酯化反應率之上升情形有分配均衡爲較宜，最後階 段之酯化反應生成物中通常在9 0 %以上，其中以能達到 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 •67- 585881 Μ Β7 ___ 65 五、發明説明（） 9 3 %以上爲理想。 (請先閱讀背面之注意事項再填寫本頁) 上述酯化反應’在不添加芳香族二羧酸和脂肪族二元: 醇以外之添加物也能實施’但在上述聚酯製造用觸媒之共 存下實施亦行。又，添加少量之三乙胺，三正丁胺’苯甲 基二甲胺等叔胺；氫氧化四乙基銨，氫氧化四丁基銨，氫 氧化三甲基苯甲銨等之氫氧化季銨；碳酸鋰’碳酸鈉’碳 酸鉀，乙酸鈉等之鹼性化合物而實施時，比較能保持聚乙 烯對苯二甲酸酯之主鏈中二氧化乙烯對苯二甲酸酯成分單 位之比率於較低水平而較宜。 據上述酯化步驟而可得酯化物（低聚合物）’該酯化 物之數平均分子量通常在5 0 0〜5 0 0 0範圍。所得低 縮聚物繼之供料至縮聚合反應（液相縮聚合反應）步驟中 (液相縮聚合步驟） 經濟部智慧財產局員工消費合作社印製 液相縮聚合反應步驟中，在上述縮聚合反應觸媒之存 在下，經酯化步驟而得之低聚合物於減壓下，且在聚酯之 熔點以上溫度（通常在2 5 0〜2 8 0 °C )加熱而進行縮 聚合反應。該縮聚合反應中，以把未反應之脂肪族二元醇 蒸餾排除在反應系外進行爲宜。 縮聚合反應可以用一個階段完成，也可以分爲數個階 段進行。例如縮聚合反應分爲數階段進行時，第一階段之 縮聚合反應通常在2 5 0〜2 9 0°C之反應溫度下，其中 較宜在260〜280 °C下，反應壓力在500〜20 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）· 68 - 585881 A7 B7 五、發明説明（66 ) τ 〇 r r下，其中較宜在200〜30T〇 r r之條件下 進行’最終階段之縮聚合反應通常在2 6 5〜3 0 0 °C之 反應溫度下，其中較宜在2 7 0〜2 9 5 °C下，反應壓力 在10〜〇 · ITor r下，其中較宜在5〜〇· 5 T ◦ r r之條件下進行。 縮聚合反應分爲兩階段進行時，第一階段和第二階段 之縮聚合反應條件分別按照上述範圍進行，分爲三階段以 上實施時，第二階段之縮聚合反應通常在2 6 0〜2 9 5 °C下，其中較宜在2 7 0〜2 8 5°C下，反應壓力通常在 5〇〜2丁〇 r r下，其中較宜在40〜5To r r之條 件下進行。上述縮聚合反應步驟之各步驟中所要達成之固 有粘度並無特別限制，但以各階段中之固有粘度之上升情 形有分配平衡爲較理想。 縮聚合反應宜在安定劑之共存下進行。安定劑之具體 例舉有三甲基磷酸酯，三乙基磷酸酯，三正丁基憐酸酯， 三辛基磷酸酯，三苯基磷酸酯等之磷酸酯類；三苯基亞磷 酸酯，三個十二烷基亞磷酸酯，三個壬基苯基亞磷酸酯等 亞磷酸酯類；單甲基磷酸酯，二甲基磷酸酯，單乙基磷酸 酯，二乙基磷酸酯，單異丙基磷酸酯，二異丙基磷酸酯， 二丁基磷酸酯，單丁基磷酸酯，二辛基磷酸酯等磷酸酯類 和磷酸，聚磷酸等之磷化合物。 上述磷化合物之添加量，對於芳香族二羧酸計，以該 磷化合物中之磷原子換算，通常在0·005〜0·2莫 耳％，其中以0 · 0 1〜0 · 1莫耳％量爲較宜。該磷化 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ----------- (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 8 5 8 Μ Β7____ 五、發明説明（67 ) 合物可以在酯化反應步驟階段供料，也可以在縮聚合反應 步驟中之第一階段供料到反應容器中。 (請先閱讀背面之注意事項再填寫本頁) 上述液相縮聚合反應步驟中所得聚酯之固有粘度通常 在〇· 40〜1 · Odl/g ，其中以0 · 50〜 〇· 9〇dl/g爲較宜，尤以〇· 55〜0 · 75dl / g爲理想。又，該液相縮聚合步驟之最終階段以外之各 階段中所能達成之固有粘度並無特別限制，但以保持各階 段中之固有粘度之上升程度有分配平衡爲理想。 又，本發明說明書中之固有粘度係將1 · 2 g之聚酯 在1 5 cc之鄰一氯化酚中加熱溶解後，冷卻在2 5 °C下測 定之溶液粘度計算而得。 該聚酯之密度通常在1 · 33〜1 · 35g/cm3爲 宜。本發明之說明書中所指聚酯之密度係使用四氯化碳和 庚烷之混合溶媒之密度梯階管在2 3 °C溫度下測定而得。 該縮聚合步驟所得聚酯通常以熔融擠壓成型成粒狀（ 小片狀）。上述粒狀聚酯通常在2 · 0〜5 . 0 m m粒徑 ，其中以具有2 · 2〜4 0 m m之平均粒徑爲理想。 經濟部智慧財產局員工消費合作社印製 上述液相縮聚步驟所得聚酯’必要時可再進行固相縮 聚合反應。 (固相縮聚合步驟） 供料到固相縮聚合步驟之粒徑聚酯’事前加熱到低於 進行固相縮合反應之溫度而進行預結晶化之後，再行供料 至固相縮聚合步驟亦可。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）-70 - 8 A7 _______B7__ 五、發明説明（68 ) (請先閲讀背面之注意事項再填寫本頁) 上述預結晶化步驟中，將粒狀聚酯在乾燥狀態下，通 常加熱至1 20〜200 t，其中在1 30〜180 t：溫 度下加熱1分鐘至4小時而進行。又，上述預結晶化也可 以在水蒸汽條件下，含水蒸汽之不活性氣體環境下，或含 水蒸汽之空氣條件下，將粒狀聚酯在1 2 〇〜2 〇 〇 r溫 度下加熱1分鐘以上而進行。 預結晶化之聚酯，其結晶化度在2 0〜5 0 %爲理想 〇 又，上述預結晶化處理中，所謂聚酯之固相縮聚合反 應不再進行，而經預結晶化之聚酯之固有粘度和液相縮聚 合後之聚酯之固有粘度幾乎相同，預結晶化後之聚酯之固 有粘度和預結晶化前之聚酯之固有粘度之差異，通常在 〇.06dl/g以下。 固相縮合步驟至少由一階段而成，反應溫度在1 9 0 〜230 °C，較宜在195〜255 °C，壓力在lkg/ c m2 G，其中以常壓至1 〇 〇 T 〇 r r之條件下，於氮， 氬，二氧化碳等不活性氣體環境中進行。其中所使用不活 性氣體以氮氣爲較宜。 經濟部智慧財產局員工消費合作社印製 經由上述固相縮聚步驟而得粒狀聚酯，例如可按照特 公平7 — 6 4 9 2 0號公報中所記載方法水處理，該水處 理係使粒狀聚酯和水，水蒸汽，含水蒸汽之不活性氣體， 含水蒸汽之空氣等接觸而進行。 按照上述所得粒狀聚酯之固有粘度通常在0 . 5 0 d Ι/g以上，其中以0 · 60〜1 · 00d ι/g爲較 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297&f ~~「71 - " 585881 A7 B7____ 五、發明説明（69 ) 宜’尤以0 · 75〜0 · 95dl/g爲理想。 (請先閱讀背面之注意事項再填寫本頁) 含有上述酯化步驟和縮聚合步驟之聚酯之製造步驟可 藉分批式、半連續式、連續式之任意方法進行。該聚酯之 密度通常在1·37g/cm3以上，其中以1·38g/ c m 3爲較宜，尤以1 · 3 9 g / c m 3以上爲理想。 按照上述製造之聚酯，可使用已往周知之添加劑，例 如安定劑、離模劑、靜電防止劑、分散劑、染料等著色劑 等’這些添加劑可在製造聚酯之任意階段添加，或在成型 加工前添加到主膠料中。 據本發明所得之聚酯可提供各種成型物之原料用途， 例如熔融成型爲瓶等之中空成型物，片狀物，薄膜，纖維 等使用，其中以提供製瓶用途爲宜。 據本發明所製得之聚酯，例如上聚乙烯對苯二甲酸酯 成型爲瓶，片狀物，薄膜，纖維等之方法，可採用已往周 知之方法而進行。 其次’就本發明之其他形態有關聚酯之製造方法說明 如下： 經濟部智慧財產局員工消費合作社印製 本發明之另一種途徑有關之聚酯之製造方法，包括將 芳香族二羧酸或其酯形成性衍生物和脂肪族二元醇或其酯 形成性衍生物加以酯化而形成低聚合物之酯化步驟，以及 在縮聚合反應觸媒之存在下，將該低聚合物縮聚合使之高 分子量化的縮聚合步驟之聚酯之製造方法中， 乃使用下列縮聚合觸媒， (I )由水解鈦化合物而成水解產物（I — j )，或 本紙張尺度適用中國國家梯準（CNS ) A4規格（210X297公釐）> ' -72- 585881 A7 B7 五、發明説明（70) 鈦化合物和鈦以外之其他元素中至少選擇一種元素之化合 物或該化合物之前驅物之混合物行水解而成水解產物 - k )所構成觸媒成分，和 (Π )由鈹、鎂、與、總、鋇、硼、銘、鎵、锰、結 、鋅、鍺、銻和磷所構成群中至少選擇一種元素之化合物 而構成輔觸媒成分而成觸媒，並且 在酯化反應開始前或酯化反應開始後立即將上述觸媒 成分（I )添加在酯化反應容器中。 上述水解鈦化合物而.成水解產物（I - j )，鈦化合 物和駄以外之其他兀素中至少選擇一種兀素之化合物或該 化合物之前驅物之混合物行水解而成之水解產物（I 一 k )’和前述水解產物（I 一 j )，水解產物（I 一 k )相 同種類。 輔觸媒成分（Π )之例舉和上述輔觸媒化合物相同者 ’其中以碳酸鎂、乙酸鎂等鎂化合物；碳酸鈣，乙酸鈣等 鈣化合物；氯化鋅，乙酸鋅等鋅化合物爲較宜。輔觸媒化 合物可以單獨一種或二種以上調配做爲輔觸媒成分使用。 包括由芳香族二羧酸或其酯形成性衍生物和脂肪族二 元醇或其酯形成性衍生物加以酯化而成低聚合物之酯化步 驟，以及在縮聚合觸媒之存在下，將該低聚合物縮聚合反 應而使高分子量化之縮聚合步驟之聚酯之製造方法，按照 上述之酯化步驟’液相縮聚合步驟’必要時再加以固相縮 聚合反應而進行。但供料至液相縮聚合步驟之酯化物係 (I )由水解產物（I 一 j )或水解產物（I 一 k ) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -- (請先閱讀背面之注意事項再填寫本頁) -訂 經濟部智慧財產局員工消費合作社印製 -73- 585881 A7 B7 五、發明説明（71) 所構成縮聚合觸媒成分，和 (請先閱讀背面之注意事項再填寫本頁) (Π )輔觸媒成分所構成縮聚合觸媒之存在下進行縮 聚合反應，上述觸媒成分中，縮聚合觸媒成分（I )可在 酯化反應步驟中，酯化反應開始前或酯化反應開始後立即 添加至反應容器中。又，本發明中所指酯化反應開始後立 即乃指酯化率在5 0 %以下之狀態。又，酯化率乃指二竣 酸等芳香族二羧酸之反應率，由反應產物之酸値（A v ) 和皂化値之比率表示之。 另一方面，輔觸媒成分（π )可在酯化反應步驟之任 意階段中添加到反應容器中，也可以在液相縮聚合反應步 驟之第一階段添加在反應容器中。當添加輔觸媒成分（π )在酯化反應步驟時，可以和觸媒成分（I )同時添加， 也可以和觸媒成分（I )分開而添加。 上述觸媒成分（1 )之使用比率，對於芳香族二羧酸 和脂肪族二元醇之混合物重量計，以觸媒成分（I )中之 金屬重量換算’通常爲〇 · 0005〜0 . 2重量％，其 中以0 · 001〜〇 · 05重量％之範圍。 經濟部智慧財產局員工消費合作社印製 輔觸媒成分（Π )之用量，以上述觸媒成分（I 一 j )中之鈦和輔觸媒成分（π )中之金屬原子（Μ)之莫耳 比率〔（Μ)/ (I 一 j)〕 ’或上述觸媒成分（I 一 k )中之鈦和其他元素，以及輔觸媒成分（π )中之金屬原 子（Μ)之莫耳比率〔（Μ)/(ι 一 k)〕計，通常在 1/50〜50/1’其中以1/40〜40/1爲較宜 ’尤以1/3 0〜3 0/1範圍用量爲理想。又，使用磷 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） -74- 585881 A7 B7 五、發明説明（72) 鹽酸或亞磷酸鹽等磷化合物時，以磷化合物中所含金屬原 子換算之。 (請先閲讀背面之注意事項再填寫本頁) 依據本發明可在短時間內獲得所期待具有固有粘度之 聚酯。 其次’再就本發明之另一種形態有關聚酯之製造方法 說明如下： 本發明之另一種形態之聚酯之製造方法乃係， 將芳香族二羧酸或其酯形成性衍生物和脂肪族二元醇 或其酯形成性衍生物在下列（1 )至（3 )項中所選擇縮 聚合觸媒’和磷酸酯之存在下進行縮聚合反應而製成聚酯 j (1 )由水解鹵化鈦化合物而成水解產物（I _ m ) 所構成縮聚合觸媒， (2 )由鹵化鈦化合物和鈦以外之元素中至少選擇一 種元素之化合物或該化合物之前驅物之混合物行水解而成 水解產物（I - η )所構成縮聚合觸媒， 經濟部智慧財產局員工消費合作社印製 (3 )上述（I — m )或（I — η )和 由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、銘、鋅、 鍺、鍊所構成群中至少選擇一種元素之化合物或磷酸鹽， 或亞磷酸鹽所構成之縮聚合觸媒。 鹵化鈦化合物經水解而成水解產物（I - rn )，鹵化 鈦化合物和鈦以外之其他元素中至少選擇一種元素之彳匕合 物或該化合物之前驅物之混合物經水解而成之水解產彳勿（ I — η )，可舉前述之水解產物（I — m )，水解產物（ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -75- 585881 A7 _____ _B7 五、發明説明（73 ) I 一 η )相同者。 (請先閱讀背面之注意事項再填寫本頁) 由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷、鋅、 鍺、銻所構成群中至少選擇一種元素之化合物或磷酸鹽， 或亞磷酸鹽（以下或簡稱爲「輔觸媒成分（na)」）， 具體言之，可舉上述輔觸媒化合物中所例舉相同化合物， 該化合物可單獨一種’或二種以上調配使用之。輔觸媒成 分（Π a )以使用碳酸鎂，乙酸鎂等鎂化合物；碳酸鈣， 乙酸鈣等鈣化合物；氯化鋅，乙酸鋅等鋅化合物爲較宜。 上述縮聚合反應之際，和上述縮聚合觸媒倂用之磷酸 酯之例舉有三甲基磷酸酯，三乙基磷酸酯，三正丁基磷酸 酯，三辛基磷酸酯，三苯基磷酸酯，三甲酚基磷酸酯等。 由芳香族二羧酸或其酯形成性衍生物和脂肪族二元醇 或其酯形成性衍生物行縮聚合反應而製造聚酯之方法，如 上述酯化步驟，液相縮聚合步驟，必要時再加以固相縮聚 合步驟而進行。 水解產物（I 一 m )或（I 一 η )之使用比率，對於 芳香族二羧酸和脂肪族二元醇之混合物重量計，以縮聚合 經濟部智慧財產局g(工消費合作社印製 計 ο 量 ο •lm 二 重 · 屬 ο 金以 之中 中其 媒， 觸 ％ ο 在 常 通 ο ο 量 二彐11 重 2 宜 較 爲 圍 範 % 量 重 5 又 2 量 ο 重 ο 子 · 原 ο 磷以 以中 量其 用， 酯% 酸量 磷重 在 常 通 - 2 1 範 ο % ο 量 . 重 使果 之效 酯異 酸優 磷之 和間 } 時 η 應 I 反 I 合 (聚 或縮 )短 m縮 I 獲 I 可 Γν ， 物時 產圍 解範 水述 。 上 宜在 爲量 圍用 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -76- 585881 A7 B7 五、發明説明（74 ) (請先閱讀背面之注意事項再填寫本頁) 輔觸媒成分（na )之用量，以上述水解產物（I 一 m)中之鈦和輔觸媒成分（Π a )中之金屬原子（M)之 旲耳比率〔（M ) / ( I - m )〕，或上述水解產物（I 一 η )中之鈦和其他元素以及輔觸媒成分（^ )中之金 屬原子（M)之莫耳比率〔（Μ)/(ι 一 n)〕計，通 常在1/5〇〜5〇/1範圍，其中以1/4 ◦〜40/ 1爲較宜，尤以在1/3 0〜3 0/1範圍用量爲理想。 又，使用磷酸鹽或亞磷酸鹽等磷化合物時，以磷化合物中 所含金屬原子換算之。 上述縮聚合觸媒和磷酸酯之供料方法，可在酯化反應 步驟階段中供料，也可以在縮聚合反應步驟之第一階段中 添加到反應容器中。 據本發明可在短時間內獲得具有所期待固有粘度之聚 酯。 又，就本發明之又一種形態有關之聚酯之製造方法說 明如下： 經濟部智慈財產局員工消費合作社印製 本發明之又一種形態有關之聚酯之製造方法乃係 將芳香族二羧酸或其酯形成性衍生物和脂肪族二元醇 或其酯形成性衍生物在下列（1 )至（3 )中所選擇縮聚 合觸媒和環狀內酯系化合物以及受阻酚系化合物中至少選 擇一種化合物之存在下縮聚合反應而製造聚酯： (1 )由水解鹵化鈦化合物而成水解產物（I 一 πι ) 所構成縮聚合觸媒， (2 )由鹵化鈦化合物和鈦以外之其他元素中至少選 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）-77 - 585881 經濟部智慧財產局員工消費合作社印製 A7 __B7 五、發明説明（75 ) 擇一種元素之化合物或該化合物之前驅物之混合物行水解 而成水解產物（I 一 η )所構成縮聚合觸媒， (3 )上述分解產物（I — m )或（I 一 η )和 由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、姑、鋅、 鍺、銻所構成群中至少選擇一種元素之化合物或磷酸鹽， 或亞磷酸鹽所構成之縮聚合觸媒。 水解鹵化鈦化合物而成之水解產物（I〜m )，鹵化 鈦化合物和鈦以外之其他元素中至少選擇一種元素之化合 物或該化合物之前驅物之混合物行水解而成之水解產物（ I 一 η )，可舉上述水解產物（I 一 m )，水解產物（I 一 η )相同種類者。 由鈹、鎂、錦、總、鋇、硼、銘、鎵、f孟、銘、鋅、 鍺、銻所構成群中至少選擇一種元素之化合物或磷酸鹽， 或亞磷酸鹽，具體例舉和上述輔觸媒成分（Π a )相同。 輔觸媒成分（Π a )以碳酸鎂，乙酸鎂等鎂化合物；碳酸 鈣，乙酸鈣等鈣化合物；氯化鋅，乙酸鋅等鋅化合物爲較 理想。 縮聚合反應之際，所使用環狀內酯系化合物和受阻酚 系化合物中至少選擇一種化合物之具體例舉有5 ，7 -二 —第三丁基—3 — (3 ，4 —二甲基苯基）—3H —苯駢 呋喃一 2 —酮， 四個（亞甲基一 3 — （3 ，5 -二第三丁基一4 —羥 基苯基）丙酸酯）甲烷， 三個（2，4 —二第三丁基苯基）隣酸醋， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）-73 - (請先閱讀背面之注意事項再填寫本頁)、 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-64-585881 A7 B7 V. Description of the invention (62) (Please read the precautions on the back and fill in this page) It belongs to the polyester manufacturing contact made of salt (D) In addition to the above catalysts, or the above-mentioned slurry-like polyacetic acid production catalysts, the above auxiliary catalyst compounds may be used as auxiliary catalyst components. As the auxiliary catalyst compound, magnesium compounds such as magnesium carbonate and magnesium acetate; calcium compounds such as calcium carbonate and calcium acetate; and zinc compounds such as zinc chloride and zinc acetate are preferably used. The above auxiliary catalyst compounds can be used alone or in combination of two or more. The amount of the auxiliary catalyst component used is the mole of the titanium (including other elements, titanium and other elements) (T i) and the metal atom (M) in the auxiliary catalyst component in the polyester production catalyst. The ratio [(M) / (丁 i)] is usually in the range of 1/50 to 50/1, of which 1/40 to 4 0/1 is more suitable, especially in the range of 1/3 0 to 3 0/1. Dosage is optimal. The auxiliary catalyst component may be added to the reaction container in the esterification reaction step, or may be added to the reaction container in the first stage of the liquid phase condensation polymerization reaction step. In addition, when rhenium is added to the auxiliary catalyst component in the esterification reaction step, it may be added at the same time as the polyester production catalyst, or may be added separately. The catalyst for polyester production according to the present invention can produce a polyester with low acetaldehyde content through high polymerization activity. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Next, the method for manufacturing polyester using the polyester manufacturing catalyst described above is described below. Polyester manufacturing method The polyester manufacturing method using the polyester manufacturing catalyst mentioned above is to apply the aromatic dicarboxylic acid or this paper standard to Chinese national standards in the presence of any of the polyester manufacturing catalysts mentioned above (CNS) A4 specification (210X29 * 7 mm) -65- 8 8 5 8 5 A7 _______ B7 V. Description of the invention (63) Its ester-forming derivative and aliphatic diol or its ester-forming derivative are added Polycondensation to make polyester. Here is an example to illustrate it. (Using raw materials) The method for producing a polyester according to the present invention is produced using an aromatic dicarboxylic acid or a cool-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof as raw materials. Examples of the above-mentioned aromatic dicarboxylic acid include aromatic dicarboxylic acid such as terephthalic acid, phosphophthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and diphenoxyethane monoresidue acid. Residual acid. Examples of the aliphatic diols include ethylene glycol, 1,3-propanediol'propylene glycol, 1,4-butanediol'neopentyl glycol, 1,6-hexanediol'dodecanediol, and the like. Aliphatic diols. In addition, in the present invention, an aliphatic dihydric alcohol such as adipic acid, azelaic acid, and decanedicarboxylic acid, and an alicyclic ring such as cyclohexane ^ a residual acid may be used together with the aromatic diresidual acid. As the raw material, a residual mono-acid or the like may be used together with the aliphatic diol, and an alicyclic diol such as cyclohexanedimethanol may also be used. Bifluorene, hydrogen-to-S ratio, 2,2-bis (4-a-B-hydroxyethoxyphenyl) propane. Aromatic diols such as 1,3-bis (2-hydroxyethoxy) benzene, 1,4 ~ bis (2-cathoxyethoxy) benzene, etc. are used as raw materials. In the present invention, polyfunctional compounds such as pyromellitic acid, trimethylacetin, trimethylolpropane, and pentaerythritol may be used as raw materials. (Esterification reaction step) This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page) Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives 585881 A7 B7 V. Description of the Invention (64) First, in the production of polyester, first, an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof are subjected to an esterification reaction. Specifically, 'a slurry is prepared containing an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof. In the above-mentioned mud, the aromatic dicarboxylic acid or its ester-forming derivative i, a mole meter, usually contains 1.005 to 1.4 moles of an aliphatic diol or an ester-forming derivative thereof. 1 · 〇1 ~ 1.3 Moore is more suitable, especially containing 1.0 ~ 3 · 3 Moore. The slurry is continuously fed and used in the esterification reaction step. The above-mentioned esterification reaction is preferably carried out by a device capable of combining two or more esterification reaction groups in series under the reflux condition of ethylene glycol, and using the distillation column to exclude the reaction system from the distillation system. The above-mentioned esterification reaction step is usually carried out in multiple stages. The first stage of the esterification reaction is usually at a reaction temperature of 240 ~ 270 ° C, of which 245 ~ 265 T is preferred, and the reaction pressure is usually at Under 0.2 ~ 3 kg / cm2G, the conditions of 0.5 ~ 2kg / crrfG are more suitable, and the esterification reaction in the final stage is usually at a reaction temperature of 250 ~ 280 ° C. Among them, 2 5 5 ~ 2 5 ° C is preferable, and the reaction pressure is usually 0 ~ 1 · 5 kg / cmG, and it is preferably performed under the conditions of q ~ 1 · 3 kg / cm2G. The esterification reaction rate in each of the above stages is not particularly limited, but it is more appropriate to have a balanced distribution of the increase in the esterification reaction rate in each stage. The final esterification reaction product is usually more than 90%. Which can reach the size of this paper and apply Chinese National Standard (CNS) A4 specifications (210X 297 mm) (Please read the precautions on the back before filling out this page) Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives • 67- 585881 Ｍ Β7 ___ 65 V. Description of the invention () 93% or more is ideal. (Please read the precautions on the back before filling in this page) The above esterification reaction 'can be carried out without the addition of aromatic dicarboxylic acids and aliphatic dibasic: Additives other than alcohol', but in the above mentioned polyester production catalysts Implementation is possible under the coexistence. In addition, a small amount of tertiary amines such as triethylamine, tri-n-butylamine 'benzyldimethylamine, and tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzyl hydroxide are added. Quaternary ammonium; lithium carbonate 'sodium carbonate' potassium carbonate, sodium acetate and other basic compounds, when implemented, can relatively maintain the polyethylene terephthalate in the main chain of ethylene dioxide terephthalate component units Ratios are preferred at lower levels. According to the above-mentioned esterification step, an esterified product (oligomer) can be obtained. The number-average molecular weight of the esterified product is usually in the range of 500 to 5000. The obtained low polycondensate is then fed to the polycondensation reaction (liquid phase polycondensation reaction) step (liquid phase polycondensation step). In the liquid phase polycondensation polymerization step printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the above polycondensation is performed. In the presence of a reaction catalyst, the low polymer obtained through the esterification step is subjected to a condensation polymerization reaction under reduced pressure and is heated at a temperature above the melting point of the polyester (usually at 250 to 280 ° C). In this polycondensation reaction, it is preferable to perform distillation by removing unreacted aliphatic diol from the reaction system. The polycondensation reaction can be carried out in one stage or divided into several stages. For example, when the polycondensation reaction is carried out in several stages, the polycondensation reaction in the first stage is usually at a reaction temperature of 250 ~ 290 ° C, which is more preferably at 260 ~ 280 ° C and the reaction pressure is 500 ~ 20 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) · 68-585881 A7 B7 V. Description of the invention (66) τ 〇rr, which is more suitable for 200 ~ 30T〇rr 'The condensation polymerization reaction in the final stage is usually at a reaction temperature of 265 to 300 ° C, which is more preferably at 270 to 295 ° C, and the reaction pressure is at 10 to 〇 ITor r, where It is preferable to carry out under the conditions of 5 to 0.5 T ◦ rr. When the polycondensation reaction is performed in two stages, the conditions of the first and second stages of the polycondensation reaction are carried out in accordance with the above ranges. When divided into three or more stages, the second stage of the polycondensation reaction is usually in the range of 260 to 2 At 95 ° C, it is more preferable to be at 270 ~ 28. At 5 ° C, the reaction pressure is usually at 50 ~ 2butorr, and more preferably at 40 ~ 5To rr. The inherent viscosity to be achieved in each step of the above-mentioned polycondensation reaction step is not particularly limited, but it is desirable to have a distribution equilibrium in which the inherent viscosity rises in each stage. The polycondensation reaction is preferably performed in the presence of a stabilizer. Specific examples of the stabilizer include phosphates such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, and triphenyl phosphate; triphenyl phosphite, Three dodecyl phosphites, three nonylphenyl phosphites, and other phosphites; monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, diethyl phosphate, mono Phosphates such as isopropyl phosphate, diisopropyl phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate and phosphorus compounds such as phosphoric acid and polyphosphoric acid. The amount of the phosphorus compound added is, in terms of the aromatic dicarboxylic acid, converted to the phosphorus atom in the phosphorus compound, and is usually in the range of 0.005 to 0.2 mole%, in which 0. 0 1 to 0. 1 mole The amount of% is more suitable. The size of this phosphated paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ----------- (Please read the notes on the back before filling this page) Order the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the employee consumer cooperative 8 5 8 Μ B7____ 5. Description of the invention (67) The compound can be fed in the esterification reaction step, or it can be fed into the reaction container in the first stage of the polycondensation reaction step. (Please read the precautions on the back before filling this page) The inherent viscosity of the polyester obtained in the above-mentioned liquid phase condensation polymerization step is usually in the range of 40 · 1 ~ 1 · Odl / g, among which 0 · 50 ~ 0 · 9〇dl / g is more suitable, especially from 0.55 to 0.775 dl / g. In addition, the inherent viscosity that can be achieved in each of the stages other than the final stage of the liquid phase condensation polymerization step is not particularly limited, but it is desirable to maintain a balanced distribution of the degree of increase in the intrinsic viscosity in each stage. In addition, the inherent viscosity in the description of the present invention is calculated by dissolving 1.2 g of polyester in 15 cc of ortho-monochlorophenol, and then cooling the solution viscosity measured at 25 ° C. The density of the polyester is usually preferably from 1.33 to 1.35 g / cm3. The density of the polyester referred to in the description of the present invention is obtained by measuring a density step tube using a mixed solvent of carbon tetrachloride and heptane at a temperature of 2 ° C. The polyester obtained in this polycondensation step is usually melt-extruded into pellets (tablets). The above-mentioned granular polyester generally has a particle diameter of 2.0 to 5.0 mm, and it is preferable to have an average particle diameter of 2.2 to 40 mm. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The polyester 'obtained in the above-mentioned liquid-phase polycondensation step may be further subjected to solid-phase polycondensation if necessary. (Solid-phase polycondensation polymerization step) The particle size polyester fed to the solid-phase polycondensation polymerization step is previously heated to a temperature lower than the temperature at which the solid-phase polycondensation reaction is performed to perform precrystallization, and then fed to the solid-phase polycondensation polymerization step. Yes. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -70-8 A7 _______B7__ V. Description of invention (68) (Please read the precautions on the back before filling this page) In the above precrystallization step In a dry state, the granular polyester is usually heated to 120 to 200 t, of which 1 to 30 to 180 t: heating for 1 minute to 4 hours. In addition, the above-mentioned precrystallization can also be performed for 1 minute at a temperature of 120-2000r under the conditions of water vapor, inert gas environment containing water vapor, or air condition containing water vapor. This is done. The degree of crystallization of the pre-crystallized polyester is preferably 20 to 50%. In the above-mentioned pre-crystallization treatment, the so-called solid phase condensation polymerization of the polyester is no longer performed, and the pre-crystallized polymer The inherent viscosity of the ester is almost the same as the inherent viscosity of the polyester after liquid phase condensation polymerization. The difference between the inherent viscosity of the polyester after precrystallization and the inherent viscosity of the polyester before precrystallization is usually 0.06 dl / g. the following. The solid-phase condensation step consists of at least one stage. The reaction temperature is from 190 to 230 ° C, preferably from 195 to 255 ° C, and the pressure is from 1 kg / cm2 G, which is from atmospheric pressure to 100 T 〇rr. Under the conditions, it is performed in an inert gas environment such as nitrogen, argon, carbon dioxide, and the like. The inert gas used therein is preferably nitrogen. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the granular polyester obtained through the above-mentioned solid-phase polycondensation step. For example, water treatment can be performed according to the method described in Japanese Patent Publication No. 7-6 4 9 2. The polyester is contacted with water, water vapor, inert gas containing water vapor, air containing water vapor, and the like. The inherent viscosity of the granular polyester obtained according to the above is usually above 0.50 d Ι / g, of which 0.60 ~ 1.00d ι / g is more than the standard of this paper. Chinese national standard (CNS) A4 specification (210x297 & f ~~ 「71-" 585881 A7 B7____ 5. The description of the invention (69) should ideally be 0 · 75 ~ 0 · 95dl / g. (Please read the notes on the back before filling this page) Including the above The polyester production step of the esterification step and polycondensation step can be performed by any method of batch type, semi-continuous type and continuous type. The density of the polyester is usually 1.37 g / cm3 or more, of which 1.38 g / cm3 cm 3 is more suitable, especially preferably 1.39 g / cm 3 or more. For polyesters manufactured as described above, conventionally known additives such as stabilizers, release agents, antistatic agents, dispersants, dyes can be used. These additives can be added at any stage of manufacturing polyester, or added to the main compound before molding. The polyester obtained according to the present invention can be used as a raw material for various moldings, such as melt molding into bottles Hollow moldings, sheets, films, etc. It can be used for maintenance, etc., among which it is suitable to provide bottle-making applications. For the polyester prepared according to the present invention, for example, the method of forming polyethylene terephthalate into bottles, sheets, films, fibers, etc., can be used The method is known in the past. Secondly, the manufacturing method of the polyester related to other forms of the present invention is described as follows: The manufacturing method of the polyester related to another way of printing the present invention by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs includes: An esterification step in which an aromatic dicarboxylic acid or its ester-forming derivative and an aliphatic diol or its ester-forming derivative are esterified to form an oligomer; and in the presence of a polycondensation catalyst, In the method for producing a polyester having a high molecular weight polycondensation step by the low-polymer polycondensation polymerization, the following polycondensation catalyst is used, (I) a hydrolyzed product (I-j) obtained by hydrolyzing a titanium compound, or Paper size applies to China National Standard (CNS) A4 (210X297 mm) > '-72- 585881 A7 B7 V. Description of the invention (70) At least one element is selected from titanium compounds and other elements other than titanium Hydrolysate-k) is composed of hydrolysate compound or precursor mixture of the compound, and (Π) is composed of beryllium, magnesium, and, total, barium, boron, indium, gallium, manganese, A catalyst composed of at least one element selected from the group consisting of zinc, germanium, antimony, and phosphorus to form a secondary catalyst component, and the catalyst component (I ) Is added to the esterification reaction vessel. The above-mentioned hydrolyzed titanium compound is converted into a hydrolysate (I-j). At least one of the compounds of the titanium compound and the other compounds other than rhenium may be selected from a compound of the element or a mixture of its precursors. The hydrolyzed product (I-k) 'obtained from the hydrolysis is the same type as the aforementioned hydrolysate (I-j) and the hydrolysate (I-k). Examples of the auxiliary catalyst component (Π) are the same as the above-mentioned auxiliary catalyst compounds. Among them, magnesium compounds such as magnesium carbonate and magnesium acetate; calcium compounds such as calcium carbonate and calcium acetate; and zinc compounds such as zinc chloride and zinc acetate are preferred. should. The auxiliary catalyst compound can be used alone or in combination of two or more as the auxiliary catalyst component. Including an esterification step of esterifying an aromatic dicarboxylic acid or an ester-forming derivative thereof with an aliphatic diol or an ester-forming derivative thereof into an oligomer, and in the presence of a polycondensation catalyst, The method for producing a polyester by subjecting this low polymer to a polycondensation polymerization step to obtain a high molecular weight polycondensation step is carried out in accordance with the above-mentioned esterification step 'liquid phase polycondensation step', if necessary, followed by solid phase polycondensation polymerization. However, the esterification system (I) supplied to the liquid phase condensation polymerization step is composed of a hydrolysate (I-j) or a hydrolysate (I-k). The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)- -(Please read the notes on the back before filling out this page)-Order printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-73- 585881 A7 B7 V. Description of the invention (71) Condensed polymer catalyst composition, and (Please (Read the precautions on the back before filling this page) (Π) The condensation polymerization reaction is performed in the presence of a condensation polymerization catalyst composed of auxiliary catalyst components. Among the above catalyst components, the condensation polymerization catalyst component (I) can be esterified. In the reaction step, it is added to the reaction vessel immediately before the start of the esterification reaction or immediately after the start of the esterification reaction. The term "esterification reaction" as used in the present invention means a state where the esterification rate is 50% or less. The esterification rate refers to the reaction rate of aromatic dicarboxylic acids, such as dicarboxylic acid, and is expressed by the ratio of the acid sulfonium (Av) and saponified hydrazone of the reaction product. On the other hand, the auxiliary catalyst component (π) may be added to the reaction vessel in any stage of the esterification reaction step, or may be added to the reaction vessel in the first stage of the liquid phase polycondensation reaction step. When the auxiliary catalyst component (π) is added in the esterification reaction step, it can be added simultaneously with the catalyst component (I), or it can be added separately from the catalyst component (I). The usage ratio of the above-mentioned catalyst component (1) is usually 0. 0005 ~ 0.2 based on the weight of the mixture of the aromatic dicarboxylic acid and the aliphatic diol based on the weight of the metal in the catalyst component (I). % By weight, in the range of 0.001 to 0.05% by weight. The consumption amount of the auxiliary catalyst component (Π) printed by the employee cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is based on the titanium in the above-mentioned catalyst component (I-j) and the metal atom (M) in the auxiliary catalyst component (π). Ear ratio [(M) / (I-j)] 'or Mohr ratio of titanium and other elements in the above-mentioned catalyst component (I-k), and the metal atom (M) in the auxiliary catalyst component (π) [(Μ) / (ι 一 k)], usually in the range of 1/50 ~ 50/1 ', which is more preferably 1/40 ~ 40/1', especially in the range of 1/3 0 ~ 3 0/1 ideal. In addition, when using phosphorus paper, the Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) is applicable. -74- 585881 A7 B7 V. Description of the invention (72) When phosphorus compounds such as hydrochloric acid or phosphite are used, Contained metal atoms converted. (Please read the precautions on the back before filling out this page.) According to the present invention, polyesters with inherent viscosity can be obtained in a short time. Secondly, the manufacturing method of polyester in another form of the present invention is described as follows: The manufacturing method of polyester in another form of the present invention is an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic Glycol or its ester-forming derivative is made into polyester j by polycondensation reaction in the presence of the polycondensation catalyst 'and the phosphate ester selected in the following items (1) to (3) (1) Hydrolysis and halogenation A polycondensation catalyst composed of a hydrolyzed product (I_m) of a titanium compound, (2) hydrolysis of a compound of at least one element selected from a titanium halide compound and an element other than titanium or a mixture of precursors of the compound The product (I-η) is a condensation polymerization catalyst. It is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (3) The above (I-m) or (I-η) and the beryllium, magnesium, calcium, scandium, barium, Boron, aluminum, gallium, manganese, indium, zinc, germanium, and chains are selected from the group consisting of at least one element compound or phosphate, or a condensation polymerization catalyst composed of phosphite. Hydrolysate produced by hydrolysis of titanium halide compound to produce hydrolysate (I-rn), at least one element selected from titanium halide compound and other elements other than titanium or mixture of precursors of the compound Don't (I — η), the aforementioned hydrolysate (I — m), hydrolysate (this paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -75- 585881 A7 _____ _B7 V. Description of the invention (73) I-η) are the same. (Please read the notes on the back before filling out this page) Select at least one element compound or a compound consisting of beryllium, magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, germanium, and antimony, or Phosphate, or phosphite (hereinafter referred to as "co-catalyst component (na)"), specifically, the same compounds as the above-mentioned co-catalyst compounds may be exemplified, and the compounds may be used alone or in combination. Use the above deployment. As the auxiliary catalyst component (Πa), magnesium compounds such as magnesium carbonate and magnesium acetate; calcium compounds such as calcium carbonate and calcium acetate; and zinc compounds such as zinc chloride and zinc acetate are preferred. In the above polycondensation reaction, examples of the phosphate ester used in the above polycondensation catalyst include trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, and triphenyl phosphate. Esters, tricresyl phosphate and the like. A method for producing a polyester by polycondensation polymerization of an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof, such as the above-mentioned esterification step and liquid-phase polycondensation step. Then, a solid phase condensation polymerization step is performed. The use ratio of the hydrolysate (I-m) or (I-η) is based on the weight of the mixture of aromatic dicarboxylic acid and aliphatic diol, based on the intellectual property bureau of the Ministry of Economics, g (printed by the Industrial and Commercial Cooperative) ο Quantities ο • lm double genus ο ο among gold and other media, touch% ο in Changtong ο quantity 彐 彐 11 weight 2 should be better than the range% quantities 5 and 2 quantities ο ο Phosphorus should be used in medium amount, ester% acid amount, phosphorus weight is in the range of Changtong-2 1 ο% ο amount. Weight of fruit effect ester isoacid isophosphoric acid sum} when η should I reverse I (poly (Shrinking) Short m shrinks I to obtain I can be Γν, and the real-time production range is explained in detail. The above should apply the Chinese National Standard (CNS) A4 specification (210X297 mm) -76- 585881 A7 for the measurement of this paper. B7 V. Description of the invention (74) (Please read the precautions on the back before filling out this page) The amount of auxiliary catalyst component (na), based on the titanium and auxiliary catalyst component (Π in the above hydrolysate (I-m)) a) the ear ratio [(M) / (I-m)] of the metal atom (M), or the above-mentioned hydrolysis product (I-η) The molar ratio [(M) / (ι-n)] of titanium and other elements and the metal atom (M) in the auxiliary catalyst component (^) is usually in the range of 1/50 ~ 5〇 / 1, Among them, 1/4 ◦ to 40/1 is preferable, and the dosage is preferably in the range of 1/3 0 to 3 0/1. When a phosphorus compound such as phosphate or phosphite is used, it is used as a phosphorus compound. In terms of metal atom conversion, the above polycondensation catalyst and phosphate ester feeding method can be fed in the esterification reaction step stage, or it can be added to the reaction vessel in the first stage of the polycondensation reaction step. The invention can obtain a polyester having a desired intrinsic viscosity in a short time. In addition, the manufacturing method of the polyester related to another aspect of the present invention is explained as follows: The employee ’s cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the invention of the present invention. A method for producing a form-related polyester is to select an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof from the following (1) to (3). Polymerization catalysts and cyclic lactone compounds and hindered phenol compounds Polyester is produced by polycondensation in the presence of at least one compound: (1) a polycondensation catalyst composed of a hydrolyzed product (I-πm) formed by hydrolyzing a titanium halide compound, and (2) a titanium halide compound and a compound other than titanium At least one of the other elements is selected. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -77-585881. Printed by A7 __B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Or a mixture of precursors of the compound is hydrolyzed to form a polycondensation catalyst composed of a hydrolysate (I-η), (3) the above-mentioned decomposition product (I-m) or (I-η) and a beryllium, magnesium, calcium Select at least one element compound or phosphate, or a polycondensation catalyst composed of phosphite, or at least one element selected from the group consisting of gadolinium, barium, boron, aluminum, gallium, manganese, manganese, zinc, germanium, and antimony. A hydrolysate (I ~ m) obtained by hydrolyzing a titanium halide compound, a hydrolysate obtained by hydrolyzing a compound selected from at least one element of the titanium halide compound and other elements other than titanium or a mixture of precursors of the compound (I-η ), The hydrolysate (I-m) and the hydrolysate (I-η) of the same kind can be mentioned. A compound or a phosphate or a phosphite of at least one element selected from the group consisting of beryllium, magnesium, bromide, total, barium, boron, indium, gallium, fmongan, indium, zinc, germanium, and antimony, specifically, and The auxiliary catalyst components (Π a) are the same. As the auxiliary catalyst component (Πa), magnesium compounds such as magnesium carbonate and magnesium acetate; calcium compounds such as calcium carbonate and calcium acetate; and zinc compounds such as zinc chloride and zinc acetate are preferable. In the polycondensation reaction, at least one compound selected from cyclic lactone-based compounds and hindered phenol-based compounds is exemplified by 5,7-di-third-butyl-3- (3,4-dimethyl) Phenyl) —3H —benzofuran-2-one, four (methylene — 3 — (3,5-di-tertiarybutyl — 4-hydroxyphenyl) propionate) methane, three (2 , 4-Di-tert-butylphenyl) ortho-acid vinegar, This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) -73-(Please read the precautions on the back before filling this page)

°«5881 Α7 Β7 &、發明説明（76) 雙（2 ，6 — 一第二丁基一 4 —苯甲基）戊四醇一 磷酸酯， 5 —二第三丁基一 4 一經基苯甲基正磷 硬脂 第 2，6 -二第三丁基酚， 3，5 —二第三丁基—4 一羥基甲苯， 正一十八院基_3_ (4 > —羥基一 3 / ，5，一二 丁基苯基）丙酸酯， 二個（3 ，5 — 一第二丁基一 4 一羥基苯基）碟酸酯 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局R工消費合作社印製 二苯基磷酸酯， 四個（2 ，4 —二第三丁基苯基）一4，4聯苯 _二磷酸酯等。 由上述之環狀內酯系化合物和受阻酚系化合物中至少 選擇一種之化合物，可單獨一種或二種以上調配而使用。 上述環狀內酯系化合物和受阻酚系化合物中至少選擇 一種之化合物中，以5 ’ 7 —二第三丁基—（3 ，4 —二 甲苯基）一 3 Η —苯駢呋喃一2 —酮和四個（亞甲基一 3 〜（3 ，5 — 一第二丁基一 4 一經基苯基）丙酸醋）甲院 以及三個（2 ，4 -二第三丁基苯基）磷酸酯之混合物爲 較宜。 芳香族二羧酸或其酯形成性衍生物和脂肪族二元醇或 其酯形成性衍生物行縮聚合反應而製造聚酯之方法，可由 上述之醋化步驟，液相縮聚合步驟，必要時再加上固相縮 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -79· 585881 A7 經濟部智慈財產局員工消費合作社印製 B7五、發明説明（77 ) 聚合步驟而進行。 水解產物（I — m )或（I 一 η )之用量，對於芳香 族二羧酸和脂肪族二元醇之混合物重量計，以縮聚合觸媒 (1)或（2)中之金屬原子換算，通常在0 . 0005 〜〇 · 2重量％ ，其中以〇 ·〇〇1〜〇.05重量％之 範圍量使用。水解產物（I — m)或（I 一 η )之使用量 在上述範圍時，可得優異之縮聚合反應時間之縮短效果。 水解產物（I 一 m )或（I 一 η )可在酯化反應步驟 中添加到反應容器中，也可以在液相縮聚合反應步驟之第 一階段添加到反應容器中。 使用輔觸媒成分（Π a )之際，其使用量以上述水解 產物（I 一 m)中之鈦和輔觸媒成分中之金屬原子（M) 之莫耳比率〔（M ) / ( I - m )〕，或水解產物（I 一 η)中之鈦和其他元素以及輔觸媒成分中之金屬原子（M )之莫耳比率〔（Μ)/(Ι-η)〕計，通常在1/ 5 0〜5 0/1範圍用量，其中以1/4 0〜4 0/1爲 較宜，尤以1/3 0〜3 0/1範圍之用量爲最理想。又 ，使用磷酸鹽或亞磷酸鹽等磷化合物之際，以磷化合物中 所含金屬原子換算之。 輔觸媒成分（Π a )可在酯化反應步驟中添加到反應 容器中’也可以在液相縮聚合反應步驟之第一階段添加到 反應容器中。又，可以和水解產物（I 一 m)或（I 一 n )同時添加，也可以分開添加之。 環狀內酯系化合物和受阻酚系化合物中至少選擇一種 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 585881 A7 B7 五、發明説明（78) 之化合物用量，對於低聚合物中之芳香族二羧酸單位計， 通常使用10〜20 OOppm，其中以30〜1000 p p m範圍量使用爲宜。上述環狀內酯系化合物和受阻酚 系化合物中選擇至少一種化合物之使用量在上述範圍時， 可得乙醒含量較少之聚酯。 環狀內酯系化合物和受阻酚系化合物中至少選擇一種 之化合物，可在酯化反應步驟中添加反應容器中，也可以 在液相縮聚合反應步驟之第一階段添加到反應容器中。又 和水解產物（I 一 m )或（I 一 η )同時添加也行，另外 分開添加也行。 又，本發明中，縮聚合反應之際，可倂用由磷酸和磷 酸酯中至少選擇一種之磷化合物，該磷酸酯可舉三甲基磷 酸酯，三乙基磷酸酯，三正丁基磷酸酯，三辛基磷酸酯， 三苯基磷酸酯，三苯甲酚磷酸酯等。 上述磷化合物之用量，對芳香族二羧酸和脂肪族二元 醇之混合物重量計，以磷原子換算，通常在〇 . 〇 〇 i〜 0 . 1重量％，其中以0 · 002〜0 · 02重量％範圍 量使用爲較宜。 磷酸酯可在酯化反應步驟中添加到反應容器中，也可 以在縮聚合反應步驟之第一階段添加到反應容器中。 按照上述方法所得聚酯，其乙醛含量較少。由該聚醋 可製得發生惡臭或異臭較少，內容物之風味，香氣變化較 少之成型物。 又，聚酯之乙醛含量可按照前述方法測定之。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）· 81 - (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 585881 Α7 Β7 五、發明説明（79) 依據本發明可藉高聚合活性而製得聚酯’所得聚醋之 乙醒含量也較少。 (請先閱讀背面之注意事項再填寫本頁) 再就本發明之另一種形態有關之聚酯之製造方法說明 如下： 本發明之另一形態有關之聚酯之製造方法中’含芳香 族二羧酸或其酯形成性衍生物和脂肪族二元醇或其醋形成 性衍生物行酯化而形成低聚合物之酯化步驟’和縮聚合觸 媒之存在下將該低聚合物縮聚合而使之高分子量化的縮聚 合步驟之聚酯之製造方法中， 縮聚合觸媒使用， (I )由水解鹵化鈦化合物而成水解產物（I 一 ηι ) ，或鹵化鈦化合物和鈦以外之其他元素中選擇至少一種元 素之化合物或該化合物之前驅物之混合物行水解而成水解 產物（I - η )所構成縮聚合觸媒成分，和 (Π )由鈹、錶、錦、總、鋇、硼、銘、鎵、猛、銘 、鋅、鍺、銻和磷所構成群中至少選擇一種元素之化合物 所構成輔觸媒成分而構成之觸媒，並且 經濟部智慧財產局g(工消費合作社印製 在上述酯化步驟或縮聚合步驟之任意步驟中添加以色 相調整劑。 水解鹵化鈦化合物而成水解產物（I - m )，鹵化鈦 化合物和鈦以外之其他元素中至少選擇一種元素之化合物 或該化合物之前驅物之混合物行水解而成之水解產物（I 一 η )，可舉前述水解產物（I — m )，水解產物（I 一 η )相同者。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 〇〇 . 585881 A7 ___ B7 五、發明説明（80) (請先閱讀背面之注意事項再填寫本頁) 由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷、鋅、 鍺 '銻和磷所構成群中至少選擇一種元素之化合物而成輔 觸媒成分（Π )之具體例舉亦和前述輔觸媒化合物相同。 輔觸媒成分（Π )以碳酸鎂，乙酸鎂等鎂化合物；碳酸鈣 ’乙酸鈣等鈣化合物；氯化鋅，乙酸鋅等鋅化合物爲較宜 。輔觸媒化合物可以單獨一種或二種以上調配使用。 含有由芳香族二羧酸或其酯形成性衍生物和脂肪族二 元醇或其酯形成性衍生物行酯化而形成低聚合物之酯化步 驟，以及縮聚合觸媒之存在下，將該低聚合物加以縮聚合 而高分子量化之縮聚合步驟之聚酯之製造，可按照上述酯 化步驟，液相縮聚合步驟，必要時再加以固相縮聚合步驟 而進行。 上述縮聚合觸媒成分（I )之使用比率，對於芳香族 二羧酸和脂肪族二元醇之混合物重量計，以該觸媒成分（ I )中之金屬重量換算，通常在〇 . 0005〜0 . 2重 量％’其中以0 · 〇〇1〜〇 · 〇5重量％範圍爲較宜。 經濟部智慧財產局員工消費合作社印製 分 C 中 1 鹽 合 成c t其 \ 酸 聚 媒} 率，ο 磷。到 觸W比13 亞之加 合元耳\ ~ 或算添 聚他莫 oo 鹽換中 縮其之5 3酸子驟 述和} 磷原步 上鈦Mol用屬應 以括 {5 以使金反 ， 包子/尤分含化 量時原 1 ，成所酯 用*0屬在宜媒中在 使元金常較觸物以 之他之通爲輔合可 } 其中 ，1，化} Π 有分計 \ 又憐 Π { 含成 Ιο 。以纟 分彳媒 } 4 想，分 成鈦觸 i ~ 理時成 媒之輔 To 爲物媒 觸中和 C 4 量合觸 輔}}\/用化輔 I i \)/ w—I 圍 纟τ Μ 以範等 本紙張尺度適用中國國家標準（CNS) Μ規格（210χ 297公釐） -83- 585881 A7 B7 五、發明説明（81) (请先閱讀背面之注意事項存填寫本頁) 反應容器中，也可以在液相縮聚合反應步驟之第1階段添 加到反應容器中。又，也可以和縮聚合觸媒成分同時添加 ，也可以分開另外添加。 上述色相調整劑可使用有機色料，無機色料，有機染 料，無機染料等。色相以藍色或紅色爲特別理想。具體言 之，例如藍色溶劑（Solvent Blue 104 )，紅色素2 6 3 (° «5881 Α7 Β7 &, Description of the invention (76) Bis (2,6—a second butyl—4 benzyl) pentaerythritol monophosphate, 5—a second butyl—4 amenthylbenzene Methyl n-phosphostearyl 2,6-di-tertiary-butylphenol, 3,5-di-tertiary-butyl-4 monohydroxytoluene, n-octadecyl _3_ (4 > -hydroxyl-3 / , 5, dibutyl phenyl) propionate, two (3,5—a second butyl-4 hydroxyphenyl) disoate (Please read the precautions on the back before filling this page) Economy The Ministry of Intellectual Property Bureau R Industrial Consumer Cooperative printed diphenyl phosphate, four (2,4-di-tert-butylphenyl), 4,4 biphenyl diphosphate, etc. A compound selected from at least one of the above-mentioned cyclic lactone-based compound and hindered phenol-based compound may be used alone or in combination of two or more. Among the compounds selected from at least one of the cyclic lactone-based compound and the hindered phenol-based compound, 5 ′ 7-di-tert-butyl- (3,4--xylyl)-3 Η-phenylhydrazone- 2- Ketones and four (methylene-3 ~ (3,5—a second butyl-4 a methyphenyl) propionic acid vinegar) a hospital and three (2,4-di third butylphenyl) Mixtures of phosphate esters are preferred. A method for producing a polyester by condensation polymerization of an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof may be performed by the above-mentioned vinegarization step and liquid-phase condensation polymerization step. In addition, the solid phase shrink paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -79 · 585881 A7 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs B7 V. Invention Description (77) Aggregation steps And proceed. The amount of the hydrolysate (I — m) or (I-η) is calculated based on the weight of the mixture of aromatic dicarboxylic acid and aliphatic diol, and is converted to the metal atom in the polycondensation catalyst (1) or (2) Generally, it is used in an amount ranging from 0.005 to 0.2% by weight, in which the amount is in the range of 0.000 to 0.05% by weight. When the amount of the hydrolysate (I-m) or (I-η) is in the above range, an excellent shortening effect of the condensation polymerization reaction time can be obtained. The hydrolysate (I-m) or (I-η) may be added to the reaction vessel in the esterification reaction step, or may be added to the reaction vessel in the first stage of the liquid phase polycondensation reaction step. When the auxiliary catalyst component (Π a) is used, the amount used is based on the molar ratio of titanium in the hydrolysate (I to m) and the metal atom (M) in the auxiliary catalyst component [(M) / (I -m)], or the molar ratio [(M) / (Ι-η)] of titanium and other elements in the hydrolysate (I-η) and the metal atom (M) in the auxiliary catalyst component, usually in Dosage in the range of 1/50 to 5 0/1, among which 1/4 0 to 4 0/1 is more suitable, especially in the range of 1/3 0 to 3 0/1. When a phosphorus compound such as phosphate or phosphite is used, it is converted into a metal atom contained in the phosphorus compound. The auxiliary catalyst component (Πa) may be added to the reaction container in the esterification reaction step 'or may be added to the reaction container in the first stage of the liquid phase condensation polymerization reaction step. It may be added simultaneously with the hydrolysate (I-m) or (I-n), or it may be added separately. Choose at least one of a cyclic lactone compound and a hindered phenol compound (please read the precautions on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 size (210X 297 mm) 585881 A7 B7 5 2. Description of the invention (78) The amount of the compound is generally 10 to 20,000 ppm for the aromatic dicarboxylic acid unit in the low polymer, and it is preferably used in the range of 30 to 1000 ppm. When the amount of at least one compound selected from the cyclic lactone-based compound and the hindered phenol-based compound is within the above range, a polyester having a low content of ethylene glycol can be obtained. A compound selected from at least one of a cyclic lactone-based compound and a hindered phenol-based compound may be added to the reaction container in the esterification reaction step, or may be added to the reaction container in the first stage of the liquid phase polycondensation reaction step. It may be added at the same time as the hydrolysate (I-m) or (I-η), or separately. In addition, in the present invention, at the time of the polycondensation reaction, a phosphorus compound selected from at least one of phosphoric acid and a phosphoric acid ester may be used. Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, and tri-n-butyl phosphate. Esters, trioctyl phosphate, triphenyl phosphate, trisphenol, etc. The amount of the above-mentioned phosphorus compound is, based on the weight of the mixture of the aromatic dicarboxylic acid and the aliphatic diol, converted into a phosphorus atom, which is usually from 0.00% to 0.1% by weight, in which 0. 002 to 0. The amount in the range of 02% by weight is preferably used. The phosphate may be added to the reaction vessel in the esterification reaction step, or may be added to the reaction vessel in the first stage of the polycondensation reaction step. The polyester obtained according to the above method has less acetaldehyde content. From this polyvinegar, a molded article having less odor or off-odor, and less content flavor and aroma change can be obtained. The acetaldehyde content of the polyester can be measured according to the aforementioned method. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) · 81-(Please read the notes on the back before filling out this page) Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives 585881 Α7 Β7 V. Inventions Explanation (79) According to the present invention, the polyester obtained by high polymerization activity can obtain less ethyl acetate. (Please read the precautions on the back before filling this page.) Then, the manufacturing method of polyester related to another form of the present invention is described as follows: In the manufacturing method of polyester related to another form of the present invention, 'contains aromatic two An esterification step in which a carboxylic acid or its ester-forming derivative and an aliphatic diol or its vinegar-forming derivative are esterified to form an oligomer, and the oligomer is polycondensed in the presence of a polycondensation catalyst. In the method for producing a polyester with a high molecular weight polycondensation step, a polycondensation catalyst is used, (I) a hydrolysate (I-ηι) obtained by hydrolyzing a titanium halide compound, or a compound other than titanium halide and titanium Among other elements, a compound selected from at least one element or a mixture of the precursors of the compound is hydrolyzed to form a polycondensation catalyst component composed of a hydrolysate (I-η), and (Π) is made of beryllium, table, brocade, total, barium , Boron, indium, gallium, manganese, indium, zinc, germanium, antimony and phosphorus in the group of at least one element selected from the group consisting of auxiliary catalyst components composed of catalysts, and the Ministry of Economic Affairs Intellectual Property Bureau Cooperation The company printed by adding a hue adjuster in any of the above-mentioned esterification step or polycondensation step. Hydrolysing the titanium halide compound to form a hydrolysate (I-m), at least one element selected from the titanium halide compound and other elements other than titanium. The hydrolyzate (I-η) obtained by hydrolyzing the compound or a mixture of the precursors of the compound may be the same as the aforementioned hydrolyzate (I-m) and the hydrolysate (I-η). The paper size is applicable to the country of China Standard (CNS) A4 specification (210X297 mm) 〇 585881 A7 ___ B7 V. Description of the invention (80) (Please read the notes on the back before filling this page) Made of beryllium, magnesium, calcium, thallium, barium, boron Specific examples of the auxiliary catalyst component (Π) selected from the group consisting of at least one element in the group consisting of aluminum, gallium, manganese, cobalt, zinc, germanium, antimony, and phosphorus are also the same as the aforementioned auxiliary catalyst compounds. The vehicle components (Π) are magnesium compounds such as magnesium carbonate and magnesium acetate; calcium compounds such as calcium carbonate and calcium acetate; zinc compounds such as zinc chloride and zinc acetate are more suitable. The auxiliary catalyst compounds may be used alone or in combination. Formulation and use: Contains an esterification step in which an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative are esterified to form an oligomer, and the presence of a polycondensation catalyst Next, the polyester is produced by subjecting the low polymer to a polycondensation and polymerizing polycondensation step according to the above-mentioned esterification step, liquid phase polycondensation step, and if necessary, a solid phase polycondensation step. 0005〜0 The ratio of use of the polycondensation catalyst component (I), based on the weight of the mixture of the aromatic dicarboxylic acid and the aliphatic diol, is converted to the weight of the metal in the catalyst component (I), usually in the range of 0.005 ~ 0 2% by weight ', which is more preferably in the range of 0. 0001 to 0. 5% by weight. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the 1 salt synthesis in C, and its acid concentration, ο phosphorus. In order to touch W than 13 Asia's plus ears \ ~ Or calculate the addition of poly tamo oo salt in exchange for the reduction of the 5 3 acid protons and} The phosphorus molybdenum step on titanium Mol should be enclosed in {5 to make gold On the contrary, the bun / special content is the original 1, and the ester used * 0 is in the appropriate medium, which can be used to make Yuan Jin often better than other materials. Among them, 1, chemical} Π has Points count \ You pity Π {含 成 Ιο. Think of the media 4 4 想, divided into titanium touch i ~ time-matched media auxiliary To To the physical media touch and C 4 volume and touch auxiliary}} \ / 化 化 助 I i \) / w—I encircle τ Μ Applicable to Chinese National Standards (CNS) Μ specifications (210χ 297 mm) at the standard paper size. -83- 585881 A7 B7 V. Description of the invention (81) (Please read the precautions on the back and fill in this page) Reaction In the container, it may be added to the reaction container in the first stage of the liquid phase polycondensation reaction step. In addition, it may be added simultaneously with the polycondensation catalyst component, or it may be added separately. Examples of the hue adjusting agent include organic colorants, inorganic colorants, organic dyes, and inorganic dyes. The hue is particularly desirable in blue or red. Specifically, for example, blue solvent (Solvent Blue 104), red pigment 2 6 3 (

Pigment Red 263 )，紅色溶劑 1 3 5 ( Solvent Red 135) ，藍色素 2 9 (Pigment Blue 29)，藍色素 1 5 : 1 (Pigment Red 263), red solvent 1 3 5 (Solvent Red 135), blue pigment 2 9 (Pigment Blue 29), blue pigment 1 5: 1 (

Pigment Blue 15:1)，藍色素 1 5 : 3 (Pigment Blue 15:3)，紅色素 1 8 7 (Pigment Red 187)，紫色素 1 9 (Pigment V1〇let 19)等（上述例舉爲比色指數名稱）。 色相調整劑可以單獨一種或二種以上調配使用。 上述色相調整劑之使用比率，對於聚酯重量計，通常 使用0 · 05〜lOOppm，其中以〇 · 1〜50 p p m範圍爲較宜。 經濟部智慧財產局員工消費合作社印製 色相調整劑可以在酯化反應步驟中添加到反應容器中 ’也可以在液相縮聚合反應步驟之第一階段添加到反應容 器中。又，可以和縮聚合觸媒成分同時添加，也可以分開 另外添加。 依據本發明，可藉高聚合活性而製造色相優異的聚酯 〇 其次，就本發明有關之聚酯之處理方法說明如下。 本發明之另一形態有關之聚酯之處理方法，乃係使用 鈦化合物觸媒而得’並且將反應終結之聚酯以濃度爲磷原 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -84- 585881 A7Pigment Blue 15: 1), blue pigment 15: 3 (Pigment Blue 15: 3), red pigment 1 8 7 (Pigment Red 187), purple pigment 1 9 (Pigment V1〇let 19), etc. (the above examples are for comparison Color index name). The hue adjusting agent can be used alone or in combination of two or more. The use ratio of the above-mentioned hue adjusting agent is usually from 0.05 to 100 ppm based on the weight of the polyester, and a range of from 0.1 to 50 p p m is preferable. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Hue adjuster can be added to the reaction vessel in the esterification reaction step, or it can be added to the reaction vessel in the first stage of the liquid phase condensation polymerization reaction step. It may be added at the same time as the polycondensation catalyst component, or may be added separately. According to the present invention, a polyester having excellent hue can be produced by high polymerization activity. Second, the processing method of the polyester related to the present invention is described below. The processing method of the polyester according to another aspect of the present invention is obtained by using a titanium compound catalyst, and the polyester at the end of the reaction is used as the phosphorus. The original paper size is applicable to China National Standard (CNS) A4 specification (210X297). Centimeters) -84- 585881 A7

五、發明説明（82) 子換算1 0 p p m以上之亞磷酸水溶液，次磷酸水溶液， 磷酸酯水溶液，亞磷酸酯水溶液或次磷酸酯水溶液接觸而 經濟部智慧財產局員工消費合作社印製 又，本發明之又一形態有關之聚酯之處理方法，乃係 使用鈦化合物觸媒而得，並且將反應終結之聚酯和有機溶 媒接觸而成。 本發明之再一種其他形態有關之聚酯之處理方法，乃 係使用駄化合物觸媒而得’並且將反應終結之聚醋，以磷 原子換算’其濃度爲1 Ο ρ p m以上之磷酸之有機溶媒溶 液，磷酸酯之有機溶媒溶液，亞磷酸之有機溶媒溶液，次 磷酸之有機溶媒溶液，亞磷酸酯之有機溶媒溶液或次磷酸 酯之有機溶媒溶液接觸而成。 本發明之處理方法中所使用聚酯乃係使用芳香族二羧 酸或其酯形成性衍生物和脂肪族二元醇或其酯形成性衍生 物，以及必要時加上多官能性化合物等爲原料製成之聚酯 ，其中以使用對苯二甲酸或其酯形成性衍生物和乙二醇或 其酯形成性衍生物爲原料所製成之聚乙烯對苯二甲酸酯爲 較宜。該聚乙烯對苯二甲酸酯尙可以有2 0莫耳％以下之 其他二羧酸和/或其他二元醇共聚合而成。 上述對苯二甲酸以外之其他二羧酸之具體例舉有苯二 甲酸，異苯二甲酸，萘二羧酸，二苯基二羧酸，二苯氧基 乙烷二羧酸等之芳香族二羧酸；己二酸，癸二酸，壬二酸 1 〇 —癸烷二羧酸等之脂 羧酸；環己基二羧 酸等之脂環族二羧酸等以及其酯形成性衍生物等。 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） — (請先閱讀背面之注意事項再填寫本頁) 訂· -· -85- ^5881 Α7 Β7 i、發明説明（83) 乙二醇以外之其他二元醇之具體例舉有1 ，3 一丙二 醇，丙二醇’ 1 ，4 — 丁二醇，新戊二醇，1 ，6〜己二 (請先閱讀背面之注意事項再填寫本頁) 1 ，1 2 -十二烷二醇等之脂肪族二元醇；環己院二 甲醇等脂環族二元醇；雙酚類，氫醌，2 ，2 —雙（4 — 点一羥基乙氧基苯基）丙烷，1 ，3 -雙（2 -經基乙氧 基）苯，1 ，4 一雙（2 -羥基乙氧基）苯等之芳香族二 元醇類，以及其酯形成性衍生物等。 本發明之處理方法中所使用聚酯，可使用含有芳香族 二羧酸或其酯形成性衍生物和脂肪族二元醇或其酯形成性 衍生物，最好是上述之苯甲二酸或其酯形成性衍生物和乙 二醇或其酯形成性衍生物之原料，按照上述進行酯化步驟 ’液相縮聚合步驟’必要時，再加以固相縮聚合步驟而製 造之。 上述之縮聚合反應’在下述縮聚合觸媒和上述安定劑 之存在下實施爲宜。 經濟部智慧財產局員工消費合作社印製 縮聚合觸媒之例舉如上述之_化駄化合物經水解而成 水解產物（I - m )或鹵化鈦化合物和鈦以外之其他元素 中至少選擇一種元素之化合物或該化合物之前驅物之混合 物行水解而成之水解產物（I - η )等可供使用。 又，做爲縮聚合觸媒用途，可使用丁氧基鈦，四異丁 氧基鈦等烷氧基鈦；鈦之乙醯丙酮鹽等有機鈦化合物；院 氧基鈦之水解而成水解產物等鈦化合物。烷氧基鈦之水解 產物可按照上述鹵化鈦化合物之水解產物之調製所使用相 同方法調製之。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -86- 585881 A7 B7 五、發明説明（84) 上述水解產物（I — m )或水解產物（I — η )(即 含鈦水解產物（Α - 2 ))在必要時和輔觸媒成分（Π ) 倂用。 輔觸媒成分（Π )可使用上述輔觸媒化合物所舉相同 化合物，其中以碳酸鎂，乙酸鎂等鎂化合物；碳酸鈣，乙 酸鈣等鈣化合物；氯化鋅，乙酸鋅等鋅化合物爲較宜。輔 觸媒化合物可單獨一種或二種以上調配做爲輔觸媒成分而 使用。 使用鎂化合物爲輔觸媒成分時，可製得透明性優異的 聚酯，特別是聚乙烯對苯二甲酸酯。 上述輔觸媒成分（Π )之使用，以上述含鈦水解產物 ((A - 2 ))中之鈦（含鈦水解產物（A - 2 )含有其 他元素時，包括鈦和其他元素），和輔觸媒成分（π )中 之金屬原子之莫耳比率〔（Π)/((A-2))〕計， 通常在1/50〜50/1 ，其中以1/4 ◦〜40/1 爲較宜’尤以1/3 0〜3 0/1範圍量使用爲理想。又 ，使用磷酸鹽或亞磷酸鹽等磷化合物時，以磷化合物中所 含金屬原子換算之。 上述縮聚觸媒之使用比率，對於芳香族二羧酸和脂肪 族二元醇之混合物重量計，縮聚合觸媒時以縮聚觸媒中之 金屬重量換算，通常在0·0005〜〇.2重量％，其 中以0 · 00 1〜0 _ 05重量％範圍爲較宜，又，安定 劑以安定劑中之磷原子重量計，通常在〇 . 〇 0 i〜 0 · 1重量％，其中以0 · 002〜〇 · 〇2重量％範圍 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ---------0^-- (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention (82) Aqueous phosphorous acid solution, hypophosphorous acid solution, phosphoric acid ester solution, phosphite solution or hypophosphite solution which is more than 10 ppm in sub-conversion is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The processing method of the polyester according to another aspect of the invention is obtained by using a titanium compound catalyst, and contacting the polyester with which the reaction has ended with an organic solvent. The processing method of the polyester related to another aspect of the present invention is an organic compound of phosphoric acid having a concentration of 1 0 ρ pm or more, obtained by using a phosphonium compound catalyst, and a polyacetate that terminates the reaction, in terms of phosphorus atoms. Solvent solution, organic solvent solution of phosphate, organic solvent solution of phosphorous acid, organic solvent solution of hypophosphorous acid, organic solvent solution of phosphite or organic solvent solution of hypophosphite. The polyester used in the processing method of the present invention is to use an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof, and to add a polyfunctional compound, etc. as necessary Among the polyesters made of raw materials, polyethylene terephthalate made of terephthalic acid or an ester-forming derivative thereof and ethylene glycol or an ester-forming derivative thereof is preferable. The polyethylene terephthalate may be copolymerized with other dicarboxylic acids and / or other diols having a content of less than 20 mol%. Specific examples of the dicarboxylic acid other than the terephthalic acid include aromatic acids such as phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and diphenoxyethanedicarboxylic acid. Dicarboxylic acids; adipic acid, sebacic acid, azelaic acid, 10-decane dicarboxylic acid, and other aliphatic carboxylic acids; cyclohexyl dicarboxylic acid, and other alicyclic dicarboxylic acids and the like; and ester-forming derivatives thereof Wait. This paper size applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) — (Please read the precautions on the back before filling this page) Order ·-· -85- ^ 5881 Α7 Β7 i. Description of the invention (83) Specific examples of glycols other than ethylene glycol include 1,3 monopropylene glycol, propylene glycol '1, 4-butanediol, neopentyl glycol, 1, 6 ~ hexanedione (please read the precautions on the back before (Fill in this page) Aliphatic diols such as 1,1,2-dodecanediol; Alicyclic diols such as cyclohexyl dimethanol; bisphenols, hydroquinone, 2, 2 —bis (4 — Aromatic diols such as monohydroxyethoxyphenyl) propane, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, And its ester-forming derivatives. The polyester used in the treatment method of the present invention may include an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof, preferably the above-mentioned benzoic acid or The raw materials of the ester-forming derivative and ethylene glycol or the ester-forming derivative thereof are prepared by performing the esterification step 'liquid phase condensation polymerization step' as necessary, and then performing the solid phase condensation polymerization step as necessary. The above-mentioned polycondensation reaction 'is preferably carried out in the presence of the following polycondensation catalyst and the above-mentioned stabilizer. An example of the condensation polymerization catalyst printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is the above-mentioned _ chemical compound is hydrolyzed to form a hydrolysate (I-m) or a titanium halide compound and at least one element other than titanium Hydrolysates (I-η) obtained by hydrolyzing the compound or a mixture of the precursors of the compound can be used. In addition, for the application of polycondensation catalysts, alkoxy titanium such as butoxy titanium and tetraisobutoxy titanium; organic titanium compounds such as acetoacetone salt of titanium; and hydrolysis products of titanium oxy titanium can be used. And other titanium compounds. The hydrolysis product of titanium alkoxide can be prepared in the same manner as in the above-mentioned preparation of the hydrolysis product of the titanium halide compound. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -86-585881 A7 B7 V. Description of the invention (84) The above-mentioned hydrolysate (I — m) or hydrolysate (I — η) (that is, titanium-containing) The hydrolysate (Α-2)) is used with the auxiliary catalyst component (Π) when necessary. As the auxiliary catalyst component (Π), the same compounds as those mentioned above can be used. Among them, magnesium compounds such as magnesium carbonate and magnesium acetate; calcium compounds such as calcium carbonate and calcium acetate; and zinc compounds such as zinc chloride and zinc acetate are preferred. should. The secondary catalyst compounds can be used alone or in combination as a secondary catalyst component. When a magnesium compound is used as the auxiliary catalyst component, a polyester having excellent transparency, particularly polyethylene terephthalate, can be obtained. The use of the above-mentioned auxiliary catalyst component (Π), the titanium in the above-mentioned titanium-containing hydrolysate ((A-2)) (when the titanium-containing hydrolysate (A-2) contains other elements, including titanium and other elements), and Mole ratio of metal atom in auxiliary catalyst component (π) [(Π) / ((A-2))], usually 1/50 ~ 50/1, among which 1/4 ◦ ~ 40/1 It is more appropriate to use it in the range of 1/3 0 ~ 3 0/1. When a phosphorus compound such as phosphate or phosphite is used, it is converted into a metal atom contained in the phosphorus compound. The use ratio of the above polycondensation catalyst is based on the weight of the mixture of the aromatic dicarboxylic acid and the aliphatic diol. When the polycondensation catalyst is converted to the weight of the metal in the polycondensation catalyst, it is usually from 0.005 to 0.2 % ， Wherein a range of 0 · 00 1 ~ 0 _ 05% by weight is more suitable. Moreover, the stabilizer is based on the weight of the phosphorus atom in the stabilizer, usually in the range of 〇0 i ~ 0 · 1% by weight, in which 0 · 002 ~ 〇 · 〇2% by weight range This paper size applies Chinese National Standard (CNS) Α4 specification (210X297 mm) --------- 0 ^-(Please read the precautions on the back before filling (This page)

、1T 經濟部智慧財產局員工消費合作社印製 -87- 585881 A7 _ B7 五、發明説明（85) 爲較宜。上述縮聚合觸媒和安定劑之供料方法，可以在酯 化反應步驟之階段中供料，也可以在縮聚合反應步驟之第 一階段供料到反應容器中。 又，本發明之聚酯爲聚乙烯對苯二甲酸酯時，由液相 縮聚合步驟之最終縮聚合反應容器所得之聚乙烯對苯二甲 酸酯，所含下列一般式所示乙烯對苯二甲酸酯成分單位之 含有率在95 · 0〜99 . 0莫耳％範圍， π /=\ η —|0C—^ COCH2OCH2^r- 而下列一般式所示二氧化乙烯對苯二甲酸酯成分單位 之含有率在1 . 0〜5 · 0莫耳％之範圍爲宜。 〇 〇 —\---COCH2CH2OCH2CH2·)— 按照上述所得聚酯之固有粘度通常爲Ο . 5 0 d 1 / g以上，其中以Ο·50〜1·50d1/g爲較宜，尤 以Ο · 7 2〜1 · 0 d 1 / g爲理想。該聚酯之密度通常 爲1 · 37g/cm3以上，其中以1 · 37〜1 .44 g/cm3 爲較宜，以 1 · 38 〜1 · 43g/cm3 爲 更佳，尤以1 _ 39〜1 · 42g/cm3以上爲理想。 又，上述聚酯中所含乙醛量通常在5 p pm以下，其 中以0〜3 p pm爲較宜，尤以0〜2 p pm爲理想。乙 醛含量可按照上述方法測定而得。 本發明有關之聚酯之處理方法裡，在上述聚酯之製造 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慈財產局員工消費合作社印製 -88- 585881 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（86) 步驟中，使用反應終結之聚酯。所謂反應終結之聚酯乃指 反應後固有粘度不再增加之聚酯，例如經過液相縮聚合步 驟之聚醋’或經過固相縮聚合步驟之聚酯。該聚酯通常爲 粒狀，但可以爲粉狀，單紗狀。 本發明實施上述聚酯，特別宜以聚乙烯對苯二甲酸酯 和亞磷酸水溶液’次磷酸水溶液，磷酸酯水溶液，亞磷酸 酯水溶液或次磷酸酯水溶液（下文中稱爲「含磷水溶液」 )接觸之含磷水溶液處理。 或實施以上述聚酯’特別宜以聚乙烯對苯二甲酸酯和 有機溶媒接觸之有機溶媒處理，或 實施以上述聚酯’特別是宜以聚乙烯對苯二甲酸酯和 磷酸之有機溶媒溶液’亞磷酸之有機溶媒溶液，次磷酸之 有機溶媒溶液，磷酸酯之有機溶媒溶液，亞磷酸酯之有機 溶媒溶液或次磷酸酯之有機溶媒溶液（下文中或稱爲「含 磷有機溶媒溶液」）接觸之含磷有機溶媒溶劑處理。 含磷水溶液處理所使用之磷酸酯，例如單甲基磷酸酯 ，二甲基磷酸酯，三甲基磷酸酯，單乙基磷酸酯，二乙基 磷酸酯，三乙基磷酸酯，三丁基磷酸酯，三正丁基磷酸酯 ，三辛基磷酸酯，三苯基磷酸酯，三甲酚基磷酸酯等；亞 磷酸酯之例舉有甲基亞磷酸酯，二甲基亞磷酸酯，三甲基 亞磷酸酯，乙基亞磷酸酯，二乙基亞磷酸酯，三乙基亞磷 酸酯，三丁基亞磷酸酯，三苯基亞磷酸酯，三個十二烷基 亞磷酸酯，三個壬基苯基亞磷酸酯等；次磷酸酯之例舉有 如次磷酸甲酯，次磷酸三甲酯等。 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -89- 585881 A7 B7 五、發明説明（87 ) 和聚酯接觸用之含磷水溶液’以碟原子換算之 l〇ppm以上’其中以10〜100〇〇〇PP 宜，1〇〇〜7〇〇〇〇ΡΡηι爲更佳，尤以1〇Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T -87- 585881 A7 _ B7 5. The invention description (85) is more appropriate. The above-mentioned method for feeding the polycondensation catalyst and stabilizer may be fed in the stage of the esterification reaction step, or may be fed into the reaction container in the first stage of the polycondensation reaction step. In addition, when the polyester of the present invention is polyethylene terephthalate, the polyethylene terephthalate obtained from the final polycondensation reaction vessel in the liquid phase condensation polymerization step contains an ethylene pair represented by the following general formula: The content rate of the phthalate component unit is in the range of 95 · 0 ~ 99.0 mole%, π / = \ η — | 0C— ^ COCH2OCH2 ^ r- The content rate of the acid ester component unit is preferably in a range of 1.0 to 5.0 mole%. 〇〇 — \ --- COCH2CH2OCH2CH2 ·) — The inherent viscosity of the polyester obtained according to the above is usually 0. 50 d 1 / g or more, of which 0 · 50 ~ 1 · 50d1 / g is preferable, especially 0 · 7 2 to 1 · 0 d 1 / g is ideal. The density of the polyester is usually 1.37 g / cm3 or more, of which 1.37 to 1.44 g / cm3 is more preferable, and 1.38 to 1.43 g / cm3 is more preferable, especially 1_39 to 1 · 42 g / cm3 or more is preferable. The amount of acetaldehyde contained in the polyester is usually 5 p pm or less, with 0 to 3 p pm being more preferred, and 0 to 2 p pm being particularly preferred. The acetaldehyde content can be determined by the method described above. In the processing method of the polyester related to the present invention, the Chinese paper standard (CNS) A4 specification (210X 297 mm) is applied to the paper size of the above-mentioned polyester-(Please read the precautions on the back before filling this page) Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-88- 585881 A7 B7 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (86) The polyester used in the reaction is terminated. The so-called reaction-terminated polyester refers to a polyester whose intrinsic viscosity does not increase after the reaction, such as a polyester which has undergone a liquid-phase condensation polymerization step or a polyester which has undergone a solid-phase condensation polymerization step. The polyester is usually granular, but may be powdery or single yarn. In the implementation of the above-mentioned polyester in the present invention, it is particularly preferable to use polyethylene terephthalate and an aqueous solution of phosphorous acid, an aqueous solution of hypophosphorous acid, an aqueous solution of phosphate, an aqueous solution of phosphite, or an aqueous solution of hypophosphite (hereinafter referred to as "phosphorus-containing aqueous solution"). ) Contact with a phosphorus-containing aqueous solution. Or the organic solvent treatment with the above-mentioned polyester 'especially with polyethylene terephthalate and organic solvent, or the organic solvent with the above-mentioned polyester' especially with polyethylene terephthalate and phosphoric acid Solvent solution 'organic solvent solution of phosphorous acid, organic solvent solution of hypophosphorous acid, organic solvent solution of phosphate, organic solvent solution of phosphite or organic solvent solution of hypophosphite (hereinafter referred to as "phosphorus organic solvent" Solution ") in contact with a phosphorus-containing organic solvent solvent. Phosphates used in the treatment of phosphorus-containing aqueous solutions, such as monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, monoethyl phosphate, diethyl phosphate, triethyl phosphate, tributyl Phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, etc .; examples of the phosphite include methyl phosphite, dimethyl phosphite, three Methyl phosphite, ethyl phosphite, diethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite, three dodecyl phosphites, Three nonylphenyl phosphites, etc .; hypophosphites are exemplified by methyl hypophosphite, trimethyl hypophosphite, and the like. (Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -89- 585881 A7 B7 V. Description of the invention (87) Phosphorus aqueous solution 'more than 10 ppm in terms of dish atoms' Among them, 10 to 100,000 PP is preferable, and 100 to 70, 000 PP is more preferable, especially 10%.

5 Ο Ο Ο Ο P P 爲理想 經 濟 部 智 慧 財 產 局 消 費 人 社 印 製 含磷水溶液之濃度在上述範圍時’所得之聚酯 之際，降低乙醒含量之增量效果局’且甚經濟。 聚酯和含磷水溶液之接觸可任意利用連續式、 而進行。 聚酯和含磷水溶液以分批式接觸時，例如可利 型之處理裝置。具體言之’將聚醋和含磷水溶液裝 中，使聚酯浸漬在含磷水溶液中。又’利用可旋轉 容器中裝入聚酯和含磷水溶液’將聚酯浸漬在含磷 中，旋轉筒型容器而接觸’可提升接觸處理之效率。 聚酯和含磷水溶液以連續式接觸時，例如利用 處理裝置，由塔型之處理裝置頂端連續供應聚酯， 順流或逆流方式將含磷水溶液連續供應到塔型之處 中，使聚酯浸漬含磷水溶液而接觸處理。 聚酯和含磷水溶液之接觸溫度，通常在0〜1 ，其中以1 0〜9 5 °C範圍爲較宜，接觸時間通常 鐘〜1 0小時，其中以3 0分鐘〜6小時爲較宜。 聚酯和含磷水溶液接觸之後，將聚酯和含磷水 離，使用粒狀振動篩機，凝膠乾燥機等去水裝置去 |燥之。和含磷水溶液接觸過之聚酯之乾燥，也可以 |常所用聚酯之乾燥方法。 濃度在 m爲較 〇〇〜 在成型 分批式 用筒倉 入筒倉 之筒型 水溶液 塔型之 另外以 理裝置 0 0 °c 在5分 溶液分 水並乾 採用通 (請先閲讀背面之注意事項再填寫本頁) 、1Τ 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公麓） 90- 585881 A7 B7 五、發明説明（88) 聚酯之連續式乾燥方法，自上端供應聚酯’由下端通 入乾燥氣體之料斗型之通風乾燥機，通常最受採用。減少 乾燥氣體量而有效乾燥之方法，例如有使用旋轉盤式加熱 方式之連續乾燥機之方法，該方法中可用少量之乾燥氣體 通風下，供應加熱熱氣，加熱熱媒等於旋轉盤或外罩，以 間接加熱乾燥方法乾燥聚酯。 使用分批式乾燥聚酯之方法，例如有使用雙錐型旋轉 乾燥機之方法，該方法中，在減壓下，或在減壓下以少量 之乾燥氣體通風，或常壓下通入乾燥氣體下乾燥之。乾燥 氣體也可以使用空氣，但防止聚酯因水解而分子量降低之 觀點，以利用乾燥氮氣或除濕空氣爲較宜。 按照上述將聚酯和含磷水溶液接觸時，成型之際可得 乙醛之增加量少，固有粘度降低較少之聚酯。此乃推測係 由於聚酯和含磷水溶液接觸，可使聚酯中之縮聚合觸媒失 去活性所造成。 由上述聚酯可製得發生惡臭或異臭較少，內容物之風 味，香氣變化較少之成型物。 上述可藉例如將聚酯在2 7 5 °C溫度下加熱熔融成型 爲階梯式矩形成型物之後，測定其乙醛之增加量而確認之 。上述階梯式矩形成型物按下述方法成型之。 首先，將預先測定過乙醛含量（X重量％)之粒狀聚 酯（顆粒狀聚酯）2 k g做爲原料，在1 4 0 °C，1 〇 T 〇 r r壓力條件下，使用層狀式之乾燥機乾燥丨6小時 以上，把粒狀聚酯之水分降到5 0 p p m以下。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公羡）,Q1 ^ ---------— (請先閱讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 585881 A7 B7____ 89 五、發明説明（） ----------- (請先閲讀背面之注意事項再填寫本頁) 其次，使用上述乾燥聚酯，藉名機製作所公司製之Μ - 7 Ο Α型之壓注模成型機加以壓注模成型而得階梯式矩 形成型物。成型在以露點爲- 7 〇 °c之氮氣自料斗上端以 分別爲5正立方公尺/小時之比率供應到螺旋型加料滑槽 ，成型以桶之設定溫度在2 7 5°C ’成型機之C l/c 2 /C 3 /噴嘴口之溫度設定爲2 6 0°C/2 9 Ot：/ 2 9 0 °C / 3 0 0 °C之各種溫度，模之冷卻溫度爲1 5 t： 之條件下進行。 階梯式矩形成型物之壓注模成型，以計量1 2秒鐘， 壓注模時間6 0秒鐘之成型條件而調整好的壓注模成型機 ，自料斗供應乾燥之粒狀聚酯而成型。又成型機內之熔融 樹脂之滯留時間約爲7 2秒鐘。又，階梯式矩形成型物之 每一個重量爲7 5 g，乙醛含量之測定用試料利用壓注模 成型開始後第1 1〜1 5個成型物之任意一個而進行。 階梯式矩形成型物具有圖2所示形狀，其A處之厚度 約爲6 · 5mm，B處之厚度約爲5mm，C處之厚度約 爲4mm。使用C處之成型物測定其乙醛含量。 經濟部智慧財產局8工消費合作社印製 其次，將成型好的階梯式矩形成型物之C處切斷爲片 狀，做爲乙醛含量測定用試料測定其乙醛含量。 按照上述方法對於聚酯，特別宜用聚乙烯對苯二甲酸 酯進行含磷水溶液處理時，可得成型時乙醛含量增加較少 ’且固有粘度降低較少之聚酯。 其次，就有機溶媒處理說明如下。 有機溶媒處理所使用之有機溶媒，例如甲醇，乙醇， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）· 92 · 585881 A7 B7 五、發明説明（9Q ) 丙醇，異丙醇，丁醇，戊醇，己醇，2 -乙基己醇，辛醇 ，十二烷醇，十八烷醇，油醇，苯甲醇，苯基乙醇，枯醇 ，異丙基苯甲醇等碳原子數在1〜1 8之醇類，其中以碳 原子數爲1〜1 0之醇類爲較宜；丙酮，甲乙基酮，甲異 丁基酮，苯乙酮，二苯甲酮，苯醌等碳原子數在3〜1 5 之酮類，其中以碳原子數爲3〜9之酮類爲較宜；丁烷， 戊烷，己烷，庚烷，辛烷，壬烷，癸烷，十一烷，十二烷 ，十三烷，十四烷，十五烷，十六烷等碳原子數在5〜 1 6之飽和碳化氫，其中以碳原子數爲5〜1 0之飽和碳 化氫爲較宜。其中尤以異丙醇或丙酮爲佳。 聚酯和有機溶媒之接觸，可任意爲連續方式，或分批 方式進行。具體而言，上述含磷水溶液處理中，以有機溶 媒代替含磷水溶液而以相同方法進行。 聚酯和有機溶媒之接觸溫度，隨使用有機溶媒之沸點 而異，通常在0〜100 °C，其中以10〜95 °C範圍爲 較宜，接觸時間通常在3分鐘〜5小時，其中以3 0分鐘 〜4小時爲理想。 聚酯和有機溶媒接觸之後，將聚酯和有機溶媒分離， 以粒狀振動篩機，凝膠乾燥機等去水裝置除去水分，並乾 燥之。和有機溶媒接觸過之聚酯之乾燥，可採用通常使用 之聚酯之乾燥方法，具體言之，例如上述之連續乾燥方法 ，分批式乾燥方法等。 如上述聚酯和有機溶媒接觸時，可得成型之際，乙醛 增加量少之聚酯。據推測這是由聚酯和有機溶媒接觸時， 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐）.93 - ---------- (請先閱讀背面之注意事項再填寫本頁)5 Ο Ο Ο Ο P P is the ideal printed by the Ministry of Economic Affairs and Intellectual Property Bureau Consumers' Agency when the concentration of the phosphorus-containing aqueous solution is in the above range ‘the obtained polyester, the incremental effect of reducing the content of dioxin is very economical. The contact between the polyester and the phosphorus-containing aqueous solution can be carried out arbitrarily by a continuous method. When the polyester and the phosphorus-containing aqueous solution are contacted in a batch manner, for example, a processing device of a favorable type can be used. Specifically, 'polyacetic acid and a phosphorus-containing aqueous solution are charged, and the polyester is immersed in the phosphorus-containing aqueous solution. Further, "the polyester and the phosphorus-containing aqueous solution are charged into a rotatable container", and the polyester is immersed in phosphorus-containing, and the cylindrical container is rotated to be brought into contact 'to improve the efficiency of the contact treatment. When the polyester and the phosphorus-containing aqueous solution are in continuous contact, for example, using a processing device, the polyester is continuously supplied from the top of the tower-type processing device, and the phosphorus-containing aqueous solution is continuously supplied to the tower type in a countercurrent or countercurrent manner to impregnate the polyester. Contact treatment with phosphorus-containing aqueous solution. The contact temperature of polyester and phosphorus-containing aqueous solution is usually in the range of 0 ~ 1, in which the range of 10 ~ 9 5 ° C is preferred, and the contact time is usually in the range of 0 ~ 10 hours, of which 30 ~ 6 hours is more suitable . After the polyester is in contact with the phosphorous-containing aqueous solution, the polyester is separated from the phosphorous-containing water, and dried using a dewatering device such as a granular shaker, gel dryer, and the like. Drying of polyesters that have been in contact with phosphorus-containing aqueous solutions can also be used. The concentration in m is more than 〇 ～~ In the forming batch type, the silo type aqueous solution tower type that uses the silo to enter the silo is separately treated with a 0 ° ° C water solution in 5 minutes and dried. Note: Please fill in this page again), 1T This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 male feet) 90-585881 A7 B7 V. Description of the invention (88) Continuous drying method for polyester Ester 'is a hopper-type ventilated drier in which a drying gas is introduced from the lower end, which is usually the most popular. There are methods for reducing the amount of drying gas to effectively dry. For example, there is a method using a continuous dryer with a rotary disk heating method. In this method, a small amount of dry gas can be used to supply heating hot air. The indirect heating drying method dries the polyester. A method of using a batch-type drying polyester is, for example, a method using a double-cone type rotary dryer. In this method, a small amount of dry gas is ventilated under reduced pressure, or under reduced pressure, or dried under normal pressure. Dry under gas. Air can be used as the drying gas, but it is preferable to use dry nitrogen or dehumidified air from the viewpoint of preventing the molecular weight of the polyester from being lowered by hydrolysis. When the polyester is contacted with the phosphorus-containing aqueous solution as described above, a polyester having a small increase in acetaldehyde and a small decrease in intrinsic viscosity can be obtained during molding. This is presumably caused by the inactivation of the polycondensation catalyst in the polyester due to the contact between the polyester and the phosphorus-containing aqueous solution. From the above-mentioned polyester, a molded article with less odor or off-odor, less flavor of the contents, and less change in aroma can be obtained. The above can be confirmed, for example, by measuring the increase in acetaldehyde after the polyester is heated and melt-molded at a temperature of 27.5 ° C into a stepped rectangular shaped article. The stepped rectangular molded article is formed in the following manner. First, 2 kg of granular polyester (granular polyester) whose acetaldehyde content (X% by weight) has been measured in advance is used as a raw material, and the layered shape is used at 140 ° C and 10 〇rr Dry with a dryer of more than 6 hours to reduce the moisture of the granular polyester to less than 50 ppm. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 public envy), Q1 ^ ---------— (Please read the precautions on the back before filling this page), 11 Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 585881 A7 B7____ 89 V. Description of the invention () ----------- (Please read the precautions on the back before filling this page) Second, use the above dry polyester, borrow name An M- 7 〇 A type injection molding machine manufactured by Koji Seisakusho Co., Ltd. was subjected to injection molding to obtain a stepped rectangular molding. Molded in nitrogen with a dew point of -70 ° c from the upper end of the hopper and supplied to the spiral feeding chute at a rate of 5 m3 / h respectively, and the molding temperature of the barrel is set at 2 7 5 ° C. The temperature of C l / c 2 / C 3 / nozzle mouth is set to 2 6 0 ° C / 2 9 Ot: / 2 9 0 ° C / 3 0 0 ° C, the cooling temperature of the mold is 1 5 t : Under the conditions. The injection molding of the stepped rectangular molding is adjusted according to the molding conditions of 12 seconds and 60 seconds of injection molding time, and the dry injection molding machine is supplied from the hopper for molding. . The residence time of the molten resin in the molding machine was about 72 seconds. The weight of each of the stepped rectangular shaped articles was 75 g, and the sample for measuring the acetaldehyde content was measured by using any one of the 11th to 15th shaped articles after the start of injection molding. The stepped rectangular shaped article has a shape as shown in Fig. 2 and has a thickness of about 6.5 mm at A, a thickness of about 5 mm at B, and a thickness of about 4 mm at C. The molded product at C was used to measure its acetaldehyde content. Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Next, the C-section of the formed stepped rectangular shaped article was cut into a sheet shape, and the acetaldehyde content was measured as a sample for measuring the acetaldehyde content. For polyesters, according to the above method, it is particularly suitable to use a polyethylene terephthalate for a phosphorus-containing aqueous solution to obtain a polyester having a small increase in acetaldehyde content during molding and a small decrease in intrinsic viscosity. Next, the organic solvent treatment will be described as follows. Organic solvents used in organic solvent processing, such as methanol, ethanol, this paper size applies Chinese National Standard (CNS) A4 (210X297 mm) · 92 · 585881 A7 B7 V. Description of the invention (9Q) Propanol, isopropanol , Butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, stearyl alcohol, oleyl alcohol, benzyl alcohol, phenylethanol, cumyl alcohol, cumyl benzyl alcohol, etc. Alcohols with 1 to 18 atoms, of which alcohols with 1 to 10 carbon atoms are preferred; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzene Ketones with 3 to 15 carbon atoms, such as quinones, of which ketones with 3 to 9 carbon atoms are preferred; butane, pentane, hexane, heptane, octane, nonane, decane , Undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane and other saturated hydrocarbons having 5 to 16 carbon atoms, of which saturated carbons having 5 to 10 carbon atoms Hydrocarbon is more suitable. Of these, isopropanol or acetone is particularly preferred. The contact between the polyester and the organic solvent may be performed arbitrarily in a continuous manner or in a batch manner. Specifically, in the aforementioned phosphorus-containing aqueous solution treatment, an organic solvent is used in place of the phosphorus-containing aqueous solution in the same manner. The contact temperature of polyester and organic solvent varies with the boiling point of the organic solvent used, usually 0 ~ 100 ° C, which is more preferably in the range of 10 ~ 95 ° C, and the contact time is usually 3 minutes ~ 5 hours. 30 minutes to 4 hours is ideal. After the polyester is contacted with the organic solvent, the polyester and the organic solvent are separated, and the water is removed by a dewatering device such as a granular shaker, a gel dryer, and the like, and dried. For the drying of the polyester which has been in contact with the organic solvent, a commonly used drying method of polyester can be adopted, specifically, for example, the above-mentioned continuous drying method, batch drying method, and the like. For example, when the above-mentioned polyester is in contact with an organic solvent, a polyester having a small amount of acetaldehyde can be obtained during molding. It is speculated that this is caused by the contact between polyester and organic solvents. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm). 93----------- (Please read the note on the back first (Fill in this page again)

、1T 經濟部智慈財產局Μ工消費合作社印製 585881 A7 B7 五、發明説明（） 聚酯中之縮聚合觸媒會失去活性所造成。 由上述聚酯可製得發生惡臭或異臭較少，內容物之風 味，香氣變化較少之成型物。 上述可藉例如將聚酯在2 7 0 °C之溫度下加熱熔融之 後，冷卻至室溫後採取試料，再依照上述方法測定其乙醛 含量而確定之。 按照上述對於聚酯，特別是對於聚乙烯對苯二甲酸酯 進行有機溶媒處理，可得成型時乙醛含量增加較少之聚酯 〇 其次，就含磷有機溶媒溶液處理說明如下： 含磷有機溶媒溶液處理所使用之磷酸酯，例如可舉上 述含磷水溶液處理所使用之相同磷酸酯。 含磷有機溶媒溶液處理所使用之有機溶媒，例如可舉 上述有機溶媒處理所使用之相同有機溶媒。 其中以異丙醇或丙酮爲理想。 和聚酯接觸之含磷有機溶媒溶液，以磷原子換算濃度 通常在lOppm以上，其中以10〜100000 Ppm爲較宜，以1〇〇〜70000ppm爲更宜，尤 以1 0 0 0〜5 0 0 0 0 p p m爲理想。 含磷有機溶媒溶液濃度在上述範圍時，所得聚酯在成 型之際，乙醛含量之增量之降低效果高，且甚經濟。 聚酯和含磷有機溶媒溶液之接觸可任意採用連續方式 或分批式。具體言之，代替含磷水溶液而使用含磷有機溶 媒溶液，按照上述含磷水溶液處理相同方法進行。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）-94 · ----------- (請先閱讀背面之注意事項再填寫本頁)Printed by 1T M Intellectual Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 585881 A7 B7 V. Description of the invention () Polycondensation catalysts in polyester will lose their activity. From the above-mentioned polyester, a molded article with less odor or off-odor, less flavor of the contents, and less change in aroma can be obtained. The above can be determined by, for example, heating and melting the polyester at a temperature of 270 ° C, cooling to room temperature, taking a sample, and measuring the acetaldehyde content according to the above method. According to the above-mentioned organic solvent treatment of polyester, especially polyethylene terephthalate, polyesters with less increase in acetaldehyde content during molding can be obtained. Second, the treatment of phosphorus-containing organic solvent solutions is described below: Phosphorous The phosphate used in the organic solvent solution treatment may be, for example, the same phosphate used in the phosphorus-containing aqueous solution treatment described above. The organic solvent used in the phosphorus-containing organic solvent solution treatment may be, for example, the same organic solvent used in the organic solvent treatment described above. Among them, isopropyl alcohol or acetone is preferable. The phosphorus-containing organic solvent solution in contact with polyester usually has a concentration of 10 ppm or more in terms of phosphorus atom, among which 10 to 100,000 Ppm is more suitable, and 100 to 70,000 ppm is more suitable, especially 1 0 0 0 to 5 0 0 0 0 ppm is ideal. When the concentration of the phosphorus-containing organic solvent solution is in the above range, the reduction effect of the increase in the acetaldehyde content of the obtained polyester upon molding is high, and it is very economical. The contact between the polyester and the phosphorus-containing organic solvent solution may be performed continuously or batchwise. Specifically, instead of the phosphorus-containing aqueous solution, a phosphorus-containing organic solvent solution was used, and the same method as in the treatment of the phosphorus-containing aqueous solution was performed. This paper size applies to Chinese National Standard (CNS) Α4 specification (210X297 mm) -94 · ----------- (Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製 585881 A7 _ B7 五、發明説明（92 ) 聚酯和含磷有機溶媒溶液之接觸溫度，隨所使用有_ 溶媒而異，但通常在〇〜1 〇 (KC範圍，其中以〇〜9 5 °C範圍爲較宜。接觸時間通常在5分鐘〜1 〇小時範圍， 其中以3 0分鐘〜6小時爲理想。 聚酯和含磷有機溶媒溶液接觸後，聚酯和含磷有機溶 媒溶液進行分離，再藉粒狀振動篩機，凝膠乾燥機等去水 裝置除水，並乾燥之。含磷有機溶媒溶液所接觸過之聚酯 之乾燥，可採用聚酯通常使用之乾燥方法，具體言之，例 如上述連續性乾燥方法，分批式乾燥方法均可採用。 按照上述聚酯以含磷有機溶媒溶液接觸時，成型之際 ’可得乙醛之增加量較少，固有粘度之降低較少之聚酯。 據推測乃是聚酯以含磷有機溶媒溶液接觸時，聚酯中之縮 聚合觸媒會失去活性所造成。 由上述聚酯可製得發生異臭或惡臭較少，內容物之風 味，香氣變化較少之成型物。 上述可藉將聚酯在2 8 5 °C溫度下加熱熔融之後，冷 卻至室溫所採取之試料，按照上述方法測定乙醛含量而確 定之。 對於上述聚酯，特別是對於聚乙烯對苯二甲酸酯進行 含磷有機溶媒溶液處理時，可得成型時乙醛含量增量少之 聚酯。 其次，本發明有關之聚酯說明如下： 聚酯（P - 1 )乃係使用上述固態狀鈦化合物（I 一 c )和輔觸媒成分（Π )所構成聚酯製造用觸媒，或使用 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-Q5 - ---------^衣-- (請先閲讀背面之注意事項再填寫本頁)， 1T printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 585881 A7 _ B7 V. Description of the invention (92) The contact temperature of polyester and phosphorus-containing organic solvent solution varies with the _ solvent used, but it is usually between 0 ~ 1 〇 (KC range, in which the range of 0 ~ 95 ° C is more suitable. The contact time is usually in the range of 5 minutes to 10 hours, of which 30 minutes to 6 hours is ideal. Polyester and phosphorus-containing organic solvent solution contact After that, the polyester and the phosphorus-containing organic solvent solution are separated, and then the water is removed by a granular shaker, gel drier and other dewatering devices, and dried. The polyester contacted by the phosphorus-containing organic solvent solution is dried, Drying methods commonly used for polyesters can be used, specifically, for example, the above-mentioned continuous drying methods and batch drying methods can be used. According to the above-mentioned polyesters contacted with a phosphorus-containing organic solvent solution, when forming Polyester with less increase in aldehyde and less decrease in intrinsic viscosity. It is speculated that when the polyester is contacted with a phosphorus-containing organic solvent solution, the polycondensation catalyst in the polyester will lose its activity. It is caused by the polyester can A molded article with less abnormal odor or malodor, less flavor, and less change in the content can be obtained. The above sample can be obtained by heating and melting the polyester at a temperature of 2 8 ° C and cooling to room temperature. The method is determined by measuring the acetaldehyde content. For the above polyester, especially when the polyethylene terephthalate is treated with a phosphorus-containing organic solvent solution, a polyester with a small increase in acetaldehyde content during molding can be obtained. Second, The polyester related to the present invention is described as follows: Polyester (P-1) is a polyester manufacturing catalyst composed of the solid titanium compound (I-c) and auxiliary catalyst component (Π) described above, or using this paper Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -Q5---------- ^ clothing-(Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製 585881 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明（93) 固態狀含鈦化合物（I - d )和必要時再加上輔觸媒成分 (Π )所構成聚酯製造用觸媒按照上述方法製造之。 聚酯（P — 1)之固有粘度通常在〇 · 50dl/g 以上’其中以0 · 50〜1 · 50d 1/ g爲較宜，尤以 0 _ 72〜1 · 〇d Ι/g爲理想。又，密度通常在 1 · 37g/cm3 以上，其中以 1 · 37 〜1 . 44g /〇1113爲較宜，以1 . 38〜1 . 43g/cm3爲更 佳，尤以1 · 39〜1 . 42g./cm3以上爲理想。 利用上述聚酯（P - 1 )，例如使用聚乙烯對苯二甲 酸酯在2 7 5 °C之成型溫度成型爲4mm厚度之板狀物時 ，所得板狀成型物之濁度通常在2 0 %以下，其中以〇〜 1〇％爲較宜。 濁度測定用之板狀成型物乃使用上述階梯式矩形成型 物之C處，該階梯式矩形成型物係使用聚酯（p - 1 )爲 測定上述乙醛之增加量所用階梯式矩形成型物相同方法製 造之。濁度測定以壓注模成型開始後第1 1〜1 5個之任 意一個爲試料而測定之。濁度測定使用濁度計（管試驗機 )H G Μ _ 2 D P型而測得。 上述聚酯（Ρ - 1 )具備優異之色相，特別是透明性 優異，乙醛含量少，該聚酯（Ρ - 1 )可提供各種成型物 之原料使用，例如熔融成型爲瓶等中空成型物，片狀物’ 薄膜，纖維等使用，其中以製瓶用途爲理想。 由聚酯（Ρ - 1 )，例如使用上述聚乙烯對苯二甲酸 酯成型爲瓶，片狀物，薄膜，纖維等之方法，可採用已往 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -96- 585881 A7 _B7__ 五、發明説明（94) 周知之方法。 (請先閱讀背面之注意事項再填寫本頁) 例如成型爲瓶時，將聚酯（P - 1 )，其中宜使用聚 乙烯對苯二甲酸酯在熔融狀態下由模擠壓而成管狀型坯， 繼之，將該型坯保持在所欲形狀之模中後，導入空氣吹塑 而製造中空成型物之方法，或將聚酯（P - 1 )，其中宜 用聚乙烯對苯二甲酸酯藉壓注模成型爲預塑物，再將該預 塑物加熱到展延用適溫，然後將該預塑物保持在所欲形狀 之模中後，導入空氣使之貼附在模上而製造中空成型物之 方法等均可採用。 成型爲薄膜或片狀物之方法，可採用已往周知之擠壓 裝置和成型條件，將熔融之聚乙烯對苯二甲酸酯由T模等 擠壓之方法，這些薄膜或片狀物可利用周知之展延方法而 展延。 成型爲纖維之方法，可將熔融之聚酯（P - 1 )，其 中宜使用聚乙烯對苯二甲酸酯通過抽絲頭擠壓之方法。據 此而得之纖維可再加展延。 經濟部智慧財產局員工消費合作社印製 本發明有關之聚酯（P - 1 )，特別是聚乙烯對苯二 甲酸酯和其成型物具有優異之透明性和色相，且乙醛含量 少〇 其次，就本發明之其他形態有關聚酯說明如下： 聚酯（P - 2 )使用下列縮聚合觸媒 (I )由水解產物（I — m )或水解產物（I 一 η ) 所構成縮聚合觸媒成分，和 (Π )輔觸媒成分所構成觸媒，且在上述酯化步驟或 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） -97- 8 8 5 8 5 A7 _— —___ B7 五、發明説明（95) 縮聚合步驟之任意步驟中添加色相調整劑而成聚酯之製造 方法而製得。 (請先閲讀背面之注意事項再填寫本頁) 聚酯（P - 2)之固有粘度通常在0 · 5〇d 1/g 以上’其中以〇 · 50〜1 · 50dl/g爲較宜，尤以 〇· 72〜1 · Od Ι/g爲理想。又，密度通常爲 1 · 37g/cm3 以上，其中以 1 . 37 〜1 · 44g / c m 3爲較宜，1 · 3 8〜1 . 4 3 g / c m 3爲更佳 ’尤以1 · 39〜1 · 42g/cm3以上爲理想。 聚酯（P - 2 )之含鈦原子量，對於聚酯重量計，在 〇·1〜2〇0ppm範圍，其中以〇.5〜1〇〇 P pm爲較宜，尤以1〜5 0 p pm含量爲理想，且含有 鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷、鋅和銻 中所選擇金屬原子（Μ )，對於聚酯重量計，0 . 1〜 500ppm，其中以〇 . 5〜30〇ppm爲較宜，尤 以1〜2 5 0 p p m含量爲理想。 經濟部智慧財產局g(工消費合作社印製 上述金屬原子（Μ )以鎂、鈣、鋅爲宜，特別以鎂爲 理想。金屬原子（Μ )可以在聚酯中含有二種以上，該時 二種以上之金屬原子（Μ)之含量合計在上述範圍。 聚酯（Ρ - 2 )所含上述欽原子以來源於鹵化鈦化合 物之水解所得縮聚合觸媒者爲宜，而上述金屬原子（Μ ) 以來源於輔觸媒成分之金屬原子爲宜。 又，前述欽原子和前述金屬原子（Μ)之莫耳比率（ 鈦原子/金屬原子Μ)通常在1/5 0〜5 0/1範圍， 其中以1/4 0〜4 0/1爲較宜，尤以1/3 0〜3 0 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -98- 585881 A7 ______B7_ 五、發明説明（96) / 1範圍爲最佳。 本發明中，聚酯中之鈦原子和金屬原子（Μ )之含量 以螢光X光分析法測定之。 聚酯CP — 2)通常含有0 · 01〜ΙΟΟρρηι之 色相調整劑’其中以含有〇 · 1〜5 0 p p m量爲較宜。 又，聚酯（P — 2)中以含有鍺原子量在5pPm以 下爲理想。 聚酯（P - 2 )以聚乙烯對苯二甲酸酯爲宜，其色相 亦較宜。 其次’就本發明之另一種形態有關聚酯說明如下： 聚酯CP — 3)之固有粘度通常在〇 · 5〇dl/g 以上’其中以〇·50〜1.50d1/g爲較宜，尤以 〇·72〜1·〇dΙ/g爲理想。又，密度通常在 1 · 37g/cm3 以上，其中以 1 · 37 〜1 · 44g /cm 3爲較宜，1 . 38〜1 . 43g/cm3爲更佳 ，尤以1 · 3 9〜1 · 4 2 g / c m 3以上爲理想。 聚酯（P - 3 )之含鈦原子量對聚酯重量計，0 · 1 〜2〇0ppm，其中以〇· 5〜l〇〇ppm爲較宜， 尤以1〜5 0 p p m量爲理想，且含有 由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷、鋅和 銻中所選擇金屬原子（Μ )，對於聚酯重量計，通常在 0·1〜50〇ppm，其中以〇·5〜300ppm爲 較宜，尤以1〜2 5 0 p pm含量爲理想。 上述金屬原子（Μ )以鎂、鈣、鋅爲宜，特別以鎂爲 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ---------- (請先閱讀背面之注意事項再填寫本頁) 、1Τ 經濟部智慈財產局員工消費合作社印製 -99- 585881 A7 B7 五、發明説明（97) 理想。金屬原子（Μ )在聚酯中可以含有二種以上，該時 以二種以上之金屬原子（Μ )之含量總計在上述範圍。 (請先閱讀背面之注意事項再填寫本頁) 又’聚酯（Ρ — 3 )之鍺原子含量以5 p pm以下爲 理想。 聚酯（P - 3 )所含上述鈦原子，以來源於鹵化鈦化 合物之水解而得縮聚合觸媒之鈦原子爲宜，上述金屬原子 (M)以來源於輔觸媒成分之金屬原子爲宜。 又’前述鈦原子和前述金屬原子（M)之莫耳比率（ 鈦原子/金屬原子（M))，通常在〇 . 〇5〜50，其 中以0.1〜30爲宜，尤以〇·2〜25範圍爲最佳。 聚酯C P — 3 )之乙醒含量（Wqp pm)通常在4 ppm以下，其中以〇·1〜3.5ppm爲宜，尤以 〇·5〜3·Oppm範圍爲理想。 又，聚酯（P — 3)(乙醛含量爲W。ppm)在 2 7 5 °C溫度下加熱熔融成型爲階梯式矩形成型物後之乙 醛含量爲〜！0 pm時，Wi — W。在1 〇 p pm以下，其 中在9 p pm以下爲較宜。 經濟部智慧財產局員工消費合作社印髮 上述聚酯（P-3)，其中聚乙烯對苯二曱酸酯之乙 醛含量少，且成型爲成型物之際，乙醛含量之增加顯著受 到抑制。例如由該聚酯（P - 3 )成型爲瓶時，塡充於該 瓶中之內容物之香和味等較不易降低。 本發明中，聚酯成型爲成型物之際，所發生乙醛之增 加量係由聚酯成型爲階梯式矩形成型物，測定該階梯式矩 形成型物中之乙醛量而藉上述相同方法求之。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 585881 A7 B7 五、發明説明（98 ) 本發明中，上述乙醛含量有， 就成型則之水醋測定之乙酵含量（WQp pm)和聚醋 在2 7 5 °C之成型溫度下壓注模成型所得成型物所測定之 乙醒含量（Wippm)。據此，本發明中由上述^:和 W ◦値計算其差値（w i 一 w Q )。 使用乙醒含量（WGp pm)少，上述所計算之Wi 一 W〇値’即成型時乙醛含量之增量在1 〇 p 以下之聚酯 時’成型物中所含乙醛量少，所以可製得發生惡臭或異臭 少’內容物之風味，香氣變化少之成型物。 聚酯（P — 3 )以聚乙烯對苯二甲酸酯爲較宜。 具有上述特性之聚酯（P 一 3)，例如按照上述聚酯 之處理方法中所使用之聚酯以相同方法製·造，對於反應終 結之聚酯進行含磷水溶液處理，有機溶媒處理或含磷有機 溶媒溶液處理而製得。 進行含磷水溶液處理，有機溶媒處理或含磷有機溶媒 處理之聚酯之乙醛含量通常在4 p pm以下，其中以 〇 · 1〜3 · 5ppm爲較宜，尤以〇 · 5〜3 · 0 p p m範圍爲理想。 上述處理中，以含磷水溶液處理和含磷有機溶媒溶液 處理爲宜，尤以含磷水溶液處理爲理想。 按照上述方法對於反應終結之聚酯施以含磷水溶液處 理，有機溶媒處理或含磷有機溶媒溶液處理，可抑制成型 時乙醛之增加。對於聚酯按照上述施以任意處理，成型時 聚酯中所含乙醛得以抑制，據推測是據上述處理可使聚酯 ----------- (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財4局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS〉Α4規格（210X 297公釐） -101 · 585881 A7 _______B7__ 五、發明説明（"） 中所含縮聚合觸媒因而失去活性，所以成型時加熱也幾乎 不再進行分解反應或酯交換反應，所以產生之乙醛量變少 〇 按照上述施加處理之聚酯，成型時乙醛之增加顯著受 到抑制。該事可由將經過上述方法處理之聚醋在2 7 5 °C 下加熱熔融成型爲階梯式矩形成型物之後，測定其乙醛含 量而得確證。 聚酯（P—3)，其乙醛含量少，成型時乙醛之增加 量也少。所以可製得乙醛含量少之瓶，薄膜，板狀物等成 型物。又，以乙醛含量多之成型物做爲飮食品容器使用時 ，會造成惡臭或異臭之原因，或內容物之風味，香氣會發 生變化。又，以乙醛含量多之聚酯製造的照相底片，容易 發生泛白現象。 聚酯（P — 3)，特別是聚乙烯對苯二甲酸酯，其乙 醛含量少，並且成型時所產生之乙醛量也少。因此，所製 得成型物中所含乙醛量也少。所以瓶爲首，他如薄膜，片 狀物等成型物，使用聚酯（P - 3 )爲原料，製造飮食品 用途之成型物容器時，其中所塡充之內容物不容易發生風 味或香氣之劣變。 其次，就本發明之其他形態有關聚酯說明如下： 聚酯（P — 4)之固有粘度通常在〇 · 5〇d 1/g 以上，其中以Ο·50〜1·50d1/g爲較宜，尤以 0 · 72〜1 · Od Ι/g爲理想。該聚酯（P — 4)之 密度通常在1 · 37g/cm3以上，其中以1 · 37〜 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-1〇2 - (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財4局員工消費合作社印製 585881 經濟部智慧財產局員工消費合作社印製 A7 _ B7__五、發明説明（1ί)〇) 1 · 44g/cm3 爲較宜，以 1 · 38 〜1 . 43g/ cm3爲更佳，尤以1 · 39〜1 · 42g/cm3以上爲 理想。 聚酯（P - 4 )之含鈦原子量，對聚酯重量計，通常 在 〇 · 1 〜200ppm，其中以 0 · 5 〜100ppm 爲較宜，尤以1〜5 Ο ρ pm量爲理想’且含有 由鈹、鎂、耗、總、鋇、硼、銘、鎵、猛、銘、鋅和 銻中所選擇金屬原子（M)，對聚酯重量計，通常在 0 · 1 〜500ppm，其中以 0 · 5 〜300ppm 爲 較宜，尤以1〜2 5 0 p pm含量爲理想。 上述金屬原子（M)以鎂、鈣、鋅爲宜，尤以鎂爲最 佳。金屬原子（M)可以在聚酯中含有二種以上，該時， 二種以上之金屬原子（M)之含量合計在上述範圍爲要。 又，聚酯（P — 4)之鍺原子含量在5ppm以下爲 宜。 聚酯（P - 4 )中所含上述鈦原子以來源於鹵化鈦化 合物之水解所得縮聚合觸媒之鈦原子爲宜，上述金屬原子 (Μ )，以來源於輔觸媒成分之金屬原子爲宜。 又，前述鈦原子和前述金屬原子（Μ)之莫耳比率（ 鈦原子/金屬原子（Μ))通常在〇 · 05〜50，其中 以0·1〜30爲較宜，尤以0·2〜25範圍爲最佳。 聚酯（Ρ — 4)係環狀三聚物（下式所示乙烯對苯二 甲酸酯之環狀三聚物）之含量（X重量％)在5重量％以 下1T printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 585881 Α7 Β7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (93) Solid titanium-containing compounds (I-d) and supplementary contact if necessary The catalyst for polyester production composed of the medium component (Π) is produced according to the method described above. The inherent viscosity of the polyester (P — 1) is usually above 0.550 dl / g. Among them, 0.50 ~ 1.50d 1 / g is preferable, and 0_72 ~ 1.〇d Ι / g is more preferable. . In addition, the density is usually 1.37g / cm3 or more. Among them, 1.37 ~ 1.44g / 〇1113 is more preferable, 1.38 ~ 1.43g / cm3 is more preferable, and 1.39 ~ 1. 42 g./cm3 or more is preferable. Using the polyester (P-1), for example, when polyethylene terephthalate is used to form a 4mm-thick plate at a molding temperature of 27.5 ° C, the turbidity of the obtained plate-shaped molded product is usually 2 0% or less, among which 0 to 10% is more suitable. The plate-shaped molded article for turbidity measurement is the C place using the above-mentioned stepped rectangular molded article. The stepped rectangular molded article uses polyester (p-1) to measure the increase amount of the acetaldehyde. Manufactured in the same way. The turbidity was measured by using any one of the 11th to 15th samples after the start of injection molding. The turbidity was measured using a turbidimeter (tube tester) H G M _ 2 D P type. The polyester (P-1) has excellent hue, especially excellent transparency, and low acetaldehyde content. The polyester (P-1) can be used as a raw material for various moldings, such as melt molding into hollow moldings such as bottles , Sheet, film, fiber, etc., which is ideal for bottle making applications. From polyester (P-1), for example, using the above polyethylene terephthalate to form bottles, sheets, films, fibers, etc., you can use the past (please read the precautions on the back before filling this page ) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -96- 585881 A7 _B7__ 5. Description of the invention (94) Well-known method. (Please read the precautions on the back before filling in this page) For example, when molding into a bottle, use polyester (P-1), which should be made of polyethylene terephthalate in a molten state and extruded into a tube. Parison, followed by holding the parison in a mold of a desired shape, and introducing air blow molding to produce a hollow molding, or polyester (P-1), of which polyethylene terephthalate is suitable The formate is formed into a preform by pressure injection molding, and then the preform is heated to a suitable temperature for extension, and then the preform is held in a mold of a desired shape, and then air is introduced to attach the preform. A method for manufacturing a hollow molded article on the mold can be adopted. The method of forming into a film or sheet can be a method of extruding molten polyethylene terephthalate through a T die or the like using a known extrusion device and molding conditions. These films or sheets can be used The extension method is well-known. The method for forming the fiber can be molten polyester (P-1), of which polyethylene terephthalate is preferably extruded through a spinneret. The resulting fibers can be further extended. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the polyester (P-1), especially polyethylene terephthalate and its moldings, with excellent transparency and hue, and the content of acetaldehyde was small. Next, the description of other polyesters related to the present invention is as follows: Polyester (P-2) uses the following polycondensation catalyst (I) to form a polycondensation product composed of a hydrolysate (I-m) or a hydrolysate (I-η). The catalyst is composed of catalyst components and (Π) auxiliary catalyst components, and the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -97- 8 8 5 8 5 A7 _ — — ___ B7 V. Description of the invention (95) It is prepared by adding a hue adjuster to a polyester in any step of the condensation polymerization step. (Please read the precautions on the back before filling in this page) The inherent viscosity of polyester (P-2) is usually above 0 · 5〇d 1 / g ', where 0.5 · 50 ~ 1 · 50dl / g is more suitable, Especially, it is preferably from 0.72 to 1 · Od 1 / g. In addition, the density is usually 1.37 g / cm3 or more. Among them, 1. 37 to 1. 44 g / cm 3 is preferable, and 1. 3 8 to 1. 4 3 g / cm 3 is more preferable. Especially, 1. 39 ~ 1 · 42 g / cm3 or more is preferable. The titanium atomic weight of the polyester (P-2) is in the range of 0.1 to 2000 ppm based on the weight of the polyester, of which 0.5 to 100 ppm is more preferred, especially 1 to 50 p The pm content is ideal and contains selected metal atoms (M) of beryllium, magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, and antimony, and 0.1 to 500 ppm for polyester weight. Among them, 0.5 to 30 ppm is more suitable, and 1 to 250 ppm is ideal. The Intellectual Property Bureau of the Ministry of Economic Affairs (the above-mentioned metal atom (M) printed by the Industrial and Consumer Cooperatives is preferably magnesium, calcium, zinc, and especially magnesium is preferred. The metal atom (M) may contain two or more kinds in polyester. At this time, The total content of two or more kinds of metal atoms (M) is in the above-mentioned range. It is preferable that the above-mentioned metal atoms contained in the polyester (P-2) are polycondensation catalysts derived from the hydrolysis of titanium halide compounds, and the above metal atoms ( M) It is preferable to use metal atoms derived from the auxiliary catalyst component. In addition, the Mohr ratio (titanium atom / metal atom M) of the aforesaid metal atom (M) is usually in the range of 1/5 0 to 5 0/1. The range of which is 1/4 0 ~ 4 0/1 is more suitable, especially 1/3 0 ~ 3 0 This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) -98- 585881 A7 ______B7_ V. Description of the invention The range of (96) / 1 is the best. In the present invention, the content of titanium atom and metal atom (M) in polyester is determined by fluorescent X-ray analysis. Polyester CP-2) usually contains 0 · 01 ~ ΙΟΟρρηι's hue adjusting agent 'It is more preferable to contain 0.001 ~ 50 0 ppm . The polyester (P-2) preferably contains a germanium atomic weight of 5 pPm or less. Polyester (P-2) is preferably polyethylene terephthalate, and its hue is also more suitable. Secondly, the description of the polyester related to another aspect of the present invention is as follows: The inherent viscosity of the polyester CP-3) is usually above 0.50 dl / g. Among them, 0.5 to 1.50 d1 / g is preferable, especially Ideally, it is 0.72 to 1.0dI / g. In addition, the density is usually 1.37 g / cm3 or more. Among them, 1.37 to 1.44 g / cm3 is preferable, 1.38 to 1.43 g / cm3 is more preferable, and 1.38 to 1.43 is particularly preferable. 4 2 g / cm 3 or more is ideal. The titanium atomic weight of the polyester (P-3) is from 0.1 to 200 ppm based on the weight of the polyester, of which 0.5 to 100 ppm is more preferable, and 1 to 50 ppm is particularly preferable. And contains selected metal atoms (M) selected from beryllium, magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, and antimony, usually 0.1 to 50 ppm for polyester weight Among them, 0.5 to 300 ppm is more suitable, and 1 to 250 p pm is particularly desirable. The above metal atoms (M) are preferably magnesium, calcium, zinc, especially magnesium-based paper standards applicable to China National Standard (CNS) A4 specifications (210X297 mm) ---------- (Please read first Note on the back, please fill out this page again), printed by the Consumer Cooperative of the Intellectual Property Bureau of 1T Ministry of Economic Affairs-99-585881 A7 B7 V. Description of the invention (97) Ideal. The metal atom (M) may contain two or more kinds in the polyester. In this case, the content of the two or more metal atoms (M) is in the above range. (Please read the notes on the back before filling out this page.) The content of germanium atoms in ‘polyester (P — 3) is ideally below 5 p pm. The titanium atom contained in the polyester (P-3) is preferably a titanium atom derived from a polycondensation catalyst derived from the hydrolysis of a titanium halide compound. The metal atom (M) is a metal atom derived from an auxiliary catalyst component as should. Also, the molar ratio (titanium atom / metal atom (M)) of the aforementioned titanium atom and the aforementioned metal atom (M) is usually in the range of 0.05 to 50, of which 0.1 to 30 is preferable, and 0.2 to 2 in particular. 25 range is best. The polyester content (Wqp pm) of the polyester C P 3) is usually less than 4 ppm, of which 0.1 to 3.5 ppm is preferable, and a range of 0.5 to 3.0 ppm is preferable. In addition, the polyester (P-3) (acetaldehyde content is W. ppm) was heated and melt-molded into a stepped rectangular molding at a temperature of 27.5 ° C to have an acetaldehyde content of ~! At 0 pm, Wi — W. It is preferably less than 10 p pm, and preferably less than 9 p pm. The above-mentioned polyester (P-3) is printed and distributed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Among them, polyethylene terephthalate has a low acetaldehyde content, and when molded into a molded article, the increase in acetaldehyde content is significantly suppressed. . For example, when the polyester (P-3) is formed into a bottle, the aroma and taste of the contents filled in the bottle are less likely to be reduced. In the present invention, when the polyester is molded into a molded article, the increase amount of acetaldehyde generated is formed from the polyester into a stepped rectangular shaped article, and the amount of acetaldehyde in the stepped rectangular shaped article is measured by the same method as described above. Of it. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 585881 A7 B7 V. Description of the invention (98) In the present invention, the above acetaldehyde content is included, and the acetic acid content (WQp) determined by water vinegar for molding pm) and ethyl acetate content (Wippm) of the molded article obtained by injection molding at a molding temperature of 27.5 ° C. Accordingly, in the present invention, the difference w (w i-w Q) is calculated from the above ^: and W ◦ 値. When the content of acetaldehyde (WGp pm) is small, the above-calculated Wi-Wo 'is the polyester with an increase in acetaldehyde content of less than 10p during molding.' The amount of acetaldehyde in the molding is small, so It is possible to produce a molded product having a low content of malodor or malodor, and a small change in aroma. Polyester (P-3) is preferably polyethylene terephthalate. Polyesters (P-3) with the above characteristics, for example, are prepared and manufactured in the same way as the polyesters used in the above-mentioned polyester processing methods. The polyesters with reaction termination are treated with a phosphorus-containing aqueous solution, organic solvent or Phosphorus organic solvent solution. The acetaldehyde content of polyesters treated with phosphorus-containing aqueous solution, organic solvent or phosphorus-containing organic solvent is usually less than 4 p pm, of which 0 · 1 ~ 3 · 5ppm is more suitable, especially 0.5 · 3 ~ 3 · The 0 ppm range is ideal. Among the above treatments, a phosphorus-containing aqueous solution treatment and a phosphorus-containing organic solvent solution treatment are preferable, and a phosphorus-containing aqueous solution treatment is particularly preferable. Applying a phosphorus-containing aqueous solution, an organic solvent treatment, or a phosphorus-containing organic solvent solution to the polyester at the end of the reaction according to the above method can suppress the increase of acetaldehyde during molding. The polyester is subjected to any treatment in accordance with the above, and the acetaldehyde contained in the polyester is suppressed during molding. It is speculated that the above treatment can make the polyester ----------- (Please read the note on the back first Please fill in this page for the items) Order the paper printed by the Employees' Cooperatives of the 4th Bureau of Smart Finance of the Ministry of Economic Affairs to apply the Chinese national standard (CNS> A4 specification (210X 297 mm) -101 · 585881 A7 _______B7__ 5. Description of the invention (") The polycondensation catalyst contained in it is therefore inactive, so the decomposition reaction or transesterification reaction is almost no longer heated during molding, so the amount of acetaldehyde produced is reduced. The polyester treated according to the above application has a significant increase in acetaldehyde during molding. Suppressed. This can be confirmed by measuring the acetaldehyde content of the polyacetate processed by the above method at 25 ° C and melting and forming it into a stepped rectangular shaped article. Polyester (P-3), which The content of acetaldehyde is small, and the increase amount of acetaldehyde is also small during molding. Therefore, bottles, films, plates, and other molded products with low acetaldehyde content can be prepared. In addition, the molded product with high acetaldehyde content is used as a food container. when using it, The cause of malodor or malodor, or the flavor and content of the contents will change. In addition, photographic negatives made of polyesters with a large acetaldehyde content are prone to whitening. Polyesters (P-3), especially Polyethylene terephthalate has less acetaldehyde content, and the amount of acetaldehyde produced during molding is also small. Therefore, the amount of acetaldehyde in the prepared molding product is also small. Therefore, the bottle is the first, and he When moldings such as films and sheets use polyester (P-3) as raw materials to make molded food containers for food applications, the contents filled therein are not prone to deterioration in flavor or aroma. Second, The description of the polyesters in other forms of the present invention is as follows: The inherent viscosity of the polyester (P-4) is usually above 0.50d 1 / g, of which 0 · 50 ~ 1 · 50d1 / g is preferable, especially 0 · 72 ~ 1 · Od Ι / g is ideal. The density of the polyester (P-4) is usually above 1. 37g / cm3, of which 1 · 37 ~ This paper size applies the Chinese National Standard (CNS) A4 specification （210X297mm） -1〇2-(Please read the notes on the back before filling this page) Order the Ministry of Economic Affairs Printed by the Employees ’Cooperatives of the 4th Bureau of Wisdom and Wealth 585881 Printed by the Consumers’ Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ B7__ V. Invention Description (1) 0) 1 · 44g / cm3 is more appropriate, 1 · 38 ~ 1. 43g / cm3 is more preferable, and more preferably 1.39 to 1.42g / cm3. The titanium atomic weight of the polyester (P-4) is usually from 0.1 to 200 ppm based on the weight of the polyester, of which 0.5 to 100 ppm is preferred, and 1 to 5 Ο ρ pm is ideal 'and Contains metal atoms (M) selected from beryllium, magnesium, consumption, total, barium, boron, indium, gallium, indium, zinc, and antimony, and is usually in the range of 0.1 to 500 ppm based on the weight of the polyester, of which 0 · 5 to 300 ppm is preferable, and 1 to 2 50 p pm is more preferable. The above metal atom (M) is preferably magnesium, calcium, and zinc, and most preferably magnesium. The metal atom (M) may contain two or more kinds in the polyester. In this case, it is necessary that the total content of the two or more kinds of metal atoms (M) is within the above range. The germanium atom content of the polyester (P-4) is preferably 5 ppm or less. The titanium atom contained in the polyester (P-4) is preferably a titanium atom derived from a polycondensation catalyst obtained by hydrolysis of a titanium halide compound, and the metal atom (M) is a metal atom derived from a secondary catalyst component should. In addition, the molar ratio (titanium atom / metal atom (M)) of the titanium atom and the metal atom (M) is usually 0.05 to 50, of which 0.1 to 30 is preferable, and 0.2 A ~ 25 range is optimal. The content of the polyester (P-4) cyclic terpolymer (cyclic terpolymer of ethylene terephthalate represented by the following formula) (X wt%) is 5 wt% or less

(請先閱讀背面之注意事項再填寫本頁) •ηϋι^· 訂 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐）-1〇3 - 585881 A7 _B7____ 五、發明説明（1C)1) —^―OC-^ "y-COCHgOCHg— (請先閲讀背面之注意事項再填寫本頁) ，其中以0·45重量％以下爲宜。 又，聚酯（P-4)(環狀三聚物含量爲X重量％) ，在2 9 0 °C下加熱熔融成型爲階梯式矩形成型物之後， 環狀三聚物含量之增加量爲y重量％時，z和y通常能滿 足 y^-0.20x + 0.20 其中以能滿足yS — 0 · 20x + 0 · 18爲較宜，尤以 能滿足y S - 0 · 2 0 X + 0 . 1 6爲理想。 經濟部智慧財產局員工消費合作社印製 上述聚酯（P - 4)，其環狀三聚物之含量少，且成 型爲成型物之際，環狀三聚物之含量之增加顯著受到抑制 ，成型時聚酯中所含環狀三聚物量少，所以不容易發生模 之污染。例如供料該聚酯（P - 4 )於壓注模成型機等而 成型中空成型物用預成型物，再將該預成型物***所定形 狀之模而展延吹塑成型後，加熱固定成型爲中空成型容器 之際，環狀三聚物不容易增加，成型時聚酯中所含環狀三 聚物量少，所以不容易造成模之污染。 聚酯（P - 4 )成型爲成型物之際，所發生環狀三聚 物之增加量，可藉將聚酯（P - 4 )成型爲階梯式矩形成 型物之後，測定其中之環狀三聚物量而求得。測定環狀三 聚物之增加量所使用階梯式矩形成型物，使用預先測定過 環狀三聚物含量（X重量％)之粒狀聚酯（P — 4)(顆 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-1〇4 - 585881 A7 B7 ___ 五、發明説明（1Q2) 粒狀聚酯）爲原料’按照測定乙醒增加量所用階梯式矩形 成型物相同方法製造之° (請先閲讀背面之注意事項再填寫本頁) 環狀三聚物含量測定用試料’以壓注模成型開始後第 1 1個〜1 5個中之任意者爲試料’將成型好的階梯式矩 形成型物之C處切斷成片狀’做爲環狀三聚物含量測定用 試料測定其含量（z重量％ ) ° 成型爲階梯式矩形成型物前之粒狀聚酯和階梯式矩形 成型物中所含環狀三聚物含量依照下述方法測定之。 將所定量之聚醋溶解於鄰一氯酌之後’使用四氫D夫喃 再析出再過濾線狀聚酯。繼之’將所得濾液藉液相層析儀 (島津製作所製品L C 7 A型）求得聚酯中所含環狀三聚 物含量，該値除以測定用聚酯量做爲聚酯中所含環狀三聚 物含量。 聚酯在2 9 0°C加熱熔融成型爲階梯式矩形成型物之 後之環狀三聚物含量之增加量（y重量％)乃係z (重量 %) - X (重量％)之差値。 本發明有關聚酯（P—4)以聚乙烯對苯二甲酸酯爲 較宜。 經濟部智慧財4局員工消費合作社印製 具有上述特性之本發明有關聚酯（P - 4 )，可對於 例如上述聚酯之處理方法使用聚酯相同方法製造，經過酯 化步驟，液相縮聚合步驟和固相縮聚合步驟而得聚酯，進 行含磷水溶液處理，有機溶媒處理或含磷有機溶媒溶液處 理而製成。進行上述任意處理之聚酯通常爲粒狀，但也可 以爲粉狀、絲狀。 -105- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 585881 A7 ____B7_______ 五、發明説明（1〇与 進行含磷水溶液處理，有機溶媒處理或含磷有機溶媒 溶液處理之聚酯之環狀三聚物含量，通常在〇 · 5重量％ 以下，其中以〇 . 4 5重量％以下爲理想。 按照上述施加處理之聚酯（P - 4 )，成型爲中空成 型物等時，其環狀三聚物之增加顯著受到抑制’此現象可 藉將施加上述處理之聚酯（P - 4 )在2 9 0 °C溫度下加 熱熔融成型爲階梯式矩形成型物之後，測定其環狀三聚物 含量而確定之。 按照上述對於聚酯施以含磷水溶液處理，有機溶媒處 理或含磷有機溶媒溶液處理，可得將該聚酯在2 9 0 °C溫 度下加熱熔融成型爲階梯式矩形成型物之際，抑制其增加 之環狀三聚物量。 按照上述對於聚酯施加含磷水溶液處理，有機溶媒處 理或含磷有機溶媒溶液處理，而能抑制成型時聚酯中所含 環狀三聚物之增加，據推測由於施加上述任意處理，可使 聚酯中所含縮聚合觸媒，例如鈦化合物縮聚合觸媒迅速失 去活性，所以成型時加熱，聚酯幾乎不再進行聚酯分解反 應或酯交換，因此所產生環狀三聚物量會變少。 由上述處理之環狀三聚物含量少之聚酯（P - 4 )， 例如利用壓注模成型爲成型物時，成型時聚酯中所含環狀 三聚物量少，所以環狀三聚物附著在模內面或模之排氣口 ，排氣管等而造成模污染較少，且環狀三聚物附著在壓注 模成型機之通風孔也較少。 本發明有關之中空成型物，由上述固有粘度在 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） n I n n I n 11· 11 (請先閱讀背面之注意事項再填寫本頁) 、v 一口 泉 經濟部智慧財產局員工消費合作社印製 -106- 585881 A7(Please read the notes on the back before filling in this page) • ηϋι ^ · The size of the paper used in the edition is subject to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -103-585881 A7 _B7____ 5. Description of the invention ) 1) — ^ ― OC- ^ " y-COCHgOCHg— (Please read the precautions on the back before filling out this page), which is preferably 0.45% by weight or less. In addition, after the polyester (P-4) (cyclic trimer content is X% by weight) was heated and melt-molded at 290 ° C to form a stepped rectangular shaped article, the increase amount of the cyclic trimer content was At y weight%, z and y can usually satisfy y ^ -0.20x + 0.20. Among them, yS — 0 · 20x + 0 · 18 is more suitable, especially y S-0 · 2 0 X + 0. 1 6 is ideal. The above-mentioned polyester (P-4) was printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The content of the cyclic trimer was small, and when it was molded into a molded article, the increase in the content of the cyclic trimer was significantly suppressed. Polyester contains a small amount of cyclic trimer during molding, so mold contamination is unlikely to occur. For example, the polyester (P-4) is fed to a compression molding machine to form a preform for a hollow molded object, and the preform is inserted into a mold of a predetermined shape to be stretch blow molded, and then heated and fixed for molding. When it is a hollow molded container, the cyclic trimer is not easy to increase, and the amount of cyclic trimer contained in the polyester is small during molding, so it is not easy to cause mold contamination. When the polyester (P-4) is molded into a molded article, the increase in the amount of cyclic terpolymers that can occur can be determined by molding the polyester (P-4) into a stepped rectangular molded article. Calculate the amount of polymer. The stepped rectangular molding used to measure the increase in the cyclic trimer is a granular polyester (P-4) whose cyclic trimer content (X% by weight) has been measured in advance (the size of this paper is applicable to China) Standard (CNS) A4 specification (210X297 mm) -104-585881 A7 B7 ___ V. Description of the invention (1Q2) Granular polyester) as raw material 'Manufactured in the same way as the stepped rectangular shaped article used to measure the increase in dioxin ° (Please read the precautions on the back before filling in this page) The sample for measuring the content of the ring-shaped trimer is 'sampled from the 11th to the 15th after the start of injection molding.' The step C of the stepped rectangular molded product is cut into a sheet shape as a sample for measuring the content of the cyclic trimer (z wt%) ° The granular polyester and the step before molding into a stepped rectangular molded product The content of the cyclic trimer contained in the formula-shaped rectangular molding was measured according to the following method. After dissolving the determined amount of polyvinegar in o-chlorochlorine, it was re-precipitated using tetrahydroDefran and the linear polyester was filtered. Then, the obtained filtrate was obtained by a liquid chromatograph (LC7A type manufactured by Shimadzu Corporation) to determine the content of cyclic trimer contained in the polyester. Contains cyclic trimer content. After the polyester is heated and melt-molded at 290 ° C to form a stepped rectangular shaped article, the increase in the cyclic trimer content (y wt%) is the difference between z (wt%)-X (wt%). The polyester (P-4) of the present invention is preferably polyethylene terephthalate. The Consumer Cooperative of the 4th Bureau of Wisdom and Finance of the Ministry of Economic Affairs prints the polyester (P-4) of the present invention with the above characteristics. The polyester can be manufactured by the same method as the processing method of the above polyester. After the esterification step, the liquid phase shrinks. The polyester is obtained by the polymerization step and the solid-phase condensation polymerization step, and the polyester is obtained by conducting a phosphorus-containing aqueous solution treatment, an organic solvent treatment, or a phosphorus-containing organic solvent solution treatment. The polyester subjected to any of the above treatments is usually granular, but may be powdery or silky. -105- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 585881 A7 ____B7_______ V. Description of the invention (10 Polyester treated with phosphorous aqueous solution, organic solvent or phosphorous organic solvent solution The content of the cyclic trimer is usually 0.5% by weight or less, and preferably 0.45% by weight or less. When the polyester (P-4) treated as described above is molded into a hollow molding, etc., The increase in the cyclic trimer is significantly suppressed. This phenomenon can be measured by heating and melting the polyester (P-4) to which the above-mentioned treatment is applied at a temperature of 290 ° C to form a stepped rectangular shaped article. According to the above, the polyester is subjected to a phosphorus-containing aqueous solution treatment, an organic solvent treatment, or a phosphorus-containing organic solvent solution treatment, and the polyester can be heated and melt-molded at a temperature of 290 ° C to form In the case of a stepped rectangular molded article, the increase in the amount of cyclic trimer is suppressed. The polyester is treated with an aqueous phosphorus solution, an organic solvent or a phosphorus organic solvent solution as described above, and Suppression of the increase in cyclic terpolymers contained in polyester during molding. It is speculated that the application of any of the above treatments can cause polycondensation catalysts contained in polyesters, such as titanium compounds, to rapidly lose activity. By heating, the polyester almost no longer undergoes polyester decomposition reaction or transesterification, so the amount of cyclic trimer produced will be reduced. Polyester (P-4) with a small cyclic trimer content treated as described above, for example, uses When injection molding is used to form a molded product, the amount of cyclic terpolymer contained in the polyester is small during molding, so the cyclic terpolymer is attached to the inner surface of the mold or the exhaust port of the mold, the exhaust pipe, etc., causing mold contamination. Less, and there are fewer ring-shaped terpolymers attached to the ventilation holes of the injection molding machine. The hollow moldings related to the present invention apply the Chinese National Standard (CNS) A4 specification (210X297) at the paper scale based on the above inherent viscosity. Mm) n I nn I n 11 · 11 (Please read the notes on the back before filling in this page), v Yiquan printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Consumption Cooperative -106- 585881 A7

經濟部智慧財產局員工消費合作社印製 五、發明説明（1〇4 〇· 5〇d l/g以上，鈦原子含量’金屬原子（M)之 含量以及鈦原子/金屬原子（Μ )之比率在特定範圍，環 狀三聚物含量在〇 · 5重量％以下，且該含量和成型爲階 梯式矩形成型物之後，環狀三聚物含量之增加量滿足特定 關係之聚酯（Ρ - 4 )，特別是聚乙烯對苯二甲酸酯所製 成，其環狀三聚物含量通常在〇 · 6重量％以下，其中以 〇.10〜0·55重量％爲較宜，尤以0·15〜 〇·50重量％範圍爲最佳。 測定中空成型物中之環狀三聚物含量，使用由中空成 型物所採取試料按照上述方法測定之。 本發明有關之中空成型物可藉已往周知方法製造之。 具體言之，首先由上述聚酯（Ρ-4)，最好使用聚乙烦 對苯二甲酸酯製得預塑物。該預塑物可按照已往周知方法 ，例如壓注模成型，擠壓成型等而製造之，成型爲預塑物 時之聚乙烯對苯二甲酸酯之加熱溫度，例如在9 0〜 1 1 0 t爲較宜，繼之，將預塑物加熱至展延適溫，然後 展延吹塑成型而製造中空成型物。 由上述環狀三聚物含量少，施加特定處理之聚酯（P - 4 )成型中空成型物時，成型時所產生環狀三聚物量少 ，因此，將該聚酯（P - 4 )供料至壓注模成型機等成型 機，成型爲中空成型物用預塑物，再將該預塑物***所定 形狀之模，展延吹塑成型後’加熱固定成爲成型物之際’ 不容易發生環狀三聚物附著模上而造成模之污染。 本發明有關之中空成型物’由上述環狀三聚物含量少 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） --------Φ衣-- (請先閲讀背面之注意事項再填寫本頁) 、11 ·—·· -107- 585881 經濟部智慈財產局8工消費合作社印製 A7 _ B7 五、發明説明（1〇今 ，經特定處理之聚酯（P - 4 )所製成，所以成型時所產 生環狀三聚物量少，因此，該中空成型物之環狀三聚物之 含量也少，其表面粗糙或白化（污染）也較少。 聚酯（P - 4 )中，以聚乙烯對苯二甲酸酯爲最宜， 其中環狀三聚物之含量少，並且在成型時所產生之環狀三 聚物之量也少。因此，成型時聚酯中所含環狀三聚物之量 少，不易發生模之污染。所以，製造成型物之際不必頻繁 進行洗淨，可以提升瓶等中空成型物或薄膜，片狀物等成 型物之生產力，且可防止所產生中空成型物或薄膜，片狀 物之白化（污染）。 本發明有關之中空成型物由上述聚酯，最好是聚乙烯 對苯二甲酸酯所製得，因此，中空成型物中之環狀三聚物 之含量少，其表面粗糙或白化（污染）也少。 其次，就本發明之另一種形態有關聚酯說明如下： 聚酯（P - 5 )係以芳香族二羧酸或其酯形成性衍生 物和脂肪族二元醇或其酯形成性衍生物，必要時再加上多 官能性化合物等爲製造，由對苯二甲酸或其酯形成性衍生 物所導致重複單位，乙二醇或其酯形成性衍生物所導致重 複單位所構成之聚乙烯對苯二甲酸酯爲較宜。該聚乙烦對 苯二甲酸酯可含有2 0莫耳％以下之其他二羧酸類和/或 其他二元醇類所導致之重複單位。 對苯二甲酸酯以外之其他二羧酸類，乙二醇以外之其 他二元醇類之具體例舉如上述相同者。 又，聚乙烯對苯二甲酸酯尙可含有由均苯三酸，三經 本纸張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (above 104.50 dl / g, the titanium atom content 'metal atom (M) content and the titanium atom / metal atom (M) ratio are between In a specific range, a polyester (P-4) having a cyclic trimer content of 0.5% by weight or less, and an increase in the cyclic trimer content that satisfies a specific relationship after being molded into a stepped rectangular shaped article , Especially made of polyethylene terephthalate, its cyclic trimer content is usually less than 0.6% by weight, of which 0.1 to 0.55% by weight is more suitable, especially 0. The range of 15 to 0. 50% by weight is optimal. The content of the cyclic trimer in the hollow molded article is measured, and it is measured according to the method described above using a sample taken from the hollow molded article. The hollow molded article of the present invention may be known in the past. Specifically, firstly, a pre-molded article is prepared from the above-mentioned polyester (P-4), preferably polyethylene terephthalate. The pre-molded article can be prepared according to a conventionally known method such as injection molding. It is manufactured by mold forming, extrusion forming, etc. The heating temperature of the polyethylene terephthalate during the pre-molding is more suitable, for example, from 90 to 110 t. Next, the pre-plastic is heated to a suitable stretching temperature, and then stretch blow-molded. Hollow molded products are produced. When the hollow molded product is molded from polyester (P-4) with a small content of the above cyclic trimer and a specific treatment is applied, the amount of cyclic trimer generated during molding is small. The ester (P-4) is fed to a molding machine such as an injection molding machine, and molded into a preform for a hollow molding, and then the premold is inserted into a mold of a predetermined shape, and then stretch-blow-molded into a heat-fixed In the case of moldings, it is not easy for the ring terpolymer to adhere to the mold and cause mold contamination. The hollow moldings related to the present invention have a small content of the above-mentioned cyclic terpolymers. The paper standard is applicable to China National Standard (CNS) A4. Specifications (210X297 mm) -------- Φ Clothing-(Please read the precautions on the back before filling this page), 11 ···· -107- 585881 Ministry of Economic Affairs, Intellectual Property Bureau, 8 workers Cooperative printed A7 _ B7 V. Description of the invention (10 to date, made of specially treated polyester (P-4) Therefore, the amount of cyclic trimer produced during molding is small, so the content of cyclic trimer of the hollow molded product is also small, and the surface is rough or whitened (pollution) is less. Polyester (P-4) Polyethylene terephthalate is the most suitable, in which the content of cyclic trimer is small, and the amount of cyclic trimer generated during molding is also small. Therefore, the polyester contained in molding The amount of ring-shaped terpolymer is small, and mold contamination is unlikely to occur. Therefore, it is not necessary to wash frequently when manufacturing a molded article, which can improve the productivity of hollow molded articles such as bottles or molded articles such as films and sheets, and prevent Whitening (contamination) of the hollow molded article or film and sheet produced. The hollow molded article of the present invention is made of the above polyester, preferably polyethylene terephthalate. Therefore, the hollow molded article The content of the cyclic terpolymer is small, and the surface is rough or whitened (pollution). Next, the description of the polyester in another form of the present invention is as follows: The polyester (P-5) is an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof. If necessary, a polyfunctional compound is added to produce a polyethylene pair consisting of terephthalic acid or an ester-forming derivative thereof, and a polyethylene pair consisting of a repeating unit of ethylene glycol or an ester-forming derivative thereof. A phthalate is preferred. The polyethylene terephthalate may contain repeating units caused by other dicarboxylic acids and / or other glycols of less than 20 mol%. Specific examples of dicarboxylic acids other than terephthalate and glycols other than ethylene glycol are the same as described above. In addition, polyethylene terephthalate may contain trimesic acid. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X29 * 7 mm) (Please read the precautions on the back before filling out (This page)

-108- 585881 kl ___B7_ 五、發明説明（10今 (請先閱讀背面之注意事項再填寫本頁) 甲基乙烷，三羥甲基丙烷，三羥甲基甲烷，異戊四醇等多 官能性化合物所導致重複單位。這種由多官能性化合物所 導致重複單位，對於二元醇所導致重複單位而言，使用〇 〜2莫耳％之比率爲宜。含有由多官能性化合物所導致重 複單位在上述範圍量之聚酯，熔融時之流動性有偏高之傾 向。 聚酯（P — 5)之固有粘度通常在0 · 50d 1/g 以上，其中以〇 . 5 0〜g/cm35 0 dl/g爲較宜 ，尤以0 _ 72〜1 · 〇d Ι/g爲最佳。又，其密度通 常在1 . 37g/cm3以上，其中以1 · 37〜1 · 4 4g/cm3 爲較宜，以 1 · 38 〜1 · 43g/cm3 爲更佳，尤以1 · 3 9〜1 . 4 2 g / c m 3爲理想。 聚酯（P - 5 )在2 9 0 °C下壓注模成型之際，其流 動長度（L )和流動寬度（T )之比率（L / T )爲Y時 ，又’前述壓注模成型所得成型物之固有粘度爲X ( d 1 / g )時，前述X和Y能滿足下述關係爲要。 經濟部智慧財產局員工消費合作社印製-108- 585881 kl ___B7_ V. Description of the invention (10 today (please read the precautions on the back before filling in this page) Methylethane, trimethylolpropane, trimethylolmethane, isopentyl alcohol and other polyfunctional The repeating unit caused by a polyfunctional compound. The repeating unit caused by a polyfunctional compound is preferably a ratio of 0 to 2 mole% for the repeating unit caused by a diol. Containing a repeating unit caused by a polyfunctional compound Polyesters having a repeating unit in the above range tend to have a higher fluidity when melted. The inherent viscosity of the polyester (P-5) is usually above 0. 50d 1 / g, of which 0.5 to 0 / g / cm35 0 dl / g is more suitable, especially 0 _ 72 ~ 1 · 〇d Ι / g. The density is usually above 1. 37g / cm3, of which 1. 37 ~ 1 · 4 4g / cm3 is more suitable, 1 · 38 ~ 1 · 43g / cm3 is more preferable, and 1 · 39 ~ 1.42 g / cm3 is more preferable. Polyester (P-5) at 2 0 0 ° C When the injection molding is performed under pressure, the ratio (L / T) of the flow length (L) to the flow width (T) is Y, and the inherent viscosity of the molded product obtained by the aforementioned injection molding is also used. When X (d 1 / g), the aforementioned X and Y meet the following relationship. Economic Affairs Intellectual Property Office employees consumer cooperatives to be printed

通吊爲 Y— 6 4 7 — 5 0 0X 較宜爲Y-647·5-500X 最佳爲 Y-648 — 500X 按照上述，在2 9 0 t下壓注模成型之際，其流動長 度（L )和流動密度（τ )之比率（L / T )爲Y時，壓 注模成型所得成型物之固有粘度爲X ( d 1 /g )時，前 述X和Y能滿足上述關係之聚酯（P 一 5 )，在高固有粘 動下，仍然有高熔融流動性，因此，其成型性優異。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -109- 585881 A7 B7 五、發明説明（1〇乃 本發明中’聚酯（P - 5 )在2 9 0 °C下壓注模成型 之際，其流動長度（L )和流動寬度（丁）之比率（l / T )按照下述方法測定之。 (請先閱讀背面之注意事項再填寫本頁) 即，將粒狀聚酯（P - 5 )(顆粒狀聚酯）取2 k g ’在溫度1 4 0 t：，壓力1 〇 丁 〇 ^ 1•之條件下使用層狀 乾燥機乾燥1 6小時以上，把粒狀聚酯（p — 5 )之水分 降低到5 Ο P P m以下。 其次’使用名機製作所公司製品之壓注模成型機 Μ 7 0 B型’將上述乾燥試料在圓筒溫度2 9 0 °C下，藉 三井化學公司製品之L / T模，設定模溫爲1 5 ，按照 下述條件進行成型加工 壓注模壓力·· 120kg/cm2 (表壓） 壓注模速度：9 0 % 計量位置：4 0 m m固定 壓注模時間：1 0秒鐘固定 壓注模時間：2 0秒鐘固定 經濟部智慧財產局員工消費合作社印製 又’ L / T模之模槽部分之形狀爲長1 2 5 c m X寬 1 0 m m X厚2 m m，在長方向之一端設置模注嘴。 所壓注之樹脂以模注嘴爲中心在模槽內以螺旋放射狀 流動’熔融樹脂保持寬1 〇 m m，厚（T ) 2 m m之形狀 下在模槽內移動。 L / T測定用試料使用成型開始後第1 1〜第2 0個 做爲試料，分別測定其流動長度（L )求其平均値，並計 算 L / 丁。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -110 - 585881 A7 B7 五、發明説明（1〇弓 ^^衣-- (請先閱讀背面之注意事項再填寫本頁) 上述壓注模成型所得成型物之固有粘度（X )，使用 酚和1 ，1 ，2 ，2 —四氯乙烷之混合溶劑（5 0 / 5 0 重里比率），調製0 · 5 g / d 1之試料溶液，在2 5 〇C 下所測定之溶液粘度計算其固有粘度。固有粘度測定用試 料從L / τ測定用試料中採取之。 聚酯（P - 5 )在2 9 0 t下壓注模成型之際，所得 流動長度和流動寬度之比率（Y )，以及前述壓注模成型 所得成型物之固有粘度（X )滿足上述關係，這種聚酯（ P - 5 )在熔融時之流動性高，成型性優異。 經濟部智慧財產局員工消費合作社印製 聚酯（P - 5)之鈦原子含量通常在1〜1 〇〇 P Pm範圍，其中尤以1〜8 0 p pm範圍爲佳，鎂原子 含量通常在1〜200ppm範圍，尤以1〜1〇〇 P P m範圍爲佳。又’該聚酯（P - 5 )中所含鈦原子和 鎂原子之重量比率（Mg/T i )通常在〇 . 〇 χ以上， 其中以0 · 06〜10爲較宜，尤以〇· 06〜5範圍內 爲最佳。鈦原子和鎂原子之重量比率（Mg/τ i )在上 述範圍內之聚酯（P - 5 )，具有透明性優異之傾向。又 ，該聚酯（P - 5 )之含氯量通常在0〜1 〇 〇 〇 p pm 範圍，尤以0〜lOOppm範圍內爲宜。 具備上述特性之聚酯（P - 5 )，例如可按照下述方 法製造之。 聚酯（P - 5 )係以芳香族二羧酸或其酯形成性衍生 物和脂肪族二元醇或其酯形成性衍生物爲原料，其中宜以 對苯二甲酸或其酯形成性衍生物和乙二醇或其酯形成性衍 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -111 - 585881 A7 _B7____ 五、發明説明（1Q9) (請先閱讀背面之注意事項再填寫本頁) 生物爲原料，必要時，再加以上述之二羧酸類，二元醇類 ，多官能性化合物爲原料，使用下述縮聚合觸媒，按照上 述之酯化步驟’液相縮聚合步驟，必要時再加以固相縮聚 合步驟等進行而製造之。 縮聚合觸媒可使用丁氧基鈦，四異丙氧基鈦等之烷氧 基鈦；鈦之乙醯丙酮鹽等有機鈦化合物；烷氧基鈦之水解 或鹵化鈦化合物之水解所得水解產物等鈦化合物觸媒。又 ，烷氧基鈦或鹵化鈦化合物之水解之際，可有其他元素之 化合物之共存。 聚酯（P — 5 )之製造中，縮聚合觸媒以使用上述水 解產物（I 一 m )或水解產物（I 一 η )(即含鈦水解產 物（Α - 2 ))爲較宜。 含鈦水解產物（A - 2 )在必要時可和輔觸媒成分（ Π )倂用。 上述輔觸媒成分（Π )可舉上述輔觸媒化合物相同者 ，其中以碳酸鎂，乙酸鎂等鎂化合物；碳酸鈣，乙酸鈣等 鈣化合物；氯化鋅，乙酸鋅等鋅化合物爲宜。輔觸媒化合 物可單獨一種或二種以上調配做爲輔觸媒成分使用。 經濟部智慧財產局員工消費合作社印製 使用錶化合物爲輔觸媒成分（Π )時，可製得透明性 優異之聚乙烯對苯二甲酸酯。 上述輔觸媒成分（Π )之使用以上述縮聚合觸媒中之 鈦（含鈦水解產物（A - 2 )含有其他元素時，包括鈦和 其他元素）（I)和輔觸媒成分中之金屬原子（Π)之莫 耳比率〔（Π)/(Ι)計，通常以1/50〜50/1 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）_ 112 585881 A7 B7 五、發明説明（110) ，其中1/40〜40/1 ，尤以1/30〜30/1範 圍量爲理想。又，使用磷酸鹽或亞磷酸鹽等磷化合物時， 以磷化合物中之金屬原子換算之。 該縮聚合觸媒之使用比率，對於芳香族二羧酸和脂肪 族二元醇之混合物重量計，縮聚合觸媒時，縮聚合觸媒中 之金屬重量計，通常爲0·0005〜0.2重量％，其 中以0·001〜0·05重量％爲宜，又使用上述之安 定劑時，以安定劑中之磷原子重量計，通常爲0·001 〜0 · 1重量％，其中以0 · 002〜0 · 02重量％範 圍爲較宜。上述縮聚合觸媒和安定劑之供料方法，可在酯 化反應步驟供應，也可以在縮聚合反應步驟之第一階段供 應到反應容器中。 按照上述方法所得聚酯（P — 5 )之固有粘度，通常 在0 · 50d Ι/g以上，其中以〇 · 50〜1 . 50 d Ι/g爲較宜，尤以0 · 72〜1 · 0d Ι/g爲最佳 。該聚酯（P — 5)之密度，通常在1 · 37g/cm3以 上，其中以1 · 37〜1 · 44g/cm3爲較宜，以 1 · 38〜1 · 43g/cm3爲更佳，尤以1 · 39〜 1·42g/cm3爲最佳。 將上述所得聚酯（P - 5 )在2 9 0°C下壓注模成型 之際，其流動長度（L )和流動寬度（T )之比率（L / T )做爲Y時，上述壓注模成型所得成型物之固有粘度爲 X (d Ι/g)時，前述X和Y之關係爲Y-647 — 500又。又，鈦原子含量通常在1〜1〇〇??111，尤 本紙張尺度適用中國國家標準（匚犯）六4規格（21〇乂297公董）-113- (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局a(工消費合作社印製 585881 A7 _____ B7 五、發明説明（111) 以1 8 0 p pm軔圍爲佳’錶原子含量通常在1〜 (請先閱讀背面之注意事項再填寫本頁) 20〇PPm，尤以1〜1 〇〇1313出範圍爲宜。又，該 聚酯（P - 5 )中所含鈦原子和鎂原子之重量比率（Mg / 丁 i)通常在0 · 01以上，其中以〇 · 〇6〜1〇爲 較且’尤以0·06〜5範圍爲最佳。又，做爲縮聚合觸 媒’使用上述縮聚合觸媒（I )，必要時，倂用輔觸媒成 分（Π )時’所得聚酯（p _ 5 )具有優異之色相和透明 性’聚酯（P - 5 )中之乙醛含量和環狀三聚物等寡聚物 含量少。 按照上述方法製造之聚酯（P — 5 )，尙可添加已往 周知之添加劑，例如安定劑，離模劑，靜電防止劑，分散 劑’染料，色料等著色劑等，上述添加劑可在製造聚酯（ P 一 5 )時之任意階段中添加，成型加工前添加在主槽中 也行。 聚酯（P - 5 )可提供各種成型物之原料用途，例如 熔融而成型爲瓶等中空成型物，片狀物，薄膜，纖維等使 用’其中以製瓶用途爲最適宜。 經濟部智慧財產局員工消費合作社印製 由聚酯（P - 5)成型爲瓶，片狀物，薄膜，纖維等 之成型方法可採用已往周知之方法，例如上述舉例之方法 皆可採用。 聚酯（P — 5 )熔融時之流動性高，成型爲中空成型 物，薄膜，片狀物，纖維等之際，其成型性優異。 本發明有關之中空成型物用預塑物和中空成型物，可 由上述聚酯（P - 5 )製得，具有優異之透明性。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-114 - 585881 A7 B7 五、發明説明（112) 本發明之效果 (請先閱讀背面之注意事項再填寫本頁) 本發明有關之聚酯製造用觸媒乃係比較已往做爲縮聚 合觸媒之鍺化合物，銻化合物可藉高觸媒活性而製造聚酯 。又，依據本發明之方法，比較使用銻化合物做爲縮聚合 觸媒時，可製得透明性，色相優異而乙醛含量少之聚酯。 本發明有關之固態狀鈦化合物（I 一 a )和/或固態 狀鈦含化合物（I - b )，必要時，再加上由下列輔觸媒 成分（Π)所構成聚酯製造用觸媒，較之已往做爲縮聚合 觸媒使用之鍺化合物，銻化合物能以高觸媒活性而製造聚 酯。又，使用該觸媒製造聚酯時，較之使用銻化合物爲縮 聚合觸媒比較可製得透明性，色相優異而乙醛含量少之聚 酯。使用本發明有關之該觸媒而製成之聚酯，例如聚乙烯 對苯二甲酸酯和由此構成之成型物，其透明性，色相優異 而乙醛含量少。 經濟部智慧財產局員工消費合作社印製 本發明有關之固態狀鈦化合物（I - c )和輔觸媒成 分（Π )所構成，或下列固態狀含鈦化合物（I 一 d )和 必要時再加上輔觸媒成分（Π )所構成之聚酯製造用觸媒 ，比較已往做爲縮聚合觸媒用之鍺化合物，銻化合物可以 高觸媒活性而製造聚酯。使用該觸媒製造聚酯，較之使用 銻化合物爲縮聚合觸媒，可得透明性，色相優異而乙醛含 量少之聚酯。 本發明有關之固態狀鈦化合物（I 一 e ) ’固態狀鈦 化合物（I — ί )，固態狀含鈦化合物（I _ g )或固態 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-115 - 585881 A7 B7 113 五、發明説明（、 (請先閲讀背面之注意事項再填寫本頁) 狀含鈦化合物（I 一 h )和必要時再加上下記輔觸媒成分 (Π )所構成之聚酯製造用觸媒，較之已往做爲縮聚合觸 媒使用之鍺化合物，銻化合物可藉高觸媒活性製造聚酯。 又，使用此觸媒製造聚酯時，較之使用銻化合物爲縮聚合 觸媒時，可得透明性，色相優異，乙醛含量少之聚酯。 本發明有關之固態狀鈦化合物（I - 1 )和必要時再 加上輔觸媒成分（Π )所構成聚酯製造用觸媒，比較已往 做爲縮聚合觸媒使用之鍺化合物，銻化合物可藉高觸媒活 性而製造聚酯。又，使用此觸媒製造聚酯時，較之使用銻 化合物爲縮聚合觸媒，可得透明性，色相優異，乙醛含量 少之聚酯。 本發明有關之聚酯製造用觸媒 (A - 1)，乃由水解產物（I — j)或水解產物（I 一 k )和鹼性化合物（B )以及脂肪族二元醇（C )之混合 物經加熱而成泥漿所構成，藉此可在短時間內製得具有所 欲固有粘度之聚酯， 經濟部智慧財產局員工消費合作社印製 本發明有關之聚酯製造用觸媒 (A - 2 )係由水解產物（I — m )或水解產物（I 一 η )和磷酸金屬鹽（D )所構成， 或由水解產物（I 一 m )或水解產物（I 一 η )和金屬化 合物（Ε )，和磷化合物（F )以及脂肪族二元醇（G ) 之混合物經加熱而得之泥漿所構成，藉此能以高聚合活性 而製造乙醛含量少之聚酯。 使用本發明有關之水解產物（I - j )和水解產物（ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）-116 - 585881 A7 B7___ 五、發明説明（114) (請先閱讀背面之注意事項再填寫本頁) I 一 k)所構成之觸媒成分（〗）以及輔觸媒成分（π) 所構成觸媒做爲縮聚合觸媒，且在酯化反應開始前或酯化 反應開始直後，將上述觸媒成分（I )添加在酯化反應容 器中之聚酯製造方法，可在短時間內製得所欲固有粘度之 聚酯。 本發明有關之芳香族二羧酸或其酯形成性衍生物和脂 肪族二元醇或其酯形成性衍生物使用 (1 ) ’水解產物（I — m )所構成縮聚合觸媒， (2 )，水解產物（I 一 η )所構成縮聚合觸媒， (3 )，水解產物（I 一 m )或水解產物（I 一 m )和金 屬化合物或磷酸鹽或亞磷酸鹽中所選擇縮聚合觸媒，以及 環狀內酯系化合物和受阻酚系化合物中所選擇至少一種之 化合物之存在下縮聚合成爲聚酯之聚酯之製造方法，可藉 高聚合活性而製得聚酯，所得聚酯之乙醛含量少。 使用本發明有關之水解產物（I 一 m )或水解產物（ I 一 η )所構成縮聚合觸媒成分（I )和輔觸媒成分（π )所構成觸媒做爲縮聚合觸媒，且 經濟部智慧財產局員工消費合作社印製 在酯化步驟或縮聚合步驟之任意步驟中添加色相調整 劑之聚酯之製造方法，可藉高聚合活性而製得色相良好之 聚酯。 本發明有關之聚酯之處理方法，可製得成型時乙醛含 量之增加少，固有粘度之降低少之聚酯。 本發明有關之聚酯（Ρ - 1 )和由此構成之成型物， 其透明性，色相優異而乙醛含量少。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）· - 585881 A7 ______B7 五、發明説明（115 ) 本發明有關之聚酯（P - 2)色相良好。 (請先閱讀背面之注意事項再填寫本頁) 本發明有關之聚酯（P - 3 )，其乙醛含釐少，且成 型爲成型物之際，乙醛含量之增加顯著受到抑制。例如以 該聚酯（P - 3 )成型瓶等時，塡充於該瓶中之內容物之 香味等之劣化較少。 本發明有關之聚酯（P - 4)，其環狀三聚物含量少 ，且成型時所產生之環狀三聚物量也少。 本發明有關之聚酯（P - 5 )，其熔融流動性高，成 型爲中空成型物，薄膜，片狀物，纖維等之際，其成型性 優異。 實施例 〔實施例4 9 5 — 1〕 固態狀鈦化合物之調製 經濟部智慧財產局員工消費合作社印製 1 ο ο 〇 d之玻璃燒坯中秤取5 ο 〇 j之去離子水， 在冰浴中冷卻下攪拌中滴加5 g之四氯化鈦、氯化氫氣體 之產生停止後，從冰浴中取出，攪拌下滴加2 5 %之氨水 ’調整溶液爲ρ Η 8。所產生之鈦氫氧化物之沈澱物藉 2 5 0 0旋轉離心1 5分鐘而和上澄液分離之。然後使用 去離子水洗淨所得鈦氫氧化物之沈澱物5次。洗淨後再以 2 5 0 0旋轉離心1 5分鐘而進行固液相之分離。洗淨後 之鈦氫氧化物在7 0 °C，1 〇 Τ ◦ r r以下，減壓乾燥 1 8小時而去除水分，獲得固態狀鈦化合物。 所得固態狀鈦化合物在做爲縮聚合觸媒使用之前，先 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐）~一 -118- 585881 A7 B7 五、發明説明（116 ) 粉碎成爲1 0 # m程度之粒狀物。 按照上述所得固態狀鈦化合物利用卡爾-費歇水分計 測定其附著水分結果得悉含有6 . 7 3重量％之水分。又 ，使用熱重量測定法測定加熱失重之結果，到達2 8 0 °C 爲止失去初重量之7 · 50重量％，280 °C至600 t 之間再失去2 _ 1 7重量％，知悉上述失重係由水和氮化 合物之脫離所造成的。觸媒中所含氮爲1 · 3重量％，含 氯量也僅爲1 4 P P m，因此，可知氮並非來源於氯化銨 ，而推測是來自氨。又，利用高頻電漿發光分析裝置所求 得固態狀鈦化合物中之含鈦量爲4 6重量％。 由上述可知所得固態狀鈦化合物之鈦和氫氧基之莫耳 比率爲1 : 0 · 1 5 7。又，藉微量總氮分析裝置（化學 發光法）分析氮，另以層析法分析氯，分別以氨，氯化氫 脫離而計算之。 〔實施例4 9 5 — 2〕 固態狀含鈦化合物之調製 1 0 0 0 J之玻璃燒枉中秤取5 0 0 W之去離子水， 加入0 · 1 5 g之無水氫氧化鎂並加以分散之。在冰浴中 冷卻後攪拌中滴加5 g之四氯化鈦。溶液變成酸性而氫氧 化鎂溶解其中。待氯化氫停止產生後取出冰浴，攪拌下滴 加2 5%之氨水，調整溶液爲pH8。所產生含鈦複合氫 氧化物之沈澱物以2 5 0 0旋轉離心1 5分鐘而和上澄液 分離之。然後使用去離子水洗淨所得含鈦複合氫氧化物之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 、τ 經濟部智慧財產局員工消費合作社印製 -119 - 585881 A 7 B7 五、發明説明（117 ) (請先閱讀背面之注意事項再填寫本頁) 沈澱物5次。洗淨後之固液相分離藉2 5 0 0旋轉離心 1 5分鐘而進行。洗淨後之含鈦複合氫氧化物在7 0 °C， 1 0 丁 〇 r r下，減壓乾燥1 8小時而去除水分，獲得固 態狀含鈦化合物。 該固態狀含鈦化合物之鈦和鎂之原子比率爲鈦原子 9 1莫耳，對於鎂原子9莫耳。所得固態狀含鈦化合物藉 熱重量測定知悉鈦對氫氧基莫耳比率爲1 : 0 . 3 1。該 固態狀含鈦化合物在做爲縮聚合.觸媒使用之前，先粉碎爲 1 0 m左右之粉狀物。 〔實施例4 9 5 - 3〕 固態狀含鈦化合物之調製 經濟部智慈財產局員工消費合作社印製 1 0 0 0 4之玻璃燒枉中秤取5 0 0 2之去離子水， 加入0 . 1 6 g之膠狀二氧化矽（商品名爲士諾得〇X S )並加以分散之。冰浴中冷卻之後，攪拌中滴加5 g之四 氯化鈦。溶液變成酸性而膠狀二氧化矽溶解其中。氯化氫 之產生停止後自冰浴取出，攪拌中滴加2 5 %之氨水，調 整溶液爲P Η 8。所產生之含鈦複合氫氧化物之沈澱物藉 2 5 0 0旋轉離心1 5分鐘而和上澄液分離。然後，使用 去離子水洗淨所得含鈦複合氫氧化物之沈澱物5次。洗淨 後以2 5 0 0旋轉離心1 5分鐘而進行固液相分離。洗淨 後之含鈦複合氫氧化物在7 0 t，1 〇 Τ ο I* r下減壓乾 燥1 8小時而去除水分，獲得固態狀含鈦化合物。該固態 狀含鈦化合物中之鈦和矽之原子比率爲鈦原子9 4莫耳對 本紙張尺度適用中國國家標準（CNS ) A4規格（210X：297公楚） •120- 585881 A7 B7 五、發明説明（118 ) (請先閱讀背面之注意事項再填寫本頁) 砂原子6莫耳。所得固態狀含鈦化合物藉熱重量測定而知 欽對氫氧基之莫耳比率爲1 : 〇 · 6 0。該固態狀含鈦化 合物做爲縮聚合觸媒使用之前，先粉碎爲1 〇 ^ m左右之 粒狀物。 〔實施例4 9 5 — 4〕 聚酯之製造 例行操作時可滯留3 3 5 0 0重量份之反應液的反應 容器中。攪拌下，氮氣中，保持26〇 °c，0 . 9kg/ c m2 G之條件下，連續供應由6 4 5 8重量份/小時之高 純度對苯二甲酸和2 6 1 5重量份/小時之乙二醇經混合 調製成之泥漿，而進行酯化反應。該酯化反應中蒸餾去除 水和乙二醇之混合液。 酯化反應產物（低聚合物）控制在平均滯留時間爲 3 · 5小時，而連續抽出到反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲60〇〜13〇〇（3〜5聚物）。 經濟部智慧財產局員工消費合作社印製 使用實施例4 9 5 - 1所調製之固態狀鈦化合物做爲 縮聚合觸媒，進行上述所得低聚合物之液相縮聚合反應。 觸媒添加量以固態狀鈦化合物之鈦原子計，對於低聚 合物中之對苯二甲酸單位計算，加入〇 · 〇 〇 5莫耳，然 後在2 8 5 °C，1 T 〇 r I·條件下進行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度（IV )達到〇 . 5 8 d 1 / g爲止所需時間（即液相縮聚合反應時間）爲9 5 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -121 - 585881 A7 _____________B7 五、發明説明（彳19 ) 分鐘。 〔實施例495-5〕 (請先閲讀背面之注意事項再填寫本頁) 實施例4 9 5 - 4中，縮聚合觸媒改爲使用實施例 4 9 5 - 2所調製之固態狀含鈦化合物之外，其餘皆按p语 實施例4 9 5 - 4同樣方法進行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度（IV )達到〇 . 5 8 d 1 / g爲止所需時間（即液相縮聚合反應時間）爲7 6 分鐘。 〔實施例4 9 5 — 6〕 實施例4 9 5 - 4中，縮聚合觸媒改用實施例4 9 5 - 3所調製固態狀含鈦化合物之外，其餘皆按照實施例 4 9 5 - 4同樣方法進行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度（TV )到達〇 . 5 8 d 1 / g爲止所需時間（液相縮聚合反應時間）爲8 5分 鐘。 經濟部智慧財產局員工消費合作社印製 〔實施例4 9 5 - 7〕 實施例4 9 5 - 4中，縮聚合觸媒改用實施例4 9 5 - 1所調製固態狀鈦化合物和碳酸鎂化合物之外，其餘皆 按照實施例4 9 5 - 4同樣進行縮聚合反應。碳酸鎂之添 加量對低聚合物中之對苯二甲酸單位計，以鎂原子換算使 用0.005莫耳％。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -122- 8 8 5 8 5 A7 _________ B7 五、發明説明（12〇 ) 聚乙烯對苯二甲酸酯之固有粘度（IV )達到〇 · 5 8 d 1 / g爲止所需時間（即液相縮聚合反應時間）爲7 5 (請先閲讀背面之注意事項再填寫本頁) 分鐘。 〔實施例4 9 5 - 8〕 實施例4 9 5 - 4中，縮聚合觸媒改用實施例4 9 5 - 1所調製之固態狀鈦化合物再加上乙酸鎂之外，其餘皆 按照實施例4 9 5 - 4所示相同方法進行縮聚合反應。乙 酸鎂之添加量爲低聚合物中之對苯二甲酸單位計，鎂原子 換算爲0.005莫耳％。 聚乙烯對苯二甲酸酯之固有粘度（IV )到達〇 . 5 8 d丨/ g爲止所需時間（即液相縮聚合反應時間）爲7 0 分鐘。 〔實施例4 9 5 — 9〕 實施例4 9 5 - 4中，縮聚合觸媒改用實施例4 9 5 經濟部智慧財產局員工消費合作社印製 - 1所調製之固態狀鈦化合物密封在容器中經室溫下保管 2個月之觸媒以外，其餘皆按照實施例4 9 5 - 4同樣進 行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度（IV)達到〇 . 5 8 d 1 / g爲止所需時間（即液相縮聚合反應時間）爲 1〇1分鐘。 由本實施例可知本發明有關之固態狀鈦化合物，不會 經時劣化，其保存性良好。又，另據特公昭 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）~' ' -123· 585881 A7 B7 五、發明説明（121) 4 7〜2 6 5 9 7號公報之比較例所示原鈦酸會經時劣化 而降低縮聚合活性。 (請先閲讀背面之注意事項再填寫本頁} 〔比較例4 9 5 — 1〕 實施例4 9 5 — 4中，改用工業上常用之乙酸銻做爲 縮聚合觸媒之，其餘皆按照實施例4 9 5 - 4所示相同方 法進行縮聚合反應。乙酸銻之添加量對於低聚合物中之對 苯二甲酸單位計，銻原子換算爲0·025莫耳％。 聚乙烯對苯二甲酸酯之固有粘度（IV)達到〇 . 5 8 d 1 / g爲止所需時間（即液相縮聚合反應時間）爲 1 2 0分鐘。 〔比較例4 9 5 - 2〕 鈦化合物之調製 實施例4 9 5 - 1中，將經去離子水洗淨後之鈦氫氧 化物以1 0 0 °C煮沸2小時後乾燥而得鈦化合物。 聚酯之製造 經濟部智慧財產局D貝工消費合作社印製 實施例4 9 5 — 4中，改用上述鈦化合物做爲縮聚合 觸媒之外，其他皆按照實施例4 9 5 一 4所示相同方法進 行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度（IV)達到〇 . 5 8 d 1 / g爲止所需時間（即液相縮聚合反應時間）爲 1 8 5分鐘。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ 124 _ " 585881 A 7 B7 122 五、發明説明（） 鈦氫氧化物在水中加熱時，已知會轉變成原鈦酸，因 此，可知經由原鈦酸而得鈦化合物之縮聚合活性較低。 (請先閲讀背面之注意事項再填寫本頁) 〔實施例4 9 6 — 7〕 在100 °C，常壓下，將76 · 8 1莫耳之高純度對 苯二甲酸和8 6 · 0 3莫耳之乙二醇供應到酯化反應容器 中，再以實施例495 — 2中所調製之0 . 0045莫耳 之固態狀含鈦化合物做爲觸媒而添加之。繼之，將反應容 器升溫至260°C，在壓力爲1 · 7kg/cnfG，氮氣 中反應3 4 0分鐘。該反應中所產生之水經常設法蒸餾排 除反應系外。 然後，將酯化反應容器中之總量移到事先加溫爲 2 6 0°C之縮聚合反應容器中之後，再於常壓下將溶解有 0·0073莫耳之三丁基磷酸酯之6·44莫耳的乙二 醇添加到上述反應容器中，使用6 0分鐘自2 6 0 °C升溫 到2 8 0 °C，同時由常壓減壓到2 T 〇 r !·。 經濟部智慧財產局8工消費合作社印製 再於縮聚合反應容器中進行1 0 8分鐘之反應後，從 反應容器中將反應產物以絲狀取出，浸漬水中加以冷卻， 利用切絲刀裁斷成爲粒狀而得聚乙烯對苯二甲酸酯。該聚 乙烯對苯二甲酸酯之固有粘度爲〇 · 65d Ι/g ，藉原 子吸光分析所測定鈦、鎂含量分別爲2 5 p p m， 2ppm，鎂/鈦重量比率爲〇 · 〇8。 再將液相縮聚合反應所得聚乙烯對苯二甲酸酯移到固 相縮聚合反應塔，在氮氣中，i 7 〇。(：下結晶化處理2小 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）-125 - 585881The through-hole is Y— 6 4 7 — 5 0 0X, more preferably Y-647 · 5-500X, and most preferably Y-648 — 500X. According to the above, when the injection molding is performed at 2 9 0 t, the flow length ( When the ratio (L / T) of L) to flow density (τ) is Y, when the inherent viscosity of the molded product obtained by injection molding is X (d 1 / g), the polyester in which the aforementioned X and Y can satisfy the above relationship (P-5), it still has high melt fluidity under high inherent viscosity, so it has excellent moldability. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -109- 585881 A7 B7 V. Description of the invention (10 is the 'polyester (P-5) in the present invention pressed at 2 90 ° C During injection molding, the ratio (l / T) of the flow length (L) to the flow width (D) is measured according to the following method. (Please read the precautions on the back before filling this page). Polyester (P-5) (granular polyester) Take 2 kg 'at a temperature of 14 0 t: and a pressure of 10 〇 〇 ^ 1 • using a layer dryer to dry for more than 16 hours, granulate The water content of polyester (p-5) was reduced to less than 5 Ο PP m. Secondly, "the injection molding machine M 7 0 B type used by the famous company Seisakusho Co., Ltd." was used to place the above-mentioned dried sample at a cylinder temperature of 2 0 0 ° C. Next, use the L / T mold of Mitsui Chemicals Corporation, set the mold temperature to 15 and perform the molding process according to the following conditions. Injection molding pressure: 120kg / cm2 (gauge pressure) Injection molding speed: 90% of the measuring position : 40 mm fixed injection molding time: 10 seconds fixed injection molding time: 20 seconds The shape of the groove section of the L / T mold printed by Fei Cooperative is 12.5 cm in length X 10 mm in width X 2 mm in thickness, and a molding nozzle is provided at one end in the long direction. The nozzle is centered in a spiral radial flow in the mold groove, and the molten resin moves in the mold groove while maintaining a shape of 10 mm in width and 2 mm in thickness (T). The sample for L / T measurement is used after the start of molding. The 20th piece was used as a sample, and its flow length (L) was measured to obtain its average 値, and L / D was calculated. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -110-585881 A7 B7 V. Description of the invention (10 bow ^^ clothing-(Please read the precautions on the back before filling this page) The inherent viscosity (X) of the molded product obtained by the above injection molding, using phenol and 1, 1, 2, 2 2—Tetrachloroethane mixed solvent (50/50 weight ratio), prepare a sample solution of 0.5 g / d1, and calculate the inherent viscosity of the solution viscosity measured at 250 ° C. Determination of intrinsic viscosity The sample was taken from the L / τ measurement sample. Polyester (P-5) was injection-molded at 290 t. At the same time, the ratio (Y) of the obtained flow length to the flow width and the inherent viscosity (X) of the molded product obtained by the aforementioned injection molding satisfy the above-mentioned relationship. This polyester (P-5) has high fluidity when melted, Excellent moldability. The titanium atom content of polyester (P-5) printed by the consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is usually in the range of 1 ~ 100P Pm, especially in the range of 1 ~ 80 p pm. Magnesium The atomic content is usually in the range of 1 to 200 ppm, particularly preferably in the range of 1 to 100 ppm. Also, the weight ratio (Mg / T i) of the titanium atom and the magnesium atom contained in the polyester (P-5) is usually greater than or equal to 〇χ, in which 0. 06 to 10 is more preferable, especially 0. The best range is 06 ~ 5. A polyester (P-5) having a weight ratio (Mg / τ i) of titanium atom and magnesium atom in the above range tends to have excellent transparency. The chlorine content of the polyester (P-5) is usually in the range of 0 to 100 ppm, particularly preferably in the range of 0 to 100 ppm. The polyester (P-5) having the above characteristics can be produced, for example, by the following method. Polyester (P-5) is based on aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative. Among them, terephthalic acid or its ester-forming derivative is preferred. Paper and ethylene glycol or its ester-forming derivative The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -111-585881 A7 _B7____ 5. Description of the invention (1Q9) (Please read the precautions on the back before Fill in this page) Biology is used as raw materials, and if necessary, the above-mentioned dicarboxylic acids, glycols, and polyfunctional compounds are used as raw materials. The following polycondensation catalyst is used, and the above-mentioned esterification step is used for liquid phase condensation polymerization It is produced by performing a solid phase condensation polymerization step and the like if necessary. Polycondensation catalysts can use titanium alkoxide such as titanium butoxide, titanium tetraisopropoxide; organic titanium compounds such as acetone and acetone salts of titanium; hydrolysis products obtained by hydrolysis of titanium alkoxide or hydrolysis of titanium halide compounds Catalysts such as titanium compounds. In the hydrolysis of titanium alkoxide or titanium halide compounds, compounds of other elements may coexist. In the production of polyester (P-5), it is preferable to use the above-mentioned hydrolysate (I-m) or hydrolysate (I-η) (i.e., titanium-containing hydrolysate (A-2)) as the polycondensation catalyst. The titanium-containing hydrolysate (A-2) can be used with the auxiliary catalyst component (Π) when necessary. The auxiliary catalyst component (Π) may be the same as the auxiliary catalyst compounds mentioned above. Among them, magnesium compounds such as magnesium carbonate and magnesium acetate; calcium compounds such as calcium carbonate and calcium acetate; and zinc compounds such as zinc chloride and zinc acetate are preferred. The auxiliary catalyst compound can be used alone or in combination of two or more as the auxiliary catalyst component. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When the surface compound is used as the auxiliary catalyst component (Π), polyethylene terephthalate with excellent transparency can be produced. The use of the auxiliary catalyst component (Π) is based on the titanium (the titanium-containing hydrolysate (A-2) containing other elements, including titanium and other elements) in the polycondensation catalyst (I) and the auxiliary catalyst component. Molar ratio of metal atom (Π) [(Π) / (Ι), usually based on 1/50 ~ 50/1 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) _ 112 585881 A7 B7 5. Description of the invention (110), wherein 1/40 ~ 40/1, especially an amount in the range of 1/30 ~ 30/1 is ideal. When a phosphorus compound such as phosphate or phosphite is used, it is converted into a metal atom in the phosphorus compound. The ratio of the polycondensation catalyst is based on the weight of the mixture of aromatic dicarboxylic acid and aliphatic diol. When the polycondensation catalyst is used, the weight of the metal in the polycondensation catalyst is usually from 0.005 to 0.2 weight %, Which is preferably from 0.001 to 0.05% by weight, and when the stabilizer is used, it is usually from 0. 001 to 0. 1% by weight based on the weight of the phosphorus atom in the stabilizer. A range of 002 to 0. 02% by weight is preferable. The above-mentioned method for feeding the polycondensation catalyst and stabilizer may be supplied in the esterification reaction step, or may be supplied to the reaction container in the first stage of the polycondensation reaction step. The inherent viscosity of the polyester (P-5) obtained according to the above method is usually above 0. 50 d Ι / g, of which 50.50 to 1. 50 d Ι / g is more preferable, especially 0. 72 to 1. 0d Ι / g is the best. The density of the polyester (P-5) is usually above 1.37g / cm3, of which 1.37 ~ 1.44g / cm3 is more preferable, and 1.38 ~ 1.43g / cm3 is more preferable, especially The optimum range is 1.39 to 1.42 g / cm3. When the polyester (P-5) obtained above is injection-molded at 290 ° C, and the ratio (L / T) of the flow length (L) to the flow width (T) is taken as Y, the above pressure When the intrinsic viscosity of the molded product obtained by injection molding is X (d I / g), the relationship between the aforementioned X and Y is Y-647 to 500. In addition, the titanium atom content is usually in the range of 1 ~ 10011, and the paper size of this paper is applicable to the national standard of China (offender) 6-4 specification (21〇297297) -113- (Please read the precautions on the back first Fill out this page again) Order the Intellectual Property Bureau of the Ministry of Economic Affairs a (printed by the Industrial and Consumer Cooperatives 585881 A7 _____ B7 V. Description of the invention (111) It is better to be around 1 800 p pm. 'The atomic content is usually 1 ~ Read the notes on the back and fill in this page again) 20〇PPm, especially in the range of 1 ~ 1001313. Also, the weight ratio (Mg) of titanium atom and magnesium atom contained in the polyester (P-5) / 丁 i) Usually 0. 01 or more, of which 0. 〇6 ~ 1〇 is more preferred, and the range of 0. 06 ~ 5 is the best. In addition, as the condensation polymerization catalyst, the above-mentioned condensation polymerization catalyst is used. Medium (I), if necessary, when using the auxiliary catalyst component (Π), 'the obtained polyester (p_5) has excellent hue and transparency', the acetaldehyde content and ring in the polyester (P-5) The content of oligomers such as trimer is small. For the polyester (P-5) produced according to the above method, conventionally known additives such as stabilizers can be added to the mold. , Antistatic agent, dispersant, dyes, colorants and other coloring agents, etc. The above additives can be added at any stage during the manufacture of polyester (P-5), and it can also be added to the main tank before molding. Polyester ( P-5) Can provide various raw materials for molding, such as melting and forming into hollow moldings such as bottles, sheets, films, fibers, etc. 'Among them, bottle making is the most suitable. Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative prints from polyester (P-5) into bottles, sheets, films, fibers, etc. The molding method can be known in the past, for example, the methods described above can be used. Polyester (P-5) melting It has high fluidity and is excellent in moldability when molded into a hollow molded article, film, sheet, fiber, etc. The present invention relates to a preform for a hollow molded article and a hollow molded article, which can be obtained from the polyester (P -5) Manufactured with excellent transparency. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -114-585881 A7 B7 V. Description of the invention (112) Effect of the invention (please read first Note on the back, please fill in this page again.) The catalyst for polyester production related to the present invention is a germanium compound that has been used as a condensation polymerization catalyst. Antimony compounds can be used to manufacture polyesters with high catalyst activity. In the method of the present invention, when an antimony compound is used as a condensation polymerization catalyst, a polyester having transparency, excellent hue, and low acetaldehyde content can be obtained. The solid titanium compound (Ia) and / or solid according to the present invention The titanium-containing compound (I-b), if necessary, is added with a catalyst for polyester production composed of the following auxiliary catalyst components (Π), compared with germanium compounds and antimony compounds that have been used as condensation polymerization catalysts Can produce polyester with high catalyst activity. Further, when a polyester is produced by using this catalyst, a polyester having a transparency, an excellent hue, and a low acetaldehyde content can be obtained compared with a polycondensation catalyst using an antimony compound. Polyesters produced using the catalyst according to the present invention, such as polyethylene terephthalate and molded articles thereof, have excellent transparency, hue, and low acetaldehyde content. Consumption cooperative of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs prints solid titanium compounds (I-c) and auxiliary catalyst components (Π) related to the present invention, or the following solid titanium-containing compounds (I-d) and if necessary Adding the auxiliary catalyst component (Π) to the polyester manufacturing catalyst, compared with the traditional germanium compound used as a condensation polymerization catalyst, the antimony compound can produce polyester with high catalyst activity. Compared with the polycondensation catalyst using an antimony compound, the polyester produced by using this catalyst can obtain a polyester having excellent transparency, excellent hue and low acetaldehyde content. The solid state titanium compound (I-e) 'solid state titanium compound (I — ί), solid state titanium-containing compound (I_g) or solid state The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 (Mm) -115-585881 A7 B7 113 V. Description of the invention (, (Please read the precautions on the back before filling out this page) in the form of a titanium-containing compound (I-h) and, if necessary, add the following auxiliary catalyst ingredients ( Π) Compared with the germanium compound that has been used as a condensation polymerization catalyst, the antimony compound can be used to make polyester with high catalyst activity. In addition, when using this catalyst to produce polyester, When an antimony compound is used as a polycondensation catalyst, a polyester having excellent transparency, excellent hue, and low acetaldehyde content can be obtained. The solid titanium compound (I-1) according to the present invention and an auxiliary catalyst component are added if necessary. (Π) Compared with the germanium compound that has been used as a condensation polymerization catalyst, the antimony compound can be used to manufacture polyester with high catalyst activity. In addition, when using this catalyst to produce polyester, Polycondensation catalyst A polyester with excellent transparency and hue and low acetaldehyde content can be obtained. The catalyst (A-1) for polyester production according to the present invention is composed of a hydrolysate (I-j) or a hydrolysate (I-k). A mixture of basic compound (B) and aliphatic diol (C) is heated to form a slurry, so that a polyester with a desired inherent viscosity can be prepared in a short time. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs The catalyst (A-2) for polyester manufacturing related to the present invention printed by a consumer cooperative is composed of a hydrolysate (I-m) or a hydrolysate (I-η) and a metal phosphate (D), or a hydrolysate (I-m) or a hydrolysate (I-η) and a metal compound (E), and a phosphorus compound (F) and a mixture of aliphatic diols (G) by heating the slurry, which can be used to High polymerization activity to produce polyester with low acetaldehyde content. Use the hydrolysate (I-j) and hydrolysate (This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -116- 585881 A7 B7___ V. Description of the invention (114) (Please read the Please fill in this page for the matters needing attention) I-k) The catalyst component (〗) and the auxiliary catalyst component (π) are used as condensation polymerization catalysts, and before the esterification reaction starts or the esterification reaction After starting straight, the polyester manufacturing method in which the catalyst component (I) is added to the esterification reaction container can obtain a polyester with a desired inherent viscosity in a short time. The aromatic dicarboxylic acid or the related dicarboxylic acid according to the present invention The ester-forming derivative and the aliphatic diol or the ester-forming derivative thereof are composed of a condensation polymerization catalyst composed of (1) 'hydrolysate (I-m), (2), and a hydrolysate (I-η). Polycondensation catalyst, (3), a hydrolysate (I-m) or a hydrolysate (I-m) and a polycondensation catalyst selected from a metal compound or a phosphate or phosphite, and a cyclic lactone-based compound and A method for producing a polyester which is polycondensed into a polyester in the presence of at least one selected compound among the hindered phenol compounds can obtain a polyester with high polymerization activity, and the obtained polyester has a low acetaldehyde content. The condensation polymerization catalyst component (I) and the auxiliary catalyst component (π) composed of the hydrolysis product (I-m) or the hydrolysis product (I-η) of the present invention are used as the condensation polymerization catalyst, and The manufacturing method of the polyester printed by the consumer co-operative of the Intellectual Property Bureau of the Ministry of Economic Affairs, which adds a hue adjuster in any step of the esterification step or polycondensation polymerization step, can obtain a good-colored polyester by high polymerization activity. The processing method of the polyester related to the present invention can obtain a polyester with little increase in acetaldehyde content and little decrease in intrinsic viscosity during molding. The polyester (P-1) according to the present invention and a molded article formed therefrom have excellent transparency, hue, and low acetaldehyde content. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ·-585881 A7 ______B7 V. Description of the invention (115) The polyester (P-2) of the present invention has a good hue. (Please read the precautions on the back before filling out this page) The polyester (P-3) related to the present invention has a small amount of acetaldehyde, and when it is molded into a molded article, the increase in acetaldehyde content is significantly suppressed. For example, when the polyester (P-3) is used to form a bottle or the like, the flavor and the like of the contents filled in the bottle are less deteriorated. The polyester (P-4) according to the present invention has a small cyclic trimer content and a small amount of cyclic trimer produced during molding. The polyester (P-5) according to the present invention has high melt fluidity and is excellent in moldability when molded into a hollow molded article, film, sheet, fiber, or the like. Example [Example 4 9 5 — 1] Preparation of solid titanium compound 5: ο 〇j deionized water was weighed out of a glass sintered glass printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and weighed in ice. 5 g of titanium tetrachloride and hydrogen chloride gas were added dropwise while stirring in the bath with cooling, and then taken out of the ice bath, and 25% ammonia water was added dropwise while stirring to adjust the solution to ρ Η 8. The resulting titanium hydroxide precipitate was separated from the supernatant by centrifugation at 2,500 ° C for 15 minutes. The precipitate of the obtained titanium hydroxide was then washed 5 times with deionized water. After washing, spin and centrifuge at 2500 for 15 minutes to separate the solid and liquid phases. After washing, the titanium hydroxide was dried at 70 ° C, 10 Torr or less, and dried under reduced pressure for 18 hours to remove water to obtain a solid titanium compound. Before using the obtained solid titanium compound as a polycondensation catalyst, the paper size shall be in accordance with the Chinese National Standard (CNS) A4 (210 × 297 mm) ~ 1-118- 585881 A7 B7. 5. Description of the invention (116) 1 0 #m granular. According to the above-mentioned solid titanium compound, the adhesion moisture was measured with a Karl Fischer moisture meter. As a result, it was found that 6.33% by weight of moisture was contained. As a result of measuring weight loss by heating using thermogravimetry, it lost 7 · 50% by weight of the initial weight up to 280 ° C, and lost 2_17% by weight between 280 ° C and 600 t. Knowing the above weight loss It is caused by the separation of water and nitrogen compounds. The nitrogen content in the catalyst is 1.3% by weight, and the chlorine content is only 14 P P m. Therefore, it is known that the nitrogen is not derived from ammonium chloride, but is estimated to be derived from ammonia. The titanium content in the solid titanium compound obtained by a high-frequency plasma emission analysis device was 46% by weight. From the above, it can be seen that the molar ratio of titanium to hydroxide of the obtained solid titanium compound is 1: 0 · 1 5 7. In addition, nitrogen was analyzed by a trace total nitrogen analyzer (chemiluminescence method), and chlorine was analyzed by chromatographic methods, which were calculated by removing ammonia and hydrogen chloride, respectively. [Example 4 9 5 — 2] Preparation of solid titanium-containing compound in glass sintered glass of 1 0 0 0 J Weigh out 5 0 0 W of deionized water, add 0. 15 g of anhydrous magnesium hydroxide and add Scatter it. After cooling in an ice bath, 5 g of titanium tetrachloride was added dropwise while stirring. The solution became acidic and magnesium hydroxide was dissolved therein. After the generation of hydrogen chloride ceased, take out the ice bath, and add 2 5% ammonia water dropwise while stirring to adjust the solution to pH 8. The resulting titanium-containing composite hydroxide precipitate was separated by centrifugation at 2,500 for 15 minutes from the supernatant. Then, the paper size of the titanium-containing composite hydroxide obtained after deionized water washing is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page), τ Wisdom of the Ministry of Economic Affairs Printed by the Consumer Affairs Cooperative of the Property Bureau -119-585881 A 7 B7 V. Description of the invention (117) (Please read the precautions on the back before filling this page) Deposit 5 times. The solid-liquid phase separation after washing was performed by spinning at 2,500 for 15 minutes. After washing, the titanium-containing composite hydroxide was dried under reduced pressure at 70 ° C, 10 butyl rr for 18 hours to remove water, thereby obtaining a solid titanium-containing compound. The atomic ratio of titanium to magnesium of the solid titanium-containing compound is 91 mols of titanium atoms, and 9 mols of magnesium atoms. The obtained solid titanium-containing compound was measured by thermogravimetry to know that the titanium-to-hydroxide molar ratio was 1: 0.31. The solid titanium-containing compound is pulverized into a powder of about 10 m before being used as a condensation polymerization catalyst. [Example 4 9 5-3] Preparation of solid state titanium-containing compound: Printed by a consumer co-operative society of the Intellectual Property Office of the Ministry of Economic Affairs, printed in 1 0 0 0 4 and weighed 5 0 2 2 of deionized water. Add 0 16 g of colloidal silicon dioxide (trade name Snox OXS) and dispersed. After cooling in an ice bath, 5 g of titanium tetrachloride was added dropwise while stirring. The solution became acidic and the colloidal silica was dissolved therein. After the generation of hydrogen chloride ceased, it was taken out of the ice bath, and 25% ammonia water was added dropwise while stirring, and the solution was adjusted to P Η 8. The resulting titanium-containing composite hydroxide precipitate was separated from the supernatant by centrifugation at 2,500 ° C for 15 minutes. Then, the obtained titanium-containing composite hydroxide precipitate was washed 5 times with deionized water. After washing, the mixture was centrifuged at 2500 for 15 minutes to perform solid-liquid separation. After washing, the titanium-containing composite hydroxide was dried under reduced pressure at 70 t, 10 Torr I * r for 18 hours to remove water, and a solid titanium-containing compound was obtained. The atomic ratio of titanium to silicon in the solid titanium-containing compound is titanium atoms 94 mol. Applicable to China Paper Standard (CNS) A4 (210X: 297) for this paper size • 120- 585881 A7 B7 V. Description of the invention (118) (Please read the notes on the back before filling out this page) Sand atom 6 mol. The obtained solid titanium-containing compound was determined by thermogravimetric measurement, and the molar ratio of Chin to hydroxyl group was 1: 0.6. Before the solid titanium-containing compound is used as a polycondensation catalyst, it is pulverized into particles of about 10 ^ m. [Example 4 9 5-4] Production of polyester During routine operation, 3,500 parts by weight of the reaction solution can be retained in a reaction container. With stirring, nitrogen was maintained at 26 ° C and 0.9 kg / c m2 G, and high-purity terephthalic acid and 2 6 15 parts by weight / hour were continuously supplied from 6 4 5 8 parts by weight / hour. The ethylene glycol is mixed to prepare a slurry, and an esterification reaction is performed. In this esterification reaction, a mixed liquid of water and ethylene glycol is distilled off. The esterification reaction product (oligomer) is controlled to an average residence time of 3.5 hours, and is continuously extracted outside the reaction system. The number average molecular weight of the oligomers of the ethylene glycol and terephthalic acid obtained above is 60 to 1300 (3 to 5 polymers). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Using the solid titanium compound prepared in Example 4 9 5-1 as a condensation polymerization catalyst, the liquid phase condensation polymerization of the obtained low polymer was performed. The amount of catalyst added is calculated based on the titanium atom of the solid titanium compound. For the terephthalic acid unit in the low polymer, add 0.005 mol, and then at 2 8 ° C, 1 T 〇r I · The polycondensation reaction is performed under the conditions. The time required for the intrinsic viscosity (IV) of polyethylene terephthalate to reach 0.5 8 d 1 / g (that is, the liquid-phase polycondensation reaction time) is 9 5 This paper applies the Chinese National Standard (CNS) A4 Specifications (210X297 mm) -121-585881 A7 _____________B7 5. Description of the invention (彳 19) minutes. [Example 495-5] (Please read the precautions on the back before filling this page) In Example 4 9 5-4, the condensation polymerization catalyst was changed to use the solid titanium-containing compound prepared in Example 4 9 5-2 The rest of the compounds were subjected to polycondensation in the same manner as in Examples 4-9 5-4. The time required for the intrinsic viscosity (IV) of the polyethylene terephthalate to reach 0.58 d 1 / g (that is, the liquid phase condensation polymerization reaction time) was 76 minutes. [Example 4 9 5-6] In Example 4 9 5-4, the condensation polymerization catalyst was changed to the solid titanium-containing compound prepared in Example 4 9 5-3, and the rest were in accordance with Example 4 9 5- 4 The condensation polymerization reaction is carried out in the same manner. The time required for the inherent viscosity (TV) of the polyethylene terephthalate to reach 0.58 d 1 / g (liquid phase condensation polymerization reaction time) was 85 minutes. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Examples 4 9 5-7] In Example 4 9 5-4, the polycondensation catalyst was replaced with the solid titanium compound and magnesium carbonate prepared in Example 4 9 5-1 The rest of the compounds were subjected to condensation polymerization in the same manner as in Example 4 9 5-4. The amount of magnesium carbonate added was 0.005 mole% in terms of magnesium atoms in terms of terephthalic acid units in the low polymer. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -122- 8 8 5 8 5 A7 _________ B7 V. Description of the invention (12) Inherent viscosity of polyethylene terephthalate (IV ) The time required to reach 0.5 8 d 1 / g (that is, the liquid phase condensation polymerization reaction time) is 7 5 minutes (please read the precautions on the back before filling this page) minutes. [Example 4 9 5-8] In Example 4 9 5-4, the condensation polymerization catalyst was changed to the solid titanium compound prepared in Example 4 9 5-1 and magnesium acetate was added. The condensation polymerization was carried out in the same manner as shown in Example 4 9 5-4. The added amount of magnesium acetate is based on the terephthalic acid unit in the low polymer, and the magnesium atom is converted into 0.005 mole%. The time required for the intrinsic viscosity (IV) of the polyethylene terephthalate to reach 0.58 d 丨 / g (that is, the liquid phase condensation polymerization reaction time) was 70 minutes. [Example 4 9 5-9] In Example 4 9 5-4, the polycondensation catalyst was changed to Example 4 9 5 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-1 The solid titanium compound prepared was sealed in Except for the catalyst stored in the container for 2 months at room temperature, the rest were subjected to condensation polymerization in the same manner as in Example 4 9 5-4. The time required for the intrinsic viscosity (IV) of the polyethylene terephthalate to reach 0.58 d 1 / g (that is, the liquid phase condensation polymerization reaction time) was 101 minutes. From this example, it can be seen that the solid titanium compound according to the present invention does not deteriorate with time, and has good preservability. In addition, according to the special paper, this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ '-123 · 585881 A7 B7 V. Description of the invention (121) 4 7 ~ 2 6 5 9 7 The orthotitanic acid shown in the comparative example deteriorates with time and reduces the polycondensation activity. (Please read the precautions on the back before filling in this page} [Comparative Example 4 9 5 — 1] In Example 4 9 5 – 4, the antimony acetate commonly used in the industry was used as the condensation polymerization catalyst, and the rest are in accordance with Example 4 A condensation polymerization reaction was carried out in the same manner as shown in Example 9 5-4. The amount of antimony acetate added was 0.025 mol% of the antimony atom based on the terephthalic acid unit in the low polymer. Polyethylene terephthalate The time required for the intrinsic viscosity (IV) of the formate to reach 0.58 d 1 / g (that is, the liquid phase condensation polymerization reaction time) was 120 minutes. [Comparative Example 4 9 5-2] Preparation of titanium compound In Example 4 9 5-1, the titanium hydroxide washed with deionized water was boiled at 100 ° C for 2 hours and then dried to obtain a titanium compound. Polyester Manufacturing Intellectual Property Bureau D Shellman In Examples 4-9 5-4 printed by the Consumer Cooperative, the above-mentioned titanium compounds were used as condensation polymerization catalysts, and the rest were subjected to condensation polymerization according to the same method as shown in Examples 4-9 5-4. Polyethylene p-benzene The time required for the intrinsic viscosity (IV) of the diformate to reach 0.5 8 d 1 / g (ie liquid phase Polymerization reaction time) is 1 8 5 minutes. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) _ 124 _ " 585881 A 7 B7 122 V. Description of the invention () Titanium hydroxide is heated in water At this time, it is known that it will be converted into orthotitanic acid, so it can be seen that the polycondensation activity of titanium compounds obtained through orthotitanic acid is low. (Please read the precautions on the back before filling this page) [Example 4 9 6 — 7] At 100 ° C under normal pressure, 76.81 mol of high-purity terephthalic acid and 86.03 mol of ethylene glycol were supplied to the esterification reaction vessel, and then Example 495-2 was used. 0.045 mole of the solid titanium-containing compound prepared in the catalyst was added as a catalyst. Next, the reaction vessel was heated to 260 ° C, and the reaction was carried out at a pressure of 1.7 kg / cnfG under nitrogen. 3 4 0 Minutes. The water produced in this reaction is often managed to distill out of the reaction system. Then, the total amount in the esterification reaction vessel is moved to a condensation polymerization reaction vessel that has been heated to 250 ° C in advance, and then it is normally 6.44 mol of ethyl tributyl phosphate dissolved in 0.0073 mol Alcohol was added to the above reaction vessel, and the temperature was raised from 260 ° C to 280 ° C in 60 minutes, and the pressure was reduced from atmospheric pressure to 2 T 〇r !. After the reaction was carried out in a condensation polymerization reaction vessel for 108 minutes, the reaction product was taken out of the reaction vessel in a filament shape, immersed in water and cooled, and cut into granules with a cutter to obtain polyethylene terephthalate. Acid ester. The intrinsic viscosity of this polyethylene terephthalate was 0.65 d I / g, and the titanium and magnesium contents were determined by atomic absorption analysis to be 2 p p m, 2 ppm, and the weight ratio of magnesium / titanium was 0.08. The polyethylene terephthalate obtained by the liquid phase polycondensation reaction was transferred to a solid phase polycondensation reaction tower, and i 7 in nitrogen. (: Lower crystallization treatment 2 small This paper size is applicable to China National Standard (CNS) A4 specifications (210X 297 mm) -125-585881

12 C A7 B7 五、發明説明（ 時之後，於2 1 0 °C下進行1 3小時之固相縮聚合反應’ 而得粒狀聚乙烯對苯二甲酸酯。該聚乙嫌對苯二甲酸酯之 固有粘度爲0 · 825d Ι/g。使用該聚乙烯對苯二甲 酸酯按照上述方法成型爲階梯式矩形成型物，測定其C處 之濁度爲1 7 · 8 %。 〔實施例496 — 8〜13 ’實施例496 — 2C〕 將觸媒和聚合反應條件按照表4 9 6 - 1所記載加以 變更之外，其他皆按照實施例4 9 6 - 7所示相同方法製 造聚乙烯對苯二甲酸酯。其結果示於表4 中 ---------— (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 126- 58588112 C A7 B7 V. Description of the invention (After this time, solid phase condensation polymerization was carried out at 2 10 ° C for 13 hours to obtain granular polyethylene terephthalate. The polyethylene was found to be terephthalic acid. The intrinsic viscosity of the formate was 0 · 825 d I / g. The polyethylene terephthalate was used to form a stepped rectangular shaped article according to the above method, and the turbidity at the C point was measured to be 17 · 8%. Examples 496 — 8 to 13 'Examples 496 — 2C] The catalyst and polymerization conditions were changed as described in Table 4 9 6-1, and the rest were manufactured by the same method as shown in Example 4 9 6-7 Polyethylene terephthalate. The results are shown in Table 4 ---------- (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 126- 585881

A B 五、發明説明（124) 經濟部智慈財/$局員工消費合作社印製 T — 9 6 1谳 濁度 (%) VO 13.7 22.4 13.7 < 固相聚合 IV (dl/g) 0.816 0.803 0.843 0.820 0.814 0.807 0.834 時間 (小時） 23.0 10.0 17.0 C^3 >* i 21.0 26.0 液相聚合 IV (dl/g) 0.643 0.657 0.660 0.651 0.644 0.665 0.653 時間 (小時） 2.62 0.93 S t Η 1.70 2.53 csj ψ H f i 3.63 殘留量 (ppm) 1 ν〇 CN cn On υη 1 Φ m I I添加量*3 (莫耳％) 1 0.020 0.020 0.020 0.020 0.020 1 m 種類 1 Mg(〇Ac)2 Mg(〇Ac)2 Mg(〇Ac)2 Ca(〇Ac)2 Zn(〇Ac)2 1 縮聚合觸媒（I ) 殘留量*4 (ppm) CN m wn CsJ ON CS) 添加量*3 (莫耳％) 0.013 0.013 0.013 0.013 0.013 0.013 0.013 種類 .丨i Csl CNl Csl CN CNl CN 實施例496-8 實施例496-9 實施例496-10 實施例496-11 實施例496-12 實施例496-13 實施例496-2C 。篇MN]:^vo)uz · &1SNJ:^νο)ΰ，纖鍫亡<〇)窆褂丑擗邻屮幽_領忉龌饀0-71龄諒褰^嵌4<1^^菽：寸* 鬆仞安尨¥tr驗画绷懿麽旮T—IILO6寸匡辑« ^ I ^ ^ - Γ ----------- (請先閱讀背面之注意事項再填寫本頁)AB 5. Description of the invention (124) Printed by the Intellectual Property Department of the Ministry of Economic Affairs / $ Bureau Consumer Cooperative Cooperative T — 9 6 1 谳 Turbidity (%) VO 13.7 22.4 13.7 < Solid Phase Polymerization IV (dl / g) 0.816 0.803 0.843 0.820 0.814 0.807 0.834 Time (hours) 23.0 10.0 17.0 C ^ 3 > * i 21.0 26.0 Liquid phase polymerization IV (dl / g) 0.643 0.657 0.660 0.651 0.644 0.665 0.653 Time (hours) 2.62 0.93 S t Η 1.70 2.53 csj ψ H fi 3.63 Residual amount (ppm) 1 ν〇CN cn On υη 1 Φ m II added amount * 3 (mole%) 1 0.020 0.020 0.020 0.020 0.020 1 m Type 1 Mg (〇Ac) 2 Mg (〇Ac) 2 Mg (〇Ac) 2 Ca (〇Ac) 2 Zn (〇Ac) 2 1 Polycondensation catalyst (I) Residual amount * 4 (ppm) CN m wn CsJ ON CS) Additive amount * 3 (mole%) 0.013 0.013 0.013 0.013 0.013 0.013 0.013 species.i Csl CNl Csl CN CNl CN Example 496-8 Example 496-9 Example 496-10 Example 496-11 Example 496-12 Example 496-13 Example 496-2C . Article MN]: ^ vo) uz · & 1SNJ: ^ νο) 鍫, the death of the fiber < 〇) 窆 ugly 擗 neighbour 屮 quietly _ collar 忉 龌 饀 0-71 ages 褰 4 4 & 1寸: inch * 仞 尨 ¥ tr inspection painting stretched 懿 T—IILO 6 inch compendium «^ I ^ ^-Γ ----------- (Please read the precautions on the back before filling (This page)

、1T 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-127 - 585881 A7 B7 五、發明説明（125) 〔比較例4 9 6 — 1〕 鈦化合物之調製 (請先閱讀背面之注意事項再填寫本頁) 實施例4 9 5 - 1中以去離子水洗淨後之鈦氫氧化物 在1 0 0 °C下煮沸2小時後乾燥而得鈦化合物。 聚酯之製造 實施例4 9 6 — 7中，改用上述鈦化合物做爲縮聚合 觸媒之外，其他皆按照實施例4 9 6 - 7所示相同方法進 行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度（IV)到達〇 · 6 5 d 1 / g所需時間（即液相縮聚合反應時間）爲2 6 3分 鐘。 鈦氫氧化物在水中加熱時，已知會轉變成原鈦酸，因 此’可知經由原鈦酸而得鈦化合物之縮聚合活性低。 又’所得聚乙烯對苯二甲酸酯之含鈦量爲2 5 p pm ’含鎂量爲1 6ppm，鎂/鈦比率（重量比率）爲 〇 · 64。又，該聚乙烯對苯二甲酸酯之含氯量爲 1 P P m以下。 經濟部智慧財產局員工消費合作社印製 〔實施例4 7 3 — 1〕 固態狀鈦化合物之調製 1 0 0 0 W之玻璃燒枉中秤取5 Ο Ο α之去離子水， 在冰浴中冷卻後攪拌下滴加5 g之四氯化鈦。氯化氫之產 生終結後從冰浴中取出，在室溫下攪拌中滴加2 5 %之氨 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）.128 585881 A7 B7 五、發明説明（126 ) 水，將溶液調整爲P Η 9。其中，室溫下攪拌中滴加1 5 %之乙酸水溶液，調整溶液爲Ρ Η 5。所產生之沈澱物藉 過濾而分離。該沈澱物以去離子水洗淨5次。洗淨後之固 液相分離同樣以過濾進行。洗淨後之鈦化合物在7 0 °C， 1 Ο T 〇 r r下減壓乾燥1 8小時而去除水分，獲得固態 狀鈦化合物。 所得固態狀鈦化合物做爲縮聚合觸媒使用之前，先粉 碎成爲1 0 # m程度之粒狀物。 按照上述所得固態狀鈦化合物，使用卡爾-費歇水分 計測定其附著水分結果知悉含有1 1 · 2 9重量％之水量 。又，據熱重量分析法測定6 0 0 t爲止之加熱失重量爲 1 3 . 6 5重量％。另一方面，測定該固態狀鈦化合物中 之含鈦量，含氮量，含氯量之結果，分別含有鈦爲4 3重 量％，含氮爲5 1〇ppm，含氯爲7 6 p pm。由上述 結果可知該固態狀鈦化合物中之鈦對氫氧基之莫耳比率爲 1 : 0 . 2 8。又，鈦係以原子吸光分析法測定之。氮以 微量總氮分析裝置（化學發光法）測定，氯藉層析法分析 ，然後分別以氨，氯化氫脫離而計算之。 〔實施例4 7 3 — 2〕 固態狀鈦化合物之調製 1 0 0 0 之玻璃燒枉中秤取5 0 0 之去離子水， 在冰浴中冷卻後攪拌下滴加5 g之四氯化鈦。氯化氫之產 生終止後自冰浴中取出，室溫下攪拌中滴加2 5 %之氨水 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -- (請先閱讀背面之注意事項再填寫本頁)、 1T This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) -127-585881 A7 B7 V. Description of the invention (125) [Comparative Example 4 9 6 — 1] Titanium compound preparation (please read the back first) (Notes on this page, please fill in this page again) In Example 4 9 5-1, the titanium hydroxide washed with deionized water was boiled at 100 ° C for 2 hours and then dried to obtain a titanium compound. Production of Polyester In Examples 4-9 6-7, the above titanium compound was used instead as the condensation polymerization catalyst, and the other methods were used for the condensation polymerization reaction in the same manner as shown in Examples 4-9 6-7. The time required for the intrinsic viscosity (IV) of the polyethylene terephthalate to reach 0.65 d 1 / g (that is, the liquid phase condensation polymerization reaction time) is 263 minutes. When the titanium hydroxide is heated in water, it is known to be converted into orthotitanic acid. Therefore, it is known that the condensation polymerization activity of the titanium compound obtained through orthotitanic acid is low. The titanium content of the obtained polyethylene terephthalate was 25 p pm. The magnesium content was 16 ppm, and the magnesium / titanium ratio (weight ratio) was 0.64. The chlorine content of the polyethylene terephthalate was 1 P P m or less. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 4 7 3 — 1] Preparation of solid titanium compounds in a glass sintered glass of 1 0 0 0 W Weigh 5 Ο Ο α deionized water in an ice bath After cooling, 5 g of titanium tetrachloride was added dropwise with stirring. After the end of the generation of hydrogen chloride, take it out of the ice bath, and add 25% ammonia dropwise while stirring at room temperature. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 128 585881 A7 B7 V. Description of the invention (126) Water, adjust the solution to P Η 9. Among them, a 15% aqueous acetic acid solution was added dropwise while stirring at room temperature, and the solution was adjusted to PΗ5. The resulting precipitate was separated by filtration. The precipitate was washed 5 times with deionized water. The solid-liquid phase separation after washing was also performed by filtration. After washing, the titanium compound was dried under reduced pressure at 70 ° C. for 10 hours for 18 hours to remove water, thereby obtaining a solid titanium compound. Before the obtained solid titanium compound is used as a condensation polymerization catalyst, it is pulverized into a granular material having a size of about 10 m. According to the solid titanium compound obtained as described above, the adhesion moisture was measured using a Karl Fischer moisture meter. As a result, it was found that the amount of water contained 1 · 29% by weight. In addition, the weight loss on heating up to 600 t was measured by thermogravimetric analysis to be 13.65 wt%. On the other hand, as a result of measuring the titanium content, nitrogen content, and chlorine content of the solid titanium compound, the titanium content was 43% by weight, the nitrogen content was 5 10 ppm, and the chlorine content was 7 6 p pm. . From the above results, it can be seen that the molar ratio of titanium to hydroxyl group in the solid titanium compound is 1: 0.28. The titanium system was measured by atomic absorption spectrometry. Nitrogen was measured by a trace total nitrogen analyzer (chemiluminescence method), chlorine was analyzed by chromatography, and then it was calculated using ammonia and hydrogen chloride respectively. [Example 4 7 3 — 2] Preparation of solid titanium compound in a glass sintering furnace of 10000 Weighing 5O0 of deionized water, cooling in an ice bath and adding 5 g of tetrachloride dropwise while stirring. titanium. After the generation of hydrogen chloride is terminated, remove it from the ice bath, and add 25% ammonia water dropwise while stirring at room temperature. This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm)-(Please read the precautions on the back first (Fill in this page again)

、1T 經濟部智慧財產局員工消費合作社印製 -129- 8 8 5 8 5 A7 ____B7 五、發明説明（127 ) (請先閱讀背面之注意事項再填寫本頁} ，調整溶液爲p Η 5。所生成之沈澱物藉過濾分離之。該 沈澱物用去離子水洗淨5次。洗淨後之固液相分離同樣使 用過濾而進行。洗淨後之鈦化合物在7 0 r，1〇 T 〇 r r下減壓乾燥1 8小時以去除水分，而得固態狀鈦 化合物。 所得固態狀鈦化合物做爲縮聚合觸媒使用之前，先粉 石午成爲1 0 // in左右之粒狀物。 按照實施例4 7 3 - 1所示相同方法，測定按照上述 方法所得固態狀鈦化合物之附著水分量，6 0 0 °C爲止之 加熱失重量，含鈦量，含氮量，含氯量。其結果由卡爾-費歇水分計所得含水量爲1 4 · 3 5重量％，6 0 〇 °C爲 止之加熱失重量爲1 6 · 8 2重量％，含鈦量爲4 0重量 %，含氮量爲9 5 0 p pm，含氯量爲5 4 p pm。由上 述結果可知該固態狀鈦化合物中之鈦對氫氧基之莫耳比率 爲 1 ·· 0 · 3 1。 〔實施例4 7 3 — 3〕 經濟部智慧財產局員工消費合作社印製 固態狀鈦化合物之調製 1 0 0 0 J之玻璃燒枉中秤取5 0 0 J之去離子水， 冰浴中冷卻後攪拌下滴加5 g之四氯化鈦。待氯化氫之產 生終止後自冰浴中取出，室溫下攪拌中滴加2 5 %之氨水 ，調整溶液爲P Η 3 . 5。所產生沈澱物以過濾分離。該 沈澱物用去離子水洗淨5次。洗淨後之固液相分離同樣以 過濾進行。洗淨後之鈦化合物在7 0 °C，1 Ο Τ 〇 r r下 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) -130- 585881 A7 B7 五、發明説明（128) 减壓乾燥1 8小時以去除水分，而得固態狀鈦化合物。 所得固態狀鈦化合物在做爲縮聚合觸媒使用之前，先 粉碎爲1 0 // m左右之粒狀物。 按照貫施例4 7 3 - 1所示相同方法，測定上述所得 固態狀欽化合物之附著水分量，6 〇 〇艺爲止之加熱失重 量’含鈦量’含氮量，含氯量。據卡爾一費歇水分計所測 得水分量爲1 2 . 24重量％ ’ 6 〇〇 °c爲止之失重量爲 14 · 36重量％ ’含鈦量爲4 1重量％，含氮量爲 1 50ppm ’含氯量爲26ppm。由上述結果可知該 固態狀鈦化合物中之駄對氣氧基之莫耳比率爲 1:0.27° 〔實施例4 7 3 - 4〕 固態狀鈦化合物之調製 1 0 0 0 mC之玻璃燒枉中坪取5 〇 〇 j之去離子水， 冰浴中冷卻後攪拌中滴加5 g之四氯化鈦。待氯化氫之產 生終止後自冰浴中取出，室溫下攪拌中滴加5 %之氫氧化 鈉水溶液’調整溶液爲p Η 5。所生成之沈澱物以過濾分 離之。該沈澱物用去離子水洗淨5次。洗淨後之固液相分 離同樣以過濾進行。洗淨後之鈦化合物在7 〇 °c，1 0 T 〇 r r下減壓乾燥1 8小時而去除水分，得固態狀鈦化 合物。 所得固態狀鈦化合物在做爲縮聚合觸媒使用之前，先 粉碎成爲1 0 // m左右之粒狀物。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ----------- (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T-129- 8 8 5 8 5 A7 ____B7 V. Description of the invention (127) (Please read the precautions on the back before filling this page}, and adjust the solution to p Η 5. The resulting precipitate was separated by filtration. The precipitate was washed 5 times with deionized water. The solid-liquid phase separation after washing was also performed using filtration. The titanium compound after washing was at 70 r, 10 T Dry under reduced pressure for 18 hours to remove water to obtain a solid titanium compound. Before the obtained solid titanium compound is used as a condensation polymerization catalyst, the powder stone is first turned into a granular material of about 10 // in. According to the same method shown in Example 4 7 3-1, the moisture content of the solid titanium compound obtained according to the above method was measured. The weight loss during heating up to 60 ° C, the titanium content, the nitrogen content, and the chlorine content were measured. As a result, the water content obtained by the Karl-Fisher moisture meter was 14 · 35% by weight, the heating loss weight up to 600 ° C was 16 · 8 2% by weight, and the titanium content was 40% by weight. The nitrogen content was 9 50 p pm and the chlorine content was 5 4 p pm. From the above results, the solid state The molar ratio of titanium to hydroxyl groups in titanium compounds is 1 ·· 0 · 3 1. [Example 4 7 3 — 3] Preparation of solid titanium compounds printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 1 0 0 5 0 J of deionized water was weighed in a 0 J glass burner. After cooling in an ice bath, 5 g of titanium tetrachloride was added dropwise with stirring. After the generation of hydrogen chloride was terminated, it was taken out of the ice bath at room temperature While stirring, 25% ammonia water was added dropwise to adjust the solution to PP3.5. The resulting precipitate was separated by filtration. The precipitate was washed 5 times with deionized water. The solid-liquid phase separation after washing was also filtered by After cleaning, the titanium compound is applied at 70 ° C, 10 Τ torr. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -130- 585881 A7 B7 V. Description of the invention (128) Dry under reduced pressure for 18 hours to remove water to obtain a solid titanium compound. Before using the obtained solid titanium compound as a condensation polymerization catalyst, pulverize it into particles of about 10 // m. According to the embodiment The same method as shown in 4 7 3-1 was used to determine the moisture content of the solid compound obtained above. Amount of heating, weight loss up to 600mm, titanium content, nitrogen content, chlorine content. According to Karl-Fisher moisture meter, the moisture content is 12.24% by weight '600 ° c The weight loss was 14.36% by weight 'The content of titanium was 41% by weight and the content of nitrogen was 150ppm' The content of chlorine was 26ppm. From the above results, it can be seen that the tritium to oxygen in the solid titanium compound Ear ratio is 1: 0.27 ° [Example 4 7 3-4] Preparation of solid titanium compound 1 000 mC glass sintered sintered plate Take 5,000 deionized water, cool in ice bath and stir 5 g of titanium tetrachloride was added dropwise. After the production of hydrogen chloride was terminated, it was taken out of the ice bath, and a 5% aqueous sodium hydroxide solution was added dropwise while stirring at room temperature to adjust the solution to pΗ5. The resulting precipitate was separated by filtration. The precipitate was washed 5 times with deionized water. The solid-liquid phase separation after washing was also performed by filtration. The washed titanium compound was dried under reduced pressure at 70 ° C and 10 Torr for 18 hours to remove water to obtain a solid titanium compound. Before the obtained solid titanium compound is used as a condensation polymerization catalyst, it is pulverized into a granular material of about 10 // m. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) ----------- (Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局8工消費合作社印製 -131 - 585881 A7 B7 五、發明説明（129 ) 按照實施例4 7 3 - 1所示相同方法，測定所得固態 狀鈦化合物之附著水分量’ 6 〇 〇 t爲止之加熱失重量， 金屬鈦，金屬鈉，含氯量。據卡爾一費歇水分計所測水分 量爲12 . 37重量％，600 t爲止之加熱失重量爲 10.12重量％’含鈦量爲4〇重量％，含氯量爲45 p p m。又，未檢出鈉之存在。由該結果可知該固態狀鈦 化合物中之駄對氣氧基之旲耳比率爲1:q 30。 〔實施例4 7 3 — 5〕 聚酯之製造 例行操作時可滯留3 3 5 0 〇重量份之反應液之反應 容器中’攪拌下，氮氣中，保持260。(：，0 · 9kg/ c ηί G之條件下，連續供應由混合6 4 5 8重量份/小時 之高純度之對苯二甲酸和2 6 1 5重量份/小時之乙二醇 所調製成之泥漿’進行酯化反應。該酯化反應中，蒸餾所 產生水和乙二醇之混合液而排除反應系外。 酯化反應產物（低聚合物）之平均滯留時間控制在 3 · 5小時下連續抽取到反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲600〜1 300 QC (3〜5聚物）。 使用實施例4 7 3 - 1所調製之固態狀鈦化合物和乙 酸鎂做爲縮聚合觸媒，將上述所得低聚合物進行液相縮聚 合反應。 觸媒添加量，對低聚合物中之對苯二甲酸單位計，以 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 -132- 585881 A7 B7 五、發明説明（13〇 ) 固態狀鈦化合物之鈦原子換算，使用0 . 0 1莫耳％，乙 酸鎂以鎂原子換算使用0 . 0 2莫耳％。 (請先閱讀背面之注意事項再填寫本頁) 縮聚合反應在2 8 0 °C，1 Ο T 〇 r r條件下進行。 其結果，聚乙烯對苯二甲酸酯之固有粘度到達0 . 6 5 d 1 / g爲止所需時間（即液相縮聚合反應時間）爲5 8 分鐘。 〔實施例4 7 3 - 6〕 實施例4 7 3 — 5中，改用實施例4 7 3 — 2中所調 製之固態狀鈦化合物爲縮聚合觸媒之外，其他皆按照實施 例4 7 3 - 5所示相同方法進行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度到達〇 . 6 5 d 1 / g爲止所需時間（即液相縮聚合反應時間）爲6 0分鐘。 〔實施例4 7 3 — 7〕 實施例4 7 3 - 5中，改用實施例4 7 3 — 3中所調 經濟部智慧財產局員工消費合作社印製 製之固態狀駄化合物爲縮聚合觸媒之外，其他皆按照實施 例4 7 3 - 5所示相同方法進行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度到達〇 · 6 5 d 1/ g爲止所需時間（即液相縮聚合反應時間）爲6 7分鐘。 〔實施例4 7 3 - 8〕 實施例4 7 3 - 5中’改用實施例4 7 3 — 4中所調 製之固態狀鈦化合物做爲縮聚合觸媒之外，其餘皆按照實 本度適用中國國家標準（CNS ) A4規格（2^10x297公楚) -133- 585881 A7 B7__ 五、發明説明（131) 施例4 7 3 — 5所示相同方法進行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度達到0 · 6 5 d 1/ (請先閱讀背面之注意事項再填寫本頁) g爲止所需時間（即液相縮聚合反應時間）爲6 5分鐘。 〔比較例4 7 3 — 1〕 實施例4 7 3 — 5中，改用工業上常用之乙酸銻做爲 縮聚合觸媒之外，其他皆按照實施例4 7 3 - 5所示相同 方法進行縮聚合反應。 乙酸銻之添加量對於低聚合物中之對苯二甲酸單位計 以銻原子換算使用0 · 〇 2 5莫耳％。 聚乙烯對苯二甲酸酯之固有粘度到達〇 · 6 5 d 1/ g爲止所需時間（即液相縮聚合反應時間）爲1 2 0分鐘 〇 〔實施例5 1 0 — 1〕 固態狀鈦化合物之調製 經濟部智慧財產局員工消費合作社印製 1 0 0 0 m£之玻璃燒枉中秤取5 0 0 m£之去離子水， 冰浴中冷卻後，攪拌中滴加5 g之四氯化鈦。該時之液溫 爲0〜5 °C。待氯化氫之產生終止後自冰浴中取出，攪拌 中滴加2 5 %之氨水，調整溶液爲ρ Ή 8。該時之液溫爲 0〜1 0 °C。所產生鈦氫氧化物之沈澱物在4 k g / c m2 壓力下以加壓過濾器過濾分離之。然後，所得鈦氫氧化物 之沈澱物以去離子水洗淨5次。洗淨後之固液相分離依照 上述在4 k g / c nf壓力下以加壓過濾器進行。洗淨後之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_巧34 585881 Μ Β7 五、發明説明（132) 鈦氫氧化物在7 0 °C，1 0 丁 〇 r r下減壓乾燥1 8小時 以去除水分而得固態狀鈦化合物。 (請先閱讀背面之注意事項再填寫本頁) 所得固態狀鈦化合物做爲縮聚合觸媒使用之前，先粉 碎爲5 0 左右之粒狀物。 分析該固態狀鈦化合物之結果，含鈦量爲4 0重量％ ，含氮量爲9 50ppm，含氯量爲54ppm，600 °C爲止之加熱失重爲1 6 . 8重量％，附著水分量爲 1 5 · 2 5重量％。由此計算之鈦和氫氧基比率（〇H/ T 1 )爲0 · 1 9 3。又，測定結晶化度之結果爲0 % ’ 即完全非晶狀。 又，實施例5 1 0 — 1 ，5 1 0 — 2，比較例5 1 0 —1 ，比較例5 1 0 - 2中其X光衍射強度以下列條件測 定之。 X 光·· C u K - Alpha l/50KV/300 mA 測角計：R I N T 2 0 0 0廣角測角計 附件：標準試料托架 濾鏡：無 經濟部智慧財產局員工消費合作社印製 計數單色光計：全自動單色光計 發散縫隙：1 / 2度 散光縫隙：1 / 2度 受光縫隙：0 · 1 5 m m 計器：閃爍計數器 掃描型：連續性 掃描速度：4 ° /分鐘 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）·，於 585881 A7 B7 五、發明説明（133) 掃描步驟：0 · 0 2 ° (請先閱讀背面之注意事項再填寫本頁) 掃描軸：2 θ / Θ 掃描範圍：1·5〜7〇° Θ偏差：0 ° 固定角：0 ° 聚酯之製造 例行操作時反應液可滯留3 3 5 0 0重量份之反應容 器中，攪拌下’氮氣中’ 26〇°C ’ 0 · 9kg/cm2G 之保持條件下，連續供應由6 4 5 8重量份/小時之高純 度對苯二甲酸和2 6 1 5重量份/小時之乙二醇所混合而 調製之泥漿，進行酯化反應。該酯化反應中，蒸餾排除所 產生水和乙二醇之混合液於反應系外。 酯化反應物（低聚合物）控制在平均滞留時間爲 3 · 5小時，並連續抽出反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲600〜1300(3〜5聚物）。 經濟部智慧財產局員工消費合作社印製 使用上述調製之固態狀鈦化合物和乙酸鎂做爲縮聚合 觸媒，就上述所得低聚合物進行縮聚合反應。 觸媒添加量以固態狀鈦化合物之鈦原子換算，對於低 聚合物中之對苯二甲酸單位計，使用〇 . 〇 1 〇 5莫耳％ ，乙酸鎂以鎂原子計，對低聚合物中之對苯二甲酸單位計 ，加入0 · 02 1莫耳％，再加上三丁基磷酸酯以磷原子 計，使用 0.0105 莫耳 ％，在 285 t：，ITorr -136- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 585881 A7 B7 五、發明説明（134) 之條件下進行縮聚合反應，而製得固有粘度爲0 . 6 5 d1/g之液相縮聚合反應產物之聚乙烯對苯二甲酸酯， 聚合所需時間爲6 5分鐘。 〔實施例5 1 0 - 2〕 固態狀鈦化合物之調製 實施例5 1 0 — 1中，改變乾燥溫度70°C爲1 0〇 °C之外，其他以相同方法製得固態狀鈦化合物。 所得固態狀鈦化合物在做爲縮聚合觸踝使用之前，先 粉碎爲5 0 //m左右之粒狀物。 分析該固態狀鈦化合物之結果，含鈦量爲4 3重量％ ’含氣星爲5 10ppm’含氯量爲7 6ppm，60〇 °C爲止之加熱失重爲1 3 · 6 5重量％，附著水分量爲 1 2 · 1 1重量％。由此計算而得氫氧基/鈦之比率爲 〇 · 1 8 2。又，測定結晶化度之結果爲7 %，可知稍爲 結晶化。 聚酯之製造 實施例5 1 0 — 1中，改用上述所調製之固態狀鈦化 合物之外，依照相同方法進行縮聚合反應，而製得固有粘 度爲0 · 6 5 d Ι/g之液相縮聚合反應產物之聚乙烯對 苯二甲酸酯，聚合時間爲6 8分鐘。 〔比較例5 1 0 - 1〕 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）· 137 -1. Printed by 8T Consumer Cooperative, 1T, Intellectual Property Bureau, Ministry of Economic Affairs -131-585881 A7 B7 5. Description of the Invention (129) According to the same method as shown in Example 4 7 3-1, determine the amount of water attached to the solid titanium compound Weight loss due to heating up to 600 t, metal titanium, metal sodium, chlorine content. The moisture content measured by Karl-Fisher moisture meter was 12.37% by weight, the heating loss weight up to 600 t was 10.12% by weight ', the titanium content was 40% by weight, and the chlorine content was 45 p pm. The presence of sodium was not detected. From this result, it was found that the ear-to-oxygen ear ratio in the solid titanium compound was 1: q 30. [Example 4 7 3-5] Production of polyester During a routine operation, 3,500 parts by weight of the reaction solution can be retained in a reaction vessel 'while being stirred, and maintained at 260 in nitrogen. (: Under the condition of 0 · 9kg / c η G, continuous supply is prepared by mixing 6 4 5 8 parts by weight of high-purity terephthalic acid and 2 6 1 5 parts by weight of ethylene glycol. The slurry 'undergoes an esterification reaction. In this esterification reaction, a mixed solution of water and ethylene glycol produced is distilled away from the reaction system. The average residence time of the esterification reaction product (oligomer) is controlled to 3.5 hours It was continuously extracted outside the reaction system. The number average molecular weight of the low polymer of ethylene glycol and terephthalic acid obtained above was 600 ~ 1 300 QC (3 ~ 5 polymer). It was prepared using Example 4 7 3-1 The solid titanium compound and magnesium acetate are used as condensation polymerization catalysts, and the low polymer obtained above is subjected to liquid phase condensation polymerization. The amount of catalyst added is based on the terephthalic acid unit of the low polymer and is applicable on the paper scale China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page), 11 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-132- 585881 A7 B7 V. Description of the invention (13 〇) Titanium precursor of solid titanium compound For sub conversion, use 0.01 mol%, and for magnesium acetate, use 0.02 mol% in terms of magnesium atoms. (Please read the precautions on the back before filling in this page.) The condensation polymerization reaction is at 28 ° C, As a result, the time required for the intrinsic viscosity of the polyethylene terephthalate to reach 0.65 d 1 / g (that is, the liquid phase condensation polymerization reaction time) was 58 minutes. [Example 4 7 3-6] In Example 4 7 3-5, the solid titanium compound prepared in Example 4 7 3-2 was used instead of the polycondensation catalyst. The others were in accordance with Example 4 7 The polycondensation reaction is carried out in the same manner as shown in 3-5. The time required for the intrinsic viscosity of the polyethylene terephthalate to reach 0.65 d 1 / g (that is, the liquid phase polycondensation reaction time) is 60 minutes. [Example 4 7 3-7] In Example 4 7 3-5, the solid rhenium compound printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs adjusted in Example 4 7 3-3 was used as the polycondensation catalyst. Except for the media, the others were subjected to polycondensation in the same manner as shown in Example 4 7 3-5. Polyethylene terephthalic acid The time required for the intrinsic viscosity to reach 0.65 d 1 / g (that is, the liquid phase condensation polymerization reaction time) is 67 minutes. [Example 4 7 3-8] In Example 4 7 3-5, it is used instead. Except for the solid titanium compound prepared in Example 4 7 3-4 as the condensation polymerization catalyst, the rest are in accordance with the actual national standard (CNS) A4 specification (2 ^ 10x297 Gongchu) -133- 585881 A7 B7__ 5. Description of the invention (131) The condensation polymerization reaction was carried out in the same manner as shown in Example 4 7 3-5. The inherent viscosity of polyethylene terephthalate reaches 0 · 6 5 d 1 / (Please read the precautions on the back before filling in this page) The time required up to g (ie liquid phase polymerization reaction time) is 6 5 minutes . [Comparative Example 4 7 3-1] In Example 4 7 3-5, the antimony acetate commonly used in the industry was used as the condensation polymerization catalyst, and the rest were performed in the same manner as shown in Example 4 7 3-5 Polycondensation. The amount of antimony acetate added to the terephthalic acid unit in the oligomer was 0. 0.25 mole% in terms of antimony atoms. The time required for the intrinsic viscosity of polyethylene terephthalate to reach 0.65 d 1 / g (ie, the liquid phase condensation polymerization reaction time) is 120 minutes. [Example 5 1 0 — 1] Solid state Modulation of titanium compounds Printed by a consumer co-operative society of the Intellectual Property Bureau of the Ministry of Economic Affairs at a cost of 10,000 m £. Weigh 50 m of deionized water in a glass burner. After cooling in an ice bath, add 5 g of Titanium tetrachloride. The liquid temperature at this time was 0 to 5 ° C. After the generation of hydrogen chloride is terminated, remove it from the ice bath, and add 25% ammonia water dropwise while stirring to adjust the solution to ρ Ή 8. The liquid temperature at this time is 0 ~ 10 ° C. The precipitate of the produced titanium hydroxide was separated by filtration under a pressure of 4 k g / cm 2 with a pressure filter. Then, the obtained titanium hydroxide precipitate was washed 5 times with deionized water. The solid-liquid phase separation after washing was performed as described above under a pressure of 4 k g / c nf with a pressure filter. The size of this paper after washing is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) _ Qiao 34 585881 Μ B7 V. Description of the invention (132) Titanium hydroxide at 70 ° C, 10 butyl rr It was dried under reduced pressure for 18 hours to remove water to obtain a solid titanium compound. (Please read the notes on the back before filling this page.) Before using the obtained solid titanium compound as a condensation polymerization catalyst, pulverize it to about 50 particles. As a result of analyzing the solid titanium compound, the titanium content was 40% by weight, the nitrogen content was 9 50ppm, the chlorine content was 54ppm, and the weight loss on heating up to 600 ° C was 16.8% by weight, and the amount of attached water was 1 5 · 2 5 wt%. The titanium-to-hydroxide ratio (OH / T 1) calculated from this was 0 · 193. The degree of crystallinity was measured and found to be 0% ', i.e. completely amorphous. In addition, the X-ray diffraction intensity in Examples 5 1 0-1, 5 1 0-2, Comparative Examples 5 1 0-1, and Comparative Examples 5 1 0-2 were measured under the following conditions. X-ray · · Cu K-Alpha l / 50KV / 300 mA goniometer: RINT 2 0 0 0 wide-angle goniometer accessory: standard sample holder filter: no counting sheet printed by the staff consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Color light meter: Full-automatic monochromatic light meter Divergence gap: 1/2 degree Astigmatism gap: 1/2 degree Light receiving gap: 0 · 1 5 mm Gauge: Flicker counter Scanning type: Continuous scanning speed: 4 ° / minute This paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm), in 585881 A7 B7 V. Description of the invention (133) Scanning steps: 0 · 0 2 ° (Please read the precautions on the back before filling this page) Scan Axis: 2 θ / Θ Scanning range: 1.5 to 70 ° Θ Deviation: 0 ° Fixed angle: 0 ° The reaction solution can stay in the reaction container of 3 3 5 0 0 parts by weight during the routine operation of polyester manufacturing. Under stirring conditions of 'in nitrogen' at 26 ° C '0 · 9kg / cm2G, continuous supply of high purity terephthalic acid from 6 4 5 8 parts by weight per hour and 2 6 15 parts by weight per hour The slurry prepared by mixing the diols undergoes an esterification reaction. In this esterification reaction, a mixed solution of water and ethylene glycol produced is removed from the reaction system by distillation. The esterification reactant (oligomer) is controlled to an average residence time of 3.5 hours, and continuously withdrawn from the reaction system. The number average molecular weight of the oligomers of ethylene glycol and terephthalic acid obtained above is 600 to 1300 (3 to 5 polymers). Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Use the solid titanium compound and magnesium acetate prepared as the condensation polymerization catalyst to perform the condensation polymerization reaction on the obtained low polymer. The addition amount of the catalyst is calculated based on the titanium atom of the solid titanium compound. For the terephthalic acid unit in the low polymer, 0.01 mol% is used. For magnesium acetate, the magnesium atom is used for the low polymer. In terms of terephthalic acid units, add 0. 02 1 mol%, plus tributyl phosphate based on phosphorus atoms, use 0.0105 mol%, at 285 t :, ITorr -136- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 585881 A7 B7 V. Condensation polymerization reaction under the conditions of the invention (134) to obtain a liquid phase condensation polymerization reaction product with an inherent viscosity of 0.6 5 d1 / g For polyethylene terephthalate, the time required for polymerization is 65 minutes. [Example 5 1 0-2] Preparation of solid titanium compound In Example 5 0-1, except that the drying temperature was changed from 70 ° C to 100 ° C, a solid titanium compound was prepared in the same manner. Before the obtained solid titanium compound is used as a polycondensation ankle, it is pulverized into granules of about 50m. As a result of analyzing the solid titanium compound, the titanium content was 43% by weight. The gas content was 5 10ppm. The chlorine content was 76 ppm. The weight loss on heating up to 60 ° C was 1 36.5% by weight. The moisture content was 1 2 · 11 1% by weight. From this calculation, the ratio of hydroxyl group / titanium was 0.182. It was found that the degree of crystallization was 7%, and it was found that there was a slight crystallization. In Production Example 5 of Polyester 5-10, instead of using the solid titanium compound prepared above, polycondensation was carried out according to the same method to obtain a liquid with an inherent viscosity of 0.65 d Ι / g The polymerization time of the polyethylene terephthalate of the condensation polymerization reaction is 68 minutes. [Comparative Example 5 1 0-1] This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) · 137-

---------- (請先閲讀背面之注意事項再填寫本頁J -訂- |丨 經濟部智慈財產局員工消費合作社印製 585881 A7 B7 五、發明説明（135> 固態狀鈦化合物之調製 (請先閱讀背面之注意事項再填寫本頁) 1 0 0 0 之玻璃燒枉中秤取5 0 0 m£之去離子水， 攪拌下滴加5 g之四氯化鈦。該時之液溫爲約2 5 t。待 氯化氫終止產生後，保持液溫在8 0 °C，攪拌下滴加2 5 %之氨水，調整溶液爲p Η 8。所生成之鈦氫氧化物之沈 澱物在4 k g / c m2之壓力下以加壓過濾器過濾分離。然 後，所得鈦氫氧化物之沈澱物用去離子水洗淨5次。洗淨 後之固液相分離依照上述同樣以4 k g/c m2之壓力下進 行加壓過濾。洗淨後之鈦氫氧化物在7 0 °C，1 0 T ◦ r I·下減壓乾燥以去除水分，而得固態狀鈦化合物。 所得固態狀鈦化合物在做爲縮聚合觸媒使用之前，先 粉碎成爲5 0 //m左右之粒狀物。 分析該固態狀鈦化合物之結果，含鈦量爲5 0重量％ ，含氮量爲5 30ppm，含氯量爲41ppm，600 °C爲止之加熱失重爲1 6 . 6 3重量％，附著水分量爲 14·68重量％。由此計算之氫氧基/鈦比率爲 〇 · 2 0 0。又’測定結晶化度之結果爲6 4 %，可知相 當結晶化。 經濟部智慧財產局員工消費合作社印製 聚酯之製造 實施例5 1 0 - 1中，改用上述所調製之固態狀鈦化 合物之外’按照相同方法進行縮聚合反應。使用2 4 0分 鐘尙無法使固有粘度到達〇 · 6 5 d 1 / g。 -138- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 585881 A7 B7 五、發明説明（13’ 〔比較例5 1 0 - 2〕 固態狀鈦化合物之調製 (請先閱讀背面之注意事項再填寫本頁) 1 0 0 0 m£之玻璃燒枉中秤取5 0 0 之去離子水， 保持在6 0 °C下’攪拌中滴加5 g之四氯化鈦。待氯化氫 終止產生後，保持液溫於8 0 °C，攪拌中滴加2 5 %之氨 水，調整溶液爲P Η 8。所產生之鈦氫氧化物之沈澱物在 4 k g / c m2之壓力下以加壓過濾器過濾分離之。然後， 所得鈦氫氧化物之沈澱物以去離子水洗淨5次。洗淨後之 固液相分離依照上述相同以4 k g / c m2之壓力下進行加 壓過濾。洗淨後之鈦氫氧化物在1 0 0 °C，1 Ο Τ ο I· I* 下減壓乾燥1 8小時以去除水分而得固態狀鈦化合物。 所得固態狀鈦化合物做爲縮聚合觸媒使用之前，先粉 碎爲5 0 //m左右之粒狀物。 經濟部智慧財產局員工消費合作社印製 分析該固態狀鈦化合物之結果，含鈦量爲4 7重量％ ，含氮量爲840ppm，含氯量爲1050ppm， 600 °C爲止之加熱失重爲15 · 95重量％，附著水分 量爲1 3 · 6 2重量％。由此計算之氫氧基/鈦比率爲 0 · 2 4 0。又，測定結晶化度之結果爲7 1 %，可知相 當結晶化。 聚酯之製造 實施例5 1 0 — 1中，改用上述調製之固態狀鈦化合 物之外’皆按照同樣方法進行縮聚合反應，使用2 4 0分 鐘尙無法縮聚合成爲固有粘度〇 · 6 5 d Ι/g之縮聚合 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ297公釐） 8 A7 _ B7 _ 五、發明説明（13乃 物。 (請先閱讀背面之注意事項再填寫本頁) 〔實施例4 9 8 - 1〕 含鈦水解產物之調製 1 0 0 0 之玻璃燒枉中秤取5 0 0 之去離子水， 在冰浴中冷卻後，攪拌下滴加5 g之四氯化鈦。待氯化氫 終止產生後自冰浴中取出，攪拌下滴加2 5 %之氨水，調 整溶液爲P Η 8。所產生鈦氫氧化物之沈澱物在3 k g / c m2壓力下以加壓過濾器過濾分離之。然後，所得鈦氫氧 化物之沈澱物用去離子水洗淨5次。洗淨後之固液相分離 按照上述相同以3 k g / c m2壓力進行加壓過濾。洗淨後 之鈦氫氧化物在7 0 °C，1 Ο T 〇 r r下減壓乾燥1 8小 時以去除水分，而得固態狀鈦化合物。 所得固態狀鈦化合物做爲縮聚合觸媒使用之前，先粉 碎爲10 左右之粒狀物。 聚酯製造用觸媒之調製 經濟部智慧財產局員工消費合作社印製 將上述含鈦水解產物10g，乙二醇65g和25g 之四乙銨氫氧化物之混合物在1 9 0 °C下加熱3小時而製 得聚酯製造用觸媒。 聚酯之製造 例行操作時反應液可滯留3 3 5 0 0重量份之反應容 器中，連續供應由混合高純度對苯二甲酸和乙二醇而調製 ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^ -140- 585881 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（138) 之泥漿，攪拌下，氮氣中，260 t，0 · 9kg/ c πί G之條件下，進行酯化反應。上述高純度對苯二甲酸 和乙二醇之泥漿乃係按照高純度對苯二甲酸爲6 4 5 8重 量份/小時，乙二醇爲2 6 1 5重量份/小時之混合比率 而調製之。 酯化反應中，蒸餾去除所產生水和乙二醇之混合液於 反應系外。酯化反應產物（低聚合物）控制在平均滯留時 間爲3 · 5小時，連續抽出到反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲600〜1300 (3〜5聚物）。 按照上述所得低聚合物中，對於低聚合物中之對苯二 甲酸單位1莫耳計，添加鈦原子換算0 · 〇 2 1莫耳％之 上述聚酯製造用觸媒，在285 °C，1 Tori·之條件下 進行液相縮聚合反應。聚乙烯對苯二甲酸酯之固有粘度到 達0 · 65d Ι/g爲止所需時間爲57分鐘。 〔實施例4 9 8 - 1 C〕 代替聚酯製造用觸媒，使用含鈦水解產物，對於低聚 合物中之對苯二甲酸單位1莫耳計，依照以鈦原子換算爲 0 · 0 2 1莫耳％量之外，其他皆按照實施例4 9 8 — 1 所示相同方法進行縮聚合反應。聚乙烯對苯二甲酸酯之固 有粘度到達0 · 6 5 d 1 / g爲止所需時間爲3小時5 5 分鐘。又，該聚乙烯對苯二甲酸酯中之乙醛含量爲5 2 ppm。 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -141 - 585881 A7 B7____ 五、發明説明（1叫 〔比較例4 9 8 - 2〕 (請先閲讀背面之注意事項再填寫本頁) 縮聚合觸媒（1 )之調製 將上述含鈦水解產物1 0 g ，乙二醇6 5 g和乙酸2 5 g之混合物在1 9 0 °C下加熱3小時而得縮聚合觸媒（ 1 ) ° 聚酯之製造 代替聚酯製造用觸媒，再改用上述縮聚合觸媒（1 ) ，對於低聚合物中之對苯二甲酸單位1莫耳計，鈦原子換 算爲0 · 0 2 1莫耳％量使用之外，其他皆按照實施例 4 9 8 — 1所示相同方法進行縮聚合反應。聚乙烯對苯二 甲酸酯之固有粘度到達〇 . 6 5 d Ι/g爲止所需時間爲 1 4 6分鐘。又，該聚乙烯對苯二甲酸酯中之乙醛含量爲 5 8 p p m 〇 〔比較例4 9 8 - 3〕 縮聚合觸媒（2)之調製 經濟部智慧財產局員工消費合作社印製 將上述含鈦水解產物1 0 g和乙二醇9 0 g之混合物 在1 9 0 °C下加熱3小時而得縮聚合觸媒（2 )。 聚酯之製造 代替聚酯製造用觸媒，使用上述縮聚合觸媒（2 ) ’ 對於低聚合物中之對苯二甲酸單位1莫耳，以鈦原子換算 -142- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 585881 A7 B7 經濟部智慈財產局員工消費合作社印製 五、發明説明（14C) 爲0 · 0 2 1莫耳％量使用之外，其他皆按照實施例 4 9 8 — 1所示相同方法進行縮聚合反應。聚乙烯對苯二 甲酸酯之固有粘度到達〇 · 6 5 d Ι/g爲止所需時間爲 1小時又5 0分鐘。 〔實施例5 0 1 — 1〕 固態狀鈦化合物之調製 1 0 0 〇m£之玻璃燒枉中秤取5 0 Om£之去離子水， 在冰浴中冷卻後，攪拌下滴加5 g之四氯化鈦。待氯化氫 之產生終了後自冰浴中取出，攪拌下滴加2 5 %之氨水， 調整溶液爲P Η 8。所產生鈦氫氧化物之沈澱物在3 k g / c m2壓力下以加壓過濾器過濾分離之。然後，所得鈦氫 氧化物之沈澱物用去離子水洗淨5次。洗淨後之固液相分 離按照上述相同以3 k g / c m2壓力下進行加壓過濾。洗 淨後之鈦氫氧化物在7 0 °C，1 Ο T 〇 r r下減壓乾燥 1 8小時以去除水分，而得固態狀鈦化合物。 所得固態狀含鈦化合物在使用前，粉碎成爲1 0 // m 左右之粒狀物。 聚酯之製造 例行操作時，反應液可滯留3 3 5 0 0重量份之反應 容器中，連續供應由混合高純度對苯二甲酸和乙二醇而調 製成之泥漿，在攪拌下，氮氣中，26 0 °C，0 · 9kg / c m2 G之條件下進行酯化反應。上述高純度對苯二甲酸 (請先閱讀背面之注意事項再填寫本頁) •會·---------- (Please read the notes on the back before filling in this page J-Order- | 丨 Printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 585881 A7 B7 V. Description of the invention (135 > solid Of titanium compound (please read the precautions on the back before filling in this page) In a glass sintering furnace of 1 0 0 0, weigh 5 000 m of deionized water and add 5 g of titanium tetrachloride dropwise while stirring. The liquid temperature at this time was about 2 5 t. After the hydrogen chloride was terminated, the liquid temperature was maintained at 80 ° C, and 25% ammonia water was added dropwise under stirring to adjust the solution to p Η 8. The titanium hydroxide produced The precipitate of the product was filtered and separated by a pressure filter under a pressure of 4 kg / c m2. Then, the obtained precipitate of the titanium hydroxide was washed 5 times with deionized water. The solid-liquid phase separation after washing was in accordance with the above Similarly, pressure filtration was performed at a pressure of 4 kg / c m2. The washed titanium hydroxide was dried under reduced pressure at 70 ° C, 10 T ◦ r I · to remove water to obtain a solid titanium compound. Before the obtained solid titanium compound is used as a condensation polymerization catalyst, it is pulverized into particles of about 50 // m. Analysis of the solid state As a result of the compound, the titanium content was 50% by weight, the nitrogen content was 5 30ppm, the chlorine content was 41ppm, and the weight loss on heating up to 600 ° C was 16.63% by weight, and the moisture content attached was 14.68% by weight. %. The hydroxyl / titanium ratio calculated from this is 0.20 0. The result of measuring the degree of crystallinity is 64%, which shows that it is quite crystallized. In Production Example 5 1-0, a condensation polymerization reaction was performed in the same manner as the solid titanium compound prepared above except that the condensation polymerization reaction was performed in the same manner. It was not possible to achieve an intrinsic viscosity of 0.65 d 1 / g after 240 minutes. -138- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 585881 A7 B7 V. Description of the invention (13 '[Comparative Example 5 1 0-2] Preparation of solid titanium compound (please read first Note on the back, please fill in this page again.) Weigh 500 g of deionized water in a glass sintered pot of 1000 m £ and keep it at 60 ° C. Add 5 g of titanium tetrachloride dropwise while stirring. After the generation of hydrogen chloride ceases, keep the liquid temperature at 80 ° C, and add 25% ammonia water dropwise while stirring. The whole solution was P Η 8. The precipitate of the titanium hydroxide produced was filtered and separated under a pressure of 4 kg / c m2 by a pressure filter. Then, the precipitate of the obtained titanium hydroxide was washed with deionized water. Clean 5 times. The solid-liquid phase separation after washing was carried out under the same pressure and pressure filtration at 4 kg / c m2. The titanium hydroxide after washing was at 100 ° C, 1 〇 Τ ο I · It was dried under reduced pressure at I * for 18 hours to remove water to obtain a solid titanium compound. Before the obtained solid titanium compound is used as a condensation polymerization catalyst, it is first pulverized into particles of about 50m. The results of printing and analysis of the solid titanium compound by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs showed that the titanium content was 47% by weight, the nitrogen content was 840ppm, the chlorine content was 1050ppm, and the heating weight loss up to 600 ° C was 15 · 95% by weight, and the adhesion moisture content was 1 3 · 62 2% by weight. The hydroxide / titanium ratio calculated from this was 0 · 2 4 0. The degree of crystallinity was measured and found to be 71%. In Production Example 5 of Polyester 5-10, the polycondensation reaction was performed in the same manner except for the solid titanium compound prepared as described above, and the polycondensation could not be reduced to an inherent viscosity of 0.65 after 2 to 40 minutes. d Ι / g shrinkage This paper is in accordance with the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) 8 A7 _ B7 _ V. Description of the invention (13 is the thing. (Please read the precautions on the back before filling (This page) [Example 4 9 8-1] Weigh 50 g of deionized water in a glass sintered glass made of 1 00 0 with titanium-containing hydrolysate. After cooling in an ice bath, add 5 g dropwise with stirring. Titanium tetrachloride. After the hydrogen chloride ceases to be produced, remove it from the ice bath, add 25% ammonia water dropwise while stirring, and adjust the solution to P Η 8. The precipitate of titanium hydroxide produced is at a pressure of 3 kg / c m2 Then, it was separated by filtration with a pressure filter. Then, the precipitate of the obtained titanium hydroxide was washed 5 times with deionized water. The solid-liquid phase separation after washing was pressurized at a pressure of 3 kg / c m2 in the same manner as above. Filtration. The washed titanium hydroxide was dried under reduced pressure at 70 ° C and 10 〇 〇rr. 18 hours to remove moisture to obtain a solid titanium compound. Before using the obtained solid titanium compound as a polycondensation catalyst, pulverize it into particles of about 10. The polyester industry catalyst is a smart property of the Ministry of Economic Affairs The bureau ’s consumer cooperative prints a mixture of 10 g of the titanium-containing hydrolysate, 65 g of ethylene glycol, and 25 g of tetraethylammonium hydroxide at 19 ° C for 3 hours to prepare a catalyst for polyester manufacturing. During the routine operation of ester production, the reaction solution can be retained in 3,500 parts by weight of the reaction container, and the continuous supply is prepared by mixing high-purity terephthalic acid and ethylene glycol. ^ Paper size applies Chinese National Standard (CNS) A4 Specifications (210X297 mm) ^ -140- 585881 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Note (138) The slurry, under stirring, in nitrogen, 260 t, 0 · 9kg / c πί G 之Under the conditions, the esterification reaction is performed. The above-mentioned slurry of high-purity terephthalic acid and ethylene glycol is based on high-purity terephthalic acid at 6 4 5 8 parts by weight / hour, and ethylene glycol is 2 6 1 5 parts by weight / Hour mixing ratio In the esterification reaction, the mixture of water and ethylene glycol produced is distilled out of the reaction system. The esterification reaction product (oligomer) is controlled to an average residence time of 3.5 hours, and is continuously extracted outside the reaction system. The number average molecular weight of the low polymer of ethylene glycol and terephthalic acid obtained above is 600 to 1300 (3 to 5 polymers). Among the low polymers obtained as described above, the terephthalic acid unit in the low polymer is 1 mole. The above-mentioned catalyst for polyester production was added to the ear meter in an amount of 0 · 〇2 to 1 mol% based on titanium atom, and a liquid phase condensation polymerization reaction was performed at 285 ° C and 1 Tori. The time required for the intrinsic viscosity of polyethylene terephthalate to reach 0.665 d I / g was 57 minutes. [Example 4 9 8-1 C] Instead of the catalyst for polyester production, a titanium-containing hydrolysate was used, and the terephthalic acid unit in the low polymer was measured in terms of 1 mol, and the titanium atom was converted to 0 · 0 2 With the exception of 1 mole%, the polycondensation reaction was carried out in the same manner as shown in Example 4 9 8-1. The time required for the intrinsic viscosity of polyethylene terephthalate to reach 0 · 6 5 d 1 / g is 3 hours 5 5 minutes. The acetaldehyde content in the polyethylene terephthalate was 5 2 ppm. (Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -141-585881 A7 B7____ 5. Description of the invention (1 called [Comparative Example 4 9 8- 2] (Please read the precautions on the back before filling this page) Preparation of condensation polymerization catalyst (1) The mixture of the above-mentioned titanium-containing hydrolysate 10 g, ethylene glycol 6 5 g and acetic acid 25 g is mixed in 19 Polycondensation catalyst (1) obtained by heating at 0 ° C for 3 hours ° Polyester production is replaced by polyester production catalyst, and the above polycondensation catalyst (1) is used instead. Formic acid unit 1 mole meter, titanium atom is converted to 0 · 0 2 1 mole%, except for the use, the other polycondensation reaction was carried out according to the same method shown in Example 4 9 8-1. Polyethylene terephthalic acid The time required for the intrinsic viscosity of the ester to reach 0.65 d Ι / g was 146 minutes. The acetaldehyde content in the polyethylene terephthalate was 5 8 ppm. [Comparative Example 4 9 8 -3] Polycondensation catalyst (2) Modified by the Intellectual Property Bureau of the Ministry of Economic Affairs, and printed by the Consumer Cooperatives to hydrolyze the above titanium A mixture of 10 g of ethylene and 90 g of ethylene glycol was heated at 190 ° C for 3 hours to obtain a polycondensation catalyst (2). Polyester production Instead of the polyester production catalyst, the above polycondensation catalyst was used. Medium (2) 'For 1 mol of terephthalic acid unit in low polymer, converted to titanium atom -142- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 585881 A7 B7 Ministry of Economic Affairs Printed by the Consumer Goods Cooperative of the Citizenship and Welfare Bureau 5. The invention description (14C) is 0 · 0 2 1 mol% except for the use of the amount, the other polycondensation reaction was carried out according to the same method shown in Example 4 9 8-1. Polyethylene The time required for the intrinsic viscosity of the terephthalate to reach 0.65 d Ι / g was 1 hour and 50 minutes. [Example 5 0 1 — 1] Preparation of solid titanium compound 1 0 0 0m Weigh 50 Om of deionized water in a glass burner, and after cooling in an ice bath, add 5 g of titanium tetrachloride dropwise with stirring. After the generation of hydrogen chloride is finished, remove it from the ice bath and stir. Add 25% ammonia water dropwise to adjust the solution to P Η 8. The precipitate of titanium hydroxide produced is at 3 kg / c m2 It was filtered and separated by a pressure filter under pressure. Then, the precipitate of the obtained titanium hydroxide was washed 5 times with deionized water. The solid-liquid phase separation after washing was performed under the same pressure at a pressure of 3 kg / c m2. It was filtered under pressure. The washed titanium hydroxide was dried under reduced pressure at 70 ° C. and 10 Torr for 18 hours to remove water to obtain a solid titanium compound. Before use, the obtained solid titanium-containing compound was pulverized into granules of about 10 // m. During the routine operation of polyester production, the reaction solution can be retained in a reaction container of 3,500 parts by weight, and a slurry prepared by mixing high-purity terephthalic acid and ethylene glycol can be continuously supplied. Under stirring, nitrogen The esterification reaction was carried out under the conditions of 26 0 ° C and 0 · 9 kg / c m2 G. The above high-purity terephthalic acid (Please read the notes on the back before filling out this page) • Yes ·

、1T •丨 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公羡）· 143 · 585881 A7 B7 五、發明説明（141) 和乙二醇之泥漿係按照高純度對苯二甲酸和乙二醇分別以 6 4 5 8重量份/小時和2 6 1 5重量份/小時之比率混 合而調製之。 (請先閲讀背面之注意事項再填寫本頁) 酯化反應中’蒸餾去除水和乙二醇之混合液於反應系 外。酯化反應產物（低聚合物）控制在平均滯留時間爲 3 . 5小時而連續抽出反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲60〇〜1300 (3〜5聚物）。 按照上述所得低聚合物中，添加上述固態狀含鈦化合 物，以該低聚合物中之對苯二甲酸單位計，按照鈦原子換 算爲0 · 0 2 1莫耳％量，另添加磷酸氫鎂以低聚合物中 之對苯二甲酸單位計，按照鎂原子換算爲〇 · 〇 2 1莫耳 %量，又添加磷酸以磷原子換算爲〇 · 〇 1 〇 5莫耳％量 ’然後在2 8 5 °C，1 T 〇 r r之條件下進行液相縮聚合 反應，聚乙烯對苯二甲酸酯之固有粘度到達〇 · 6 5 d 1 /g爲止所需時間爲5 7分鐘，所得聚乙烯對苯二甲酸酯 之乙醛含量爲60ppm。 經濟部智慧財產局員工消費合作社印製 〔實施例5 0 1 — 2〕 代替磷酸氫鎂，改用二磷酸三鎂之外，其他皆按照實 施例5 0 1 — 1所示相同方法進行縮聚合反應。聚乙烯對 苯二甲酸酯之固有粘度到達〇 · 6 5 d 1 /g爲止所需時 間爲6 7分鐘，所得聚乙烯對苯二甲酸酯中之乙醛含量爲 5 7 p p m 〇 -144- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公楚） 585881 A7 B7 五、發明説明（143 〔實施例5 0 1 — 1 C〕 (請先閱讀背面之注意事項再填寫本頁) 代替磷酸氫鎂，改用乙酸鎂之外’其他皆按照實施例 5 0 1 — 1所示相同方法進行縮聚合反應。聚乙燒對苯二 甲酸酯之固有粘度到達0 · 6 5 d 1 / g爲止所需時間爲 1〇0分鐘，所得聚乙烯對苯二甲酸酯中之乙酵含量爲 7 0 p p m 〇 〔實施例4 9 7 — 1〕 固態狀含鈦化合物之調製 經濟部智慧財產局員工消費合作社印製 1 0 0 0 之玻璃燒枉中秤取5 0 0 4之去離子水， 在冰浴中冷卻之後，攪拌下滴加5 g之四氯化鈦。待氯化 氫之產生終止後自冰浴中取出，攪拌下滴加2 5 %之氨水 ，調整溶液爲P Η 8。所產生之鈦氫氧化物之沈澱物在3 k g / c m2之壓力下以加壓過濾器過濾分離之。然後，所 得鈦氫氧化物之沈澱物用去離子水洗淨5次。洗淨後之固 液相分離按照上述同樣以3 k g / c m2之壓力下進行加壓 過濾。洗淨後之鈦氫氧化物在7 0 °C，1 Ο T 〇 r r下減 壓乾燥1 8小時以去除水分而得固態狀含鈦化合物。 所得固態狀含鈦化合物做爲縮聚合觸媒使用之前，先 粉碎成1 0 //m左右之粒狀物。 聚酯之製造 例行操作時，反應液可滯留3 3 5 0 0重量份之反應 -145- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） 585881 A7 B7 五、發明説明（143 (請先閲讀背面之注意事項再填寫本頁) 容器中，連續供應由混合高純度對苯二甲酸和乙二醇而調 製之泥漿，攪拌下，氮氣中，260 t，〇 .9kg/ c m2 — G之條件下，進行酯化反應。上述高純度對苯二甲 酸和乙二醇之泥漿係按照高純度對苯二甲酸和乙二醇分別 以6 4 5 8重量份/小時和2 6 1 5重量份/小時之比率 混合而調製之。 又，開始酯化反應之前，添加固態狀含鈦化合物，乙 酸鎂和三丁基磷酸酯。固態狀含鈦化合物之添加量，以對 苯二甲酸單位計，鈦原子換算爲〇 · 〇 2 1莫耳％用量， 乙酸鎂之添加量以對苯二甲酸單位計，鎂原子換算爲 0·021莫耳％用量，三丁基磷酸酯之添加量，以對苯 二甲酸單位計，磷原子換算爲0.0105莫耳％用量。 酯化反應中，蒸餾去除水和乙二醇之混合液於反應系 外。酯化反應產物（低聚合物）控制在平均滯留時間爲 3 · 5小時而連續抽出到反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲600〜1300 (3〜5聚物）。 經濟部智慧財產局員工消費合作社印製 按照上述所得低聚合物在2 8 5 °C，1 Τ ο !· I·條件 下，進行液相縮聚合反應。聚乙烯對苯二甲酸酯之固有粘 度到達0 · 6 5 d Ι/g爲止所需時間爲5 6分鐘。 〔實施例4 9 7 - 1 C〕 在酯化反應過程中不添加固態狀含鈦化合物，而在液 相縮聚合步驟中之第一階段添加固態狀含鈦化合物之外， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）.146 . 585881 A7 B7 五、發明説明（144) 其他皆按照實施例4 9 7 - 1所示相同方法製造聚乙烯對 苯二甲酸酯。液相縮聚合步驟中，聚乙烯對苯二甲酸酯之 固有粘度到達0 · 6 5 d 1 / g爲止所需時間爲4小時。 (請先閲讀背面之注意事項再填寫本頁) 〔實施例4 9 9 — 1〕 固態狀含鈦化合物之調製 1 0 0 0 J之玻璃燒枉中秤取5 0 0 m£之去離子水， 冰浴中冷卻之後，攪拌下滴加5 g之四氯化駄。待氯化氫 之產生終止後自冰浴中取出，攪拌下滴加2 5 %之氨水， 調整溶液爲P Η 8。所產生之鈦氫氧化物之沈澱物在3 k g / c m2之壓力下加壓過濾器過濾分離之。然後，所得 鈦氫氧化物之沈澱物用去離子水洗淨5次。洗淨後之固液 相分離按照上述同樣以3 k g/c m2之壓力下進行加壓過 濾。洗淨後之鈦氫氧化物在7 0 °C，1 Ο T 〇 r I·下減壓 乾燥1 8小時以去除水分，而得固態狀含鈦化合物。 所得固態狀含鈦化合物在使用之前，先粉碎成爲1 0 "m左右之粉狀物。 經濟部智慧財產局員工消費合作社印製 聚酯之製造 例行操作時，反應液可滯留3 3 5 0 0重量份之反應 容器中，連續供應由混合高純度對苯二甲酸和乙二醇而調 製成之泥漿，攪拌下，氮氣中，260 t：，0 · 9kg/ c nf - G之條件下進行酯化反應。上述高純度對苯二甲酸 和乙二醇之泥漿係按照高純度對苯二甲酸和乙二醇分別爲 •147- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 8 8 5 8 5 A7 B7 五、發明説明（145) 6 4 5 8重量份/小時和2 6 1 5重量份/小時之比率混 合而調製之。 醋化反應中，蒸態去除水和乙二醇之混合液於反應系 外。酯化反應產物（低聚合物）控制在平均滯留時間爲 3 · 5小時而連續抽出到反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲600〜1300 (3〜5聚物）。 上述所得低聚合物中，添加固態狀含鈦化合物和三丁 基磷酸酯，在2 8 5 °C，1 T 〇 r r之條件下進行液相縮 聚合反應。固態狀含鈦化合物之添加量，以低聚合物中之 對苯二甲酸單位1莫耳計，酞原子換算爲〇 · 〇 2 1莫耳 %用量，三丁基磷酸酯之添加量，以低聚合物中之對苯二 甲酸單位1莫耳％，磷原子換算爲〇 · 〇 1 〇5莫耳％用 量而添加。聚乙烯對苯二甲酸酯之固有粘度到達〇 · 6 5 d 1 / g爲止所需時間爲6 0分鐘。 〔實施例4 9 9 — 2〕 經濟部智慧財產局員工消費合作社印製 代替三丁基磷酸酯，改用三辛基磷酸酯之外，其他皆 依照實施例4 9 9 - 1所示相同方法進行縮聚合反應。聚 乙嫌對苯二甲酸酯之固有粘度到達〇 · 6 5 ^丨/g爲止 所需時間爲6 0分鐘。 〔實施例4 9 9 一 3〕 代替三丁基磷酸酯，改用三苯基磷酸酯之外，其他皆 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公餐） -148- 585881 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（146) 依照實施例4 9 9 一 1所示相同方法進行縮聚合反應。聚 乙烯對苯二甲酸酯之固有粘度到達〇 · 6 5 d丨/g爲止 所需時間爲6 0分鐘。 〔貫施例4 9 9 一 4〕 代替三丁基磷酸酯，改用三甲基磷酸酯之外，其他皆 依照實施例4 9 9 一 1所示相同方法進行縮聚合反應。聚 乙烯對苯二甲酸酯之固有粘度到達〇 · 6 5 d丨/g爲止 所需時間爲7 5分鐘。 〔實施例5 0 0 — 1〕 固態狀含鈦觸媒之調製 1 0 0 Om£之玻璃燒枉中秤取5 〇 〇m£之去離子水， 冰浴中冷卻之後，攪拌下滴加5 g之四氯化鈦。待氯化氫 之產生終止後自冰浴中取出，攪拌下滴加2 5 %之氨水， 調整溶液爲p Η 8。所產生之鈦氫氧化物之沈澱物在3 k g / c m2之壓力下以加壓過濾器過濾分離之。然後，所 得鈦氫氧化物之沈澱物用去離子水洗淨5次。洗淨後之固 液相分離按照上述相同以3 k g / c m2之壓力進行加壓過 。洗淨後之鈦氫氧化物在7 0 °C，1 Ο T 〇 r r下減壓 乾燥1 8小時以去除水分，而得固態狀含鈦化合物。 所得固態狀含鈦化合物在使用前，先粉碎爲1 〇 V m 左右之粒狀物。 ---------Φ ! (請先閲讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -149- 585881 A7 B7 五、發明説明（ 聚酯之製造 例行操作時，反應液可滯留3 3 5 0 0重量份之反應 容器中，繼續供應由混合高純度對苯二甲酸和乙二醇而調 製之泥漿，攪拌下，氮氣中，260 °C，0 · 9kg/ c πί - G之條件下進行酯化反應。上述高純度對苯二甲酸 和乙二醇之泥漿係由高純度對苯二甲酸和乙二醇分別以 6 4 5 8重量份/小時和2 6 1 5重量份/小時之混合比 率而調製之。 酯化反應中，蒸餾去除水和乙二醇之混合液於反應系 外。酯化反應產物（低聚合物）控制在平均滯留時間爲 3 . 5小時而連續抽出到反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲600〜1300 (3〜5聚物）。 經濟部智慧財產局員工消費合作社印製 上述所得低聚合物中，添加固態狀含鈦化合物，乙酸 鎂和四個（亞甲基一 3 — (3 ，5 —二第三丁基—4 —羥 基苯基）丙酸酯）甲烷，在285°C，ITorr之條件 下進行液相縮聚合反應。固態狀含鈦化合物之添加量，以 低聚合物中之對苯二甲酸單位計，鈦原子換算爲 0 · 021莫耳％用量，乙酸鎂之添加量，以低聚合物中 之對苯二甲酸單位計，鎂原子換算爲〇 · 〇 2 1莫耳％用 量，而四個（亞甲基—3 — （3 ，5 —二第三丁基一4 — 羥基苯基）丙酸酯）甲烷之添加量，對低聚合物計6 0 0 P P m用量而添加之。 聚乙烯對苯二甲酸酯之固有粘度到達〇 . 6 5 d 1/ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -150- 585881 A7 B7 _ 五、發明説明（148) g爲止所需時間爲5 0分鐘，所得聚乙烯對苯二甲酸酯中 之乙醛含量爲60ppm。 (請先閲讀背面之注意事項再填寫本頁) 〔實施例5〇0 — 2〕 代替四個（亞甲基一 3 — (3 ，5 —二第三丁基一 4 一羥基苯基）丙酸酯）甲烷，改用雙（2，6 -二第三丁 基- 4 -苯甲基）異戊四醇—二亞磷酸酯，對低聚合物計 以3 0 0 p p m量而使用之外，其他皆依照實施例5 0 〇 - 1所示相同方法進行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度到達0 · 6 5 d 1/ g爲止所需時間爲4 8分鐘，所得聚乙烯對苯二甲酸酯中 之乙醛含量爲52ppm。 〔實施例5 0 0 — 3〕 經濟部智慧財產局員工消費合作社印製 代替四個（亞甲基一 3 — (3 ，5 —二第三丁基—4 一羥基苯基）丙酸酯）甲烷，改用3 ，5 -二第三丁基一 4 -羥基苯甲基磷酸二硬脂基酯，對低聚合物計以4 0 0 P P m量使用之外，其他皆按照實施例5 0 0 - 1所示相 同方法進行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度到達〇 · 6 5 d 1/ g爲止所需時間爲4 6分鐘，所得聚乙烯對苯二甲酸酯中 之乙醒含量爲5 8 p pm。 〔實施例5 0 〇 — 4〕 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -151 - 585881 A7 B7 五、發明説明（149) 代替四個（亞甲基—3 — (3 ，5_二第三丁基—4 一羥基苯基）丙酸酯）甲烷，改用四個（亞甲基一 3—( (請先閲讀背面之注意事項再填寫本頁) 3 ，5 —二第三丁基一 4 一羥基苯基）丙酸酯）甲烷和5 ，7 —二第三丁基_3 —（3 ，4 一二甲基苯基）—3h 一苯駢d夫喃一 2 -酮以及二個（2 ’ 4 一二第三丁基苯基 )亞磷酸酯之混合物（混合比率爲4 2 · 5 : 1 5 : 4 2.5)，其添加量對於低聚合物計，使用5 〇 〇 p p m之外，其餘皆按照實施例5 0 〇 — 1所示相同方法 進行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度到達0 · 6 5 d 1 / g爲止所需時間爲4 9分鐘，所得聚乙烯對苯二甲酸中之 乙醛含量爲55ppm。 〔實施例500 — 5〕 經濟部智慧財產局員工消費合作社印製 代替四個（亞甲基一 3 —（3 ，5 —二第三丁基一 4 -羥基苯基）丙酸酯）甲烷，改用三丁基磷酸酯以低聚合 物中之對苯二甲酸單位計，磷原子換算爲0·0105莫 耳％量添加之外，其他皆按照實施例5 0 0 - 1所示相同 方法進行縮聚合反應。 聚乙烯對苯二甲酸酯之固有粘度到達0 · 6 5 d 1/ g爲止所需時間爲5 0分鐘，所得聚乙烯對苯二甲酸酯中 之乙酵含量爲5 0 p pm。 〔實施例5 0 0 - 1 C〕 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-152 - 585881 A7 B7 五、發明説明（150> (請先閲讀背面之注意事項再填寫本頁) 代替四個（亞甲基一 3 — （3 ，5 —二第三丁基一 4 一羥基苯基）丙酸酯）甲烷，改用磷酸以低聚合物中之對 苯二甲酸單位計，磷原子換算爲0.0105莫耳％用量 之外，其他皆按照實施例5 0 0 - 1所示相同方法進行縮 聚合反應。 聚乙烯對苯二甲酸酯之固有粘度到達0 · 6 5 d 1/ g爲止所需時間爲7 0分鐘，所得聚乙烯對苯二甲酸酯中 之乙醒含量爲7 Oppm。 〔實施例5 0 2 - 1〕 固態狀含鈦化合物之調製 經濟部智慧財產局員工消費合作社印製 1 0 0 0 之玻璃燒枉中秤取5 0 0 之去離子水， 冰浴中冷卻之後，攪拌下滴加5 g之四氯化鈦。待氯化氫 之產生終止後自冰浴中取出，攪拌下滴加2 5 %之氨水， 調整溶液爲p Η 8。所產生鈦氫氧化物之沈澱物在3 k g / c m2壓力下以加壓過濾器過濾分離。然後所得鈦氫氧化 物之沈澱物用去離子水洗淨5次。洗淨後之固液相分離按 照上述同樣以3 k g / c m2壓力進行加壓過濾。洗淨後之 鈦氫氧化物在7 0 °C，1 0 T 〇 r r下減壓乾燥1 8小時 以去除水分，而得固態狀含鈦化合物。 所得固態狀含鈦化合物做爲縮聚合觸媒使用之前，先 粉碎爲1 0 // m左右之粉狀物。 聚酯之製造 -153- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 8 8 5 8 5 A7 B7 五、發明説明（151) ΦII (請先閱讀背面之注意事項再填寫本頁) 例行操作時’反應液可滯留3 3 5 0 0重量份之反應 容器中，連續供應由混合高純度對苯二甲酸和乙二醇而調 製成之泥漿，攪拌下’氮氣中’ 260°C ’ 0 · 9kg/ c πί - G之條件下，進行酯化反應。上述高純度對苯二甲 酸和乙二醇之泥漿係由高純度對苯二甲酸和乙二醇分別以 6 4 5 8重量份/小時和2 6 1 5重量份/小時之比率混 合而調製。 又，酯化反應開始前，添加固態狀含鈦化合物。乙酸 鎂，三丁基磷酸酯和色相調整劑於反應容器中。固態狀含 鈦化合物之添加量，對聚乙烯對苯二甲酸酯計，鈦原子換 算爲1 2 p pm用量，乙酸鎂之添加量以聚乙烯對苯二甲 酸酯計，鎂原子換算爲2 5 p pm用量，三丁基磷酸酯之 添加量以聚乙烯對苯二甲酸酯計，磷原子換算爲1 5 P P m用量，色相調整劑（藍色溶劑1 0 4 )之添加量’ 以聚乙烯對苯二甲酸酯計，5 · Oppm用量而添加之。 酯化反應中，蒸餾去除水和乙二醇之混合液於反應系 外。酯化反應產物（低聚合物）控制在平均滯留時間爲 3 · 5小時而連續抽出到反應系外。 經濟部智慧財產局員工消費合作社印製 由上述所得乙二醇和對苯二甲酸之低聚合物之數平均 分子量爲600〜1 300 (3〜5聚物）。 上述所得低聚合物在2 8 5 °C，1 Τ ο I* r之條件下 ，進行縮聚合反應。 上述所製得之聚酯片之色調用4 5 °擴散方式色差計（ 曰本電色公司製品，S Q 3 0 0 Η型）測定之。其結果示 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -154- 8 8 5 8 5 A7 _ B7___ 五、發明説明（152) 於表5〇2—1中。 〔實施例502 — 2〜502 — 5 ，實施例5〇2 — lc ] 按照表5 0 2 - 1中所示改變色相調整劑之種類和添 加量之外，其他皆按照實施例5 0 2 - 1所示相同方法製 造聚酯。測定該聚酯片之色調之結果示於表5 0 2 - 1中 〔實施例502 — 6〜502 - 1 1 ，實施例502-2C 〜502 — 4C〕 按照表5 0 2 - 1中所示改變固態狀含鈦化合物，乙 酸鎂，磷化合物之添加量，色相調整劑之種類和添加量也 按照表5 0 2 — 1所示變更之外，其他皆依照實施例 5 0 2 - 1所示相同方法製造聚酯。該聚酯片之色調之測 定結果示於表5 0 2 — 1中。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -155- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 585881、 1T • 丨 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 public envy) · 143 · 585881 A7 B7 V. Description of the invention (141) and glycol slurry are based on high purity terephthalic acid and ethyl acetate The diol was prepared by mixing at a ratio of 6 4 5 8 parts by weight / hour and 2 6 1 5 parts by weight / hour. (Please read the precautions on the back before filling in this page) In the esterification reaction, the mixture of water and ethylene glycol is distilled away from the reaction system. The esterification reaction product (oligomer) was controlled to have an average residence time of 3.5 hours while continuously withdrawing from the reaction system. The number average molecular weight of the oligomers of the ethylene glycol and terephthalic acid obtained above is 60 to 1300 (3 to 5 polymers). According to the above-mentioned low polymer, the above solid titanium-containing compound is added, and the amount of titanium atom converted to the terephthalic acid unit in the low polymer is 0. 0 2 1 mol%, and magnesium hydrogen phosphate is further added. Based on the terephthalic acid unit in the low polymer, the amount of magnesium atom is converted to 0.001% by mole, and the amount of phosphoric acid is added to convert the phosphorus atom to 0.001% by mole. The liquid phase polycondensation reaction was performed under the conditions of 85 ° C and 1 T rr. The time required for the intrinsic viscosity of polyethylene terephthalate to reach 0.65 d 1 / g was 5 7 minutes. The ethylene terephthalate had an acetaldehyde content of 60 ppm. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 5 0 1 — 2] Instead of using magnesium hydrogen phosphate and using trimagnesium diphosphate, the others were subjected to condensation polymerization in the same manner as in Example 5 0 1 — 1 reaction. The time required for the intrinsic viscosity of polyethylene terephthalate to reach 0.65 d 1 / g is 67 minutes, and the acetaldehyde content in the obtained polyethylene terephthalate is 57 ppm 〇-144 -This paper size is in accordance with China National Standard (CNS) A4 specification (210X297). 585881 A7 B7 5. Description of the invention (143 [Example 5 0 1 — 1 C] (Please read the precautions on the back before filling out this page) Instead of magnesium hydrogen phosphate, other than magnesium acetate was used. All other polycondensation reactions were carried out in the same manner as shown in Example 5 0 1-1. The inherent viscosity of polyethylene terephthalate reached 0 · 6 5 d 1 The time required up to / g is 100 minutes, and the acetic acid content in the obtained polyethylene terephthalate is 70 ppm. [Example 4 9 7 — 1] Modulation of Ministry of Economic Affairs Weighed 5 000 4 of deionized water in a glass burner printed by 1 000 of the consumer cooperative of the property bureau. After cooling in an ice bath, 5 g of titanium tetrachloride was added dropwise with stirring. Wait for the generation of hydrogen chloride. After termination, remove from the ice bath, add 25% ammonia water dropwise with stirring, adjust the solution to P Η 8. The precipitate of the produced titanium hydroxide was filtered and separated by a pressure filter under a pressure of 3 kg / cm2. Then, the precipitate of the obtained titanium hydroxide was washed 5 times with deionized water. Washing The solid-liquid phase separation after cleaning was carried out under the same pressure and pressure filtration at a pressure of 3 kg / cm2 as described above. The washed titanium hydroxide was dried under reduced pressure at 70 ° C and 10 〇 rr for 18 hours. The solid titanium-containing compound is obtained by removing water. Before the obtained solid titanium-containing compound is used as a condensation polymerization catalyst, it is pulverized into granules of about 10 // m. During the routine operation of polyester production, the reaction The liquid can retain 3 3 5 0 0 parts by weight of the reaction -145- This paper size applies Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) 585881 A7 B7 V. Description of the invention (143 (Please read the note on the back first) Please fill in this page again) In the container, continuously supply the slurry prepared by mixing high-purity terephthalic acid and ethylene glycol, under stirring, under nitrogen, 260 t, 0.9 kg / c m2 — G Esterification reaction. The above-mentioned slurry of high purity terephthalic acid and ethylene glycol is based on High-purity terephthalic acid and ethylene glycol are mixed at a ratio of 6 4 5 8 parts by weight / hour and 2 6 15 parts by weight / hour, respectively. In addition, before starting the esterification reaction, a solid titanium-containing compound is added. , Magnesium acetate and tributyl phosphate. The amount of solid titanium-containing compound added, based on terephthalic acid units, the titanium atom is converted to 0.002 mol%, and the amount of magnesium acetate added In terms of formic acid units, magnesium atoms are converted into an amount of 0.021 mol%, and in terms of the amount of tributyl phosphate added, based on terephthalic acid units, phosphorus atoms are converted into an amount of 0.0105 mol%. In the esterification reaction, a mixed solution of water and ethylene glycol is distilled out of the reaction system. The esterification reaction product (oligomer) is controlled to be continuously extracted out of the reaction system with an average residence time of 3.5 hours. The number average molecular weight of the oligomers of the ethylene glycol and terephthalic acid obtained above is 600 to 1300 (3 to 5 polymers). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs According to the above-mentioned low polymer, a liquid phase condensation polymerization reaction was performed under the conditions of 2 8 ° C and 1 Τ! · I ·. The time required for the intrinsic viscosity of polyethylene terephthalate to reach 0.65 d Ι / g is 56 minutes. [Example 4 9 7-1 C] The solid titanium-containing compound was not added during the esterification reaction, and the solid titanium-containing compound was added in the first stage of the liquid phase condensation polymerization step. This paper is applicable to China National Standard (CNS) A4 specification (210X297 mm). 146. 585881 A7 B7 V. Description of the invention (144) Others The polyethylene terephthalate was manufactured according to the same method as shown in Example 4 9 7-1. In the liquid phase condensation polymerization step, the time required for the intrinsic viscosity of the polyethylene terephthalate to reach 0.65 d 1 / g was 4 hours. (Please read the precautions on the back before filling in this page) [Example 4 9 9 — 1] Preparation of solid titanium-containing compound 1 0 0 0 J in a glass burner, weigh 5 000 m of deionized water After cooling in an ice bath, 5 g of osmium tetrachloride was added dropwise with stirring. After the generation of hydrogen chloride is terminated, remove it from the ice bath, and add 25% ammonia water dropwise with stirring to adjust the solution to P Η 8. The precipitate of titanium hydroxide produced was separated by filtration under a pressure of 3 k g / cm 2 under a pressure filter. Then, the obtained titanium hydroxide precipitate was washed 5 times with deionized water. The solid-liquid phase separation after washing was carried out under the same pressure and filtration under a pressure of 3 k g / c m2 as described above. The washed titanium hydroxide was dried under reduced pressure at 70 ° C, 100 Torr I · for 18 hours to remove water, and a solid titanium-containing compound was obtained. The obtained solid titanium-containing compound is pulverized into a powder of about 10 " m before use. During the routine operation of manufacturing polyester printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the reaction solution can be retained in a reaction container of 3,500 parts by weight, and continuous supply of mixed high-purity terephthalic acid and ethylene glycol is provided. The prepared slurry was subjected to an esterification reaction under agitation in nitrogen at 260 t: 0 · 9 kg / c nf-G. The above-mentioned high-purity terephthalic acid and ethylene glycol slurries are • 147- according to the high-purity terephthalic acid and ethylene glycol, respectively. This paper size applies to China National Standard (CNS) A4 (210X297 mm) 8 8 5 8 5 A7 B7 V. Description of the invention (145) 6 4 5 8 parts by weight / hour and 2 6 1 5 parts by weight / hour are mixed and prepared. In the vinegarization reaction, a mixed solution of water and ethylene glycol is removed from the reaction system by evaporation. The esterification reaction product (oligomer) is controlled to be continuously extracted out of the reaction system with an average residence time of 3.5 hours. The number average molecular weight of the oligomers of the ethylene glycol and terephthalic acid obtained above is 600 to 1300 (3 to 5 polymers). To the oligomer obtained above, a solid titanium-containing compound and tributyl phosphate were added, and a liquid-phase polycondensation reaction was performed under the conditions of 2 8 ° C and 1 Torr. The amount of solid titanium-containing compound is calculated based on 1 mole of terephthalic acid unit in the low polymer, and the amount of phthalate atom is converted to 0.02 mol%. The amount of tributyl phosphate is low. A terephthalic acid unit in the polymer was added in an amount of 1 mole%, and a phosphorus atom was converted into an amount of 0.005 mole%. The time required for the intrinsic viscosity of polyethylene terephthalate to reach 0.65 d 1 / g was 60 minutes. [Example 4 9 9 — 2] Printed in place of tributyl phosphate and replaced with trioctyl phosphate by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the other methods are the same as those shown in Example 4 9 9-1 A polycondensation reaction is performed. It takes 60 minutes for the inherent viscosity of polyethylene terephthalate to reach 0.65 ^ 丨 / g. [Example 4 9 9 1-3] Instead of tributyl phosphate, use triphenyl phosphate, all other paper sizes apply Chinese National Standard (CNS) A4 specification (210X297 meal) -148- 585881 Economy Printed by the Intellectual Property Bureau employee consumer cooperative A7 B7 V. Invention description (146) The condensation polymerization reaction was carried out according to the same method as shown in Example 4 9 9-11. The time required for the intrinsic viscosity of the polyethylene terephthalate to reach 0.65 d 丨 / g is 60 minutes. [Consistent Example 4 9 9-1] Instead of tributyl phosphate, trimethyl phosphate was used, and the polycondensation reaction was carried out in the same manner as shown in Example 4 9 9-1. The time required for the intrinsic viscosity of polyethylene terephthalate to reach 0.65 d 丨 / g is 75 minutes. [Example 5 0-0 — 1] Preparation of solid titanium-containing catalyst in a glass burner with a size of 100 Om £, weighed 5000 m of deionized water, and after cooling in an ice bath, 5 was added dropwise with stirring. g of titanium tetrachloride. After the generation of hydrogen chloride is terminated, remove it from the ice bath, and add 25% ammonia water dropwise with stirring to adjust the solution to p Η 8. The precipitate of the generated titanium hydroxide was separated by filtration under a pressure of 3 k g / cm 2 with a pressure filter. Then, the precipitate of the obtained titanium hydroxide was washed 5 times with deionized water. After washing, the solid-liquid phase separation was pressurized at a pressure of 3 kg / cm2 as described above. After washing, the titanium hydroxide was dried under reduced pressure at 70 ° C and 10 Torr for 18 hours to remove water to obtain a solid titanium-containing compound. Prior to use, the obtained solid titanium-containing compound was pulverized into granules of about 10 V m. --------- Φ! (Please read the precautions on the back before filling this page) The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -149- 585881 A7 B7 V. Description of the invention (During the routine operation of the production of polyester, the reaction solution can be retained in a reaction container of 3,500 parts by weight, and the slurry prepared by mixing high-purity terephthalic acid and ethylene glycol is continuously supplied. Esterification was carried out under nitrogen at 260 ° C and 0 · 9kg / c πί-G. The above-mentioned slurry of high-purity terephthalic acid and ethylene glycol was composed of high-purity terephthalic acid and ethylene glycol, respectively. It is prepared by mixing ratios of 6 4 5 8 parts by weight / hour and 2 6 1 5 parts by weight / hour. In the esterification reaction, the mixed solution of water and ethylene glycol is distilled out of the reaction system. The esterification reaction product (low The polymer) is controlled so that the average residence time is 3.5 hours and continuously extracted outside the reaction system. The number average molecular weight of the low polymer of ethylene glycol and terephthalic acid obtained above is 600 to 1300 (3 to 5 polymers). The Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the above-mentioned low aggregation In the solid state, add a titanium-containing compound, magnesium acetate and four (methylene-3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate) methane at 285 ° C, ITorr The liquid phase polycondensation reaction is carried out under the conditions. The addition amount of the solid titanium-containing compound is based on the terephthalic acid unit in the low polymer, and the titanium atom is converted into an amount of 0. 021 mol%. Based on the terephthalic acid units in the oligomer, the magnesium atom is converted to 0. 002 1 mol%, and four (methylene-3— (3, 5—di-tert-butyl-4— The hydroxyphenyl) propionate) methane is added in an amount of 600 PP m based on the low polymer. The inherent viscosity of polyethylene terephthalate reaches 0.6 5 d 1 / the paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) -150- 585881 A7 B7 _ 5. Description of the invention (148) The time required is 50 minutes, and the ethylene in the obtained polyethylene terephthalate The aldehyde content is 60 ppm. (Please read the precautions on the back before filling in this page) [Example 50,000 — 2] Substitute four (methylene-3- (3,5-di-tertiary-butyl-4 4-hydroxyphenyl) propionate) methane and use bis (2,6-di-tertiary-butyl-4-benzene Methyl) isopentaerythritol-diphosphite was subjected to polycondensation according to the same method as shown in Example 500-1 except that 300 ppm was used as the low polymer. The time required for the intrinsic viscosity of the terephthalate to reach 0.65 d 1 / g was 48 minutes, and the acetaldehyde content in the obtained polyethylene terephthalate was 52 ppm. [Example 5 0 — 3] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs instead of four (methylene-3— (3,5-di-third-butyl-4—hydroxyphenyl) propionate) Methane was changed to 3,5-di-tert-butyl- 4-hydroxybenzyl distearyl phosphate, and it was used in accordance with Example 50 except that it was used in an amount of 400 PP m for the low polymer. Polycondensation is carried out in the same manner as shown in 0-1. The time required for the intrinsic viscosity of the polyethylene terephthalate to reach 0.65 d 1 / g was 46 minutes, and the ethylene content in the obtained polyethylene terephthalate was 5 8 p pm. [Example 5 00—4] This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -151-585881 A7 B7 V. Description of the invention (149) Instead of four (methylene-3 — ( 3,5_Di-tertiary butyl-4 monohydroxyphenyl) propionate) methane, use four (methylene-3— ((Please read the precautions on the back before filling out this page) 3,5 —Di-tertiary-butyl-4 monohydroxyphenyl) propionate) methane and 5,7-di-tertiarybutyl-3— (3,4-dimethylphenyl) —3h monophenylhydrazine A mixture of 2-ketone and two (2 '4 -di-tert-butylphenyl) phosphites (mixing ratio is 4 2 · 5: 1 5: 4 2.5), the amount of addition is based on low polymer, With the exception of 5,000 ppm, the rest were subjected to polycondensation according to the same method as shown in Example 500-1. The time required for the intrinsic viscosity of the polyethylene terephthalate to reach 0.65 d 1 / g was 49 minutes, and the acetaldehyde content in the obtained polyethylene terephthalic acid was 55 ppm. [Example 500-5] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs instead of four (methylene-3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate) methane, Instead of using tributyl phosphate based on the terephthalic acid unit in the low polymer, the phosphorus atom is converted to 0.010105 mole%, and the rest are performed in the same manner as shown in Example 5 0 0-1 Polycondensation. The time required for the intrinsic viscosity of the polyethylene terephthalate to reach 0.65 d 1 / g was 50 minutes, and the acetic acid content in the obtained polyethylene terephthalate was 50 p pm. [Example 5 0 0-1 C] This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -152-585881 A7 B7 V. Description of the invention (150 > (Please read the notes on the back before filling in (This page) instead of four (methylene-3- (3,5-di-tertiary-butyl-4 4-hydroxyphenyl) propionate) methane, use phosphoric acid as the terephthalic acid unit in the low polymer In addition, the phosphorus atom is converted into 0.0105 mol%, and the polycondensation reaction is performed in the same manner as in Example 5 0-1. The intrinsic viscosity of polyethylene terephthalate reaches 0 · 6 5 d The time required up to 1 / g is 70 minutes, and the content of ethyl acetate in the obtained polyethylene terephthalate is 7 Oppm. [Example 5 0 2-1] Solid state titanium-containing compound Modified Ministry of Economic Affairs Intellectual Property Bureau staff consumer cooperative printed 1 000 glass decanter and weighed 5 0 0 deionized water. After cooling in an ice bath, 5 g of titanium tetrachloride was added dropwise under stirring. Take out in an ice bath, add 25% ammonia water dropwise while stirring, and adjust the solution to p Η 8. Produced The precipitate of the raw titanium hydroxide was filtered and separated under a pressure of 3 kg / c m2 using a pressure filter. Then the precipitate of the obtained titanium hydroxide was washed 5 times with deionized water. The solid and liquid phases were separated after washing. Pressure filtration was performed at a pressure of 3 kg / cm2 according to the above. The washed titanium hydroxide was dried under reduced pressure at 70 ° C and 10 T rr for 18 hours to remove moisture, and a solid content was obtained. Titanium compound. The obtained solid titanium-containing compound is crushed into a powder of about 10 // m before being used as a polycondensation catalyst. Manufacture of polyester -153- This paper applies Chinese national standard (CNS) A4 Specifications (210X297 mm) 8 8 5 8 5 A7 B7 V. Description of the invention (151) ΦII (Please read the precautions on the back before filling this page) Routine operation 'Reaction liquid can be retained 3 3 5 0 0 parts by weight In the reaction vessel, a slurry prepared by mixing high-purity terephthalic acid and ethylene glycol is continuously supplied, and esterified under the condition of 'in nitrogen' 260 ° C '0 · 9kg / c πί -G under stirring. Reaction. The above-mentioned slurry of high-purity terephthalic acid and ethylene glycol Dicarboxylic acid and ethylene glycol are mixed at a ratio of 6 4 5 8 parts by weight / hour and 2 6 15 parts by weight / hour, respectively. In addition, before the esterification reaction is started, a solid titanium-containing compound is added. Magnesium acetate, three Butyl phosphate and hue adjuster are in the reaction container. The amount of titanium-containing compound in solid state is calculated based on polyethylene terephthalate. The amount of titanium atom is 12 p pm, and the amount of magnesium acetate is polymerized. For ethylene terephthalate, the amount of magnesium atom is converted to 2 5 p pm, the amount of tributyl phosphate is added to polyethylene terephthalate, and the amount of phosphorus atom is converted to 1 5 PP m. The hue is adjusted The amount of the additive (blue solvent 104) is added based on polyethylene terephthalate at 5 · Oppm. In the esterification reaction, a mixed solution of water and ethylene glycol is distilled out of the reaction system. The esterification reaction product (oligomer) is controlled to be continuously extracted out of the reaction system with an average residence time of 3.5 hours. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The number average molecular weight of the low polymer of ethylene glycol and terephthalic acid obtained from the above is 600 ~ 1 300 (3 ~ 5 polymers). The obtained oligomer undergoes polycondensation under the conditions of 2 8 ° C and 1 T ο I * r. The color of the polyester sheet prepared above was measured by a 45 ° diffusion method color difference meter (a product of Benden Electric Color Co., Ltd., S Q 3 0 0 Η). The results show that the paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -154- 8 8 5 8 5 A7 _ B7___ 5. The description of the invention (152) is shown in Table 50-2. [Examples 502-2 to 502-5, Example 50-2 — lc] The types and addition amounts of the hue adjusting agent were changed as shown in Table 5 0 2-1, and the rest were the same as in Example 5 0 2- Polyester was produced in the same manner as shown in 1. The results of measuring the color tone of the polyester sheet are shown in Table 5 0 2-1 [Examples 502-6 to 502-1 1 and Examples 502-2C to 502-4C] According to Table 5 0 2-1 The solid titanium-containing compounds, magnesium acetate, and phosphorus compounds were added, and the types and amounts of hue adjusting agents were changed as shown in Table 50-2. The rest were in accordance with Example 5 02-1. Polyester was made in the same way. The measurement results of the color tone of the polyester sheet are shown in Table 50-2-1. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -155- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 585881

A 五、發明説明（153) 經濟部智慧財產局員工消費合作社印製 O un p 寸 〇j p 寸· t · i v〇 un 〇 ψ i t < 1 寸 O OO oo o p i 4 ON un 〇 ON 寸 o r- o w "丨崤 o oo CNi csi o CN) VO o oc oi o 寸 οό o CN 1 c5 cn cn cs τ3| CN 寸· OO o； 〇\ un 寸 卜 O oo On 寸 oo η-3 u〇 un 06 un un v〇 VO 1 ___H cn wo s MD un s s un υη s υη m 薇 锲 1 1 1 1 1 1 1 un 1 〇 un O CN 1 p 〇 o4 1 §: i 鎞 ptic7 mu. ΠΖΙ cn rsi 酱 1 o cn oo r—H VsO o o v〇 1 un 1 1 1 1 1 1 t 1 ί] g 1 '< 锲 τώΊ o wn o un 〇 cn p ^ i 1 1 0 01 C^* 1 1 1 1 in i i CN 1 <p 1 趟 <Π B υο 安 m 丄1 wn CXi i Ή H H n 1： 1： ψ 1 i n 1： IS： m m N3 wo 叫 oo <T) csi oo -H a ίϋ n i 1 i El EE f i K <Π CNl OO un csi oo <ίίΙ a ^ ϋ： 1： 1： n i 4 E E 1： fK 画 < 111 H 1 csi rn v〇 u _丨丨蜻 1 vxp rp 1 oo On u cn 〇 i 1 ， A t i 1 u s § S \y^) CN C<l 〇 V/^J s l/^N g g |V^v s l/^v s 1/^ s 1/^ S 1/^ s s s m m m ^ ) m i ^ J w 1 m ^ i w ) m i vr ) m 囊 m m m 蓉 m m 琴 變 IK u 麵 IS S -¾ -¾ u u IK s n IS -¾ ---------— (請先閱讀背面之注意事項再填寫本頁) 、\=口 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ 156 - 經濟部智慧財產局8工消費合作社印製 585881 A7 B7 五、發明説明（154) 〔實施例4 6 4 - 1〕 固有粘度爲0 · 85d Ι/g ，密度爲1 . 4〇g/ cm3，乙醛含量爲1 · 5 p pm之粒狀聚乙烯對苯二甲酸 酯2 · 5kg，浸漬在容有0 · 0695重量％ (以磷原 子換算爲1 6 1 ppm)之磷酸三甲酯水溶液4kg之不 銹鋼容器中，在常溫下保持4小時之後，分離粒狀聚乙烯 對苯二甲酸酯和磷酸三甲酯水溶液，排除水分後，在 1 6 0 °C下氮氣流中乾燥5小時。所得聚乙烯對苯二甲酸 酯使用前述方法成型爲階梯狀矩形成型物，其乙醛含量爲 7 . 7ppm，固有粘度爲 0 · 821dl/g。 〔實施例4 6 4 - 2〕 使用實施例4 6 4 — 1所採用相同粒狀聚乙烯對苯二 甲酸酯2 · 5kg ，浸漬在容有〇 · 0695重量％ (磷 原子換算爲1 6 1 ppm)之磷酸三甲酯水溶液4kg之 不銹鋼容器中。繼之，將容有聚乙烯對苯二甲酸酯和磷酸 三甲酯水溶液之不銹鋼容器自外部加熱，控制其內溫爲 9 5 °C，保持4小時進行加熱處理之後，分離粒狀聚乙烯 對苯二甲酸酯和磷酸三甲酯水溶液，排除水分後，在 1 6 0 °C下氮氣流中乾燥5小時。使用所得聚乙烯對苯二 甲酸酯按照上述方法成型爲階梯狀矩形成型物’其乙醛含 量爲8 · 5ppm，固有粘度爲〇 · 802d Ι/g。 〔實施例4 6 4 — 1 C〕 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）.仂7 - ------------Ί--、玎------« (請先閱讀背面之注意事項再填寫本頁} 585881 A7 B7 五、發明説明（155 ) (請先閱讀背面之注意事項再填寫本頁) 使用實施例4 6 4 - 1所採用相同粒狀聚乙烯對苯：；： 甲酸酯，但不以含磷水溶液接觸處理，直接以上述方法成 型爲階梯狀矩形成型物，其乙醛含量爲1 1 p p m，固有 粘度爲 0 . 833d 1/ g。 〔實施例464-2C〕 代替磷酸三甲酯水溶液，改用相同濃度（ 0 · 0508重量％，磷原子換算爲161ppm)之磷 酸水溶液之外，其他皆依照實施例4 6 4 - 1所示相同方 法處理粒狀聚乙烯對苯二甲酸酯。使用所得聚乙烯對苯二 甲酸酯按照上述方法成型爲階梯狀矩形成型物，其乙醛含 量爲8 · 3ppm，固有粘度爲〇.814d 1/g。 〔比較例4 6 4 — 3〕 經濟部智慧財產局員工消費合作社印製 代替磷酸三甲酯水溶液，使用磷酸水溶液之外，其餘 皆按照實施例4 6 4 - 2所示相同方法處理粒狀聚乙烯對 苯二甲酸酯。使用所得聚乙烯對苯二甲酸酯按照上述方法 成型爲階梯狀矩形成型物，其乙醛含量爲1 0 · 0 P P m ，固有粘度爲0.788dl/g。 〔實施例4 6 5 — 1〕 固態狀含鈦化合物之調製 1 0 0 0 d之玻璃燒枉中秤取5 0 〇 j之去離子水， 在冰浴中冷卻之後，攪拌下滴加5 g之四氯化鈦。待氯化 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -158- 585881 A7 B7 五、發明説明（156) 氫之產生終止後自冰浴中取出，攪拌下滴加2 5 %之氨水 調整溶液爲p Η 8。所產生之鈦氫氧化物之沈澱物在3 k g / c m2之壓力下以加壓過濾器過濾分離。然後，所得 鈦氫氧化物之沈澱物用去離子水洗淨5次。洗淨後之固液 相分離以上述相同方法在3 k g / c m2之壓力下進行加壓 過濾。洗淨後之鈦氫氧化物在7 0 °C，1 Ο T 〇 r r下減 壓乾燥1 8小時以去除水分，而得固態狀含鈦化合物。 所得固態狀含鈦化合物在使甩之前，先粉碎爲1 0 # m左右之粒狀物。 聚乙烯對苯二甲酸酯之製造 例行操作時，反應液可滯留3 3 5 0 0重量份之反應 容器中，連續供應由混合高純度對苯二甲酸和乙二醇而調 製成之泥漿，攪拌下，氮氣中，260 °C，0 . 9kg/ c rrf - G之條件下進行酯化反應。上述高純度對苯二甲酸 和乙二醇之泥漿係由高純度對苯二甲酸和乙二醇分別以 6 4 5 8重量份/小時和2 6 1 5重量份/小時之比率混 合而調製之。 酯化反應中，蒸餾去除水和乙二醇之混合液於反應系 外。酯化反應產物（低聚合物）控制在平均滯留時間爲 3 · 5小時而連續抽出反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲600〜1300 (3〜5聚物）。 上述所得低聚合物中，添加固態狀含鈦化合物，乙酸 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇><297公釐） ---------•裝-- (請先閲讀背面之注項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -159- 585881 A7 _B7____ 五、發明説明（157) 鎂和三丁基磷酸酯，在285 °C，lTor r之條件下進 行液相縮聚合反應，而得固有粘度爲〇 · 6 5 d Ι/g之 聚乙烯對苯二甲酸酯。固態狀含鈦化合物之添加量，對低 聚合物中之對苯二甲酸單位計，鈦原子換算爲〇 · 〇 2 1 莫耳％用量，乙酸鎂之添加量，對低聚合物中之對苯二甲 酸單位計，鎂原子換算爲〇 · 〇 2 1莫耳％用量，三丁基 磷酸酯之添加量，對低聚合物中之對苯二甲酸單位計，磷 原子換算爲0 · 0 1 0 5莫耳％用量添加之。 然後’更將上述液相縮聚合反應終了之聚乙烯對苯二 甲酸酯加以固相縮聚合，製得固有粘度爲〇 · 8 1 d 1/ g ’祀、度爲1 · 40g / cm3，乙醒含量爲1 · 〇ppm 之粒狀聚乙烯對苯二甲酸酯。 聚乙烯對苯二甲酸酯之處理 上述粒狀聚乙烯對苯二甲酸酯1 〇 g和異丙醇4 〇 g 放入1 0 0 之燒瓶中，迴流下加熱4小時。然後在7 0 °C下乾燥1 6小時，在2 7 0 °C下加熱熔融6分鐘之後， 冷卻至室溫，再採取試料測定乙醛含量之結果爲5 . 2 p p m 〇 〔實施例4 6 5 - 2〕 代替異丙醇，改用甲醇之外，其他皆依照實施例 4 6 5 — 1所示相同方法使粒狀聚乙烯對苯二甲酸醋和有 機溶劑接觸，按照實施例4 6 5 — 1所示相同方法測定乙 本紙張尺度適用中國國家標準（CNS )八4規格（210X297公釐） I---------- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -160- 8 5 8 A7 B7 -------^ 五、發明説明（158) 醒含量之結果爲6.4ppm。 〔實施例4 6 5 — 3〕 --------ΦI — (請先閲讀背面之注意事項再填寫本頁} 代替異丙醇，改用丙酮之外，其他皆依照實施例 4 6 5 - 1所示相同方法使粒狀聚乙烯對苯二甲酸醋和有 機溶劑接觸，再按照實施例4 6 5 — 1所示相同方法測定 乙醒含量之結果爲6 · 7 p pm。 〔實施例4 6 5 - 4〕 代替異丙醇’改用己烷之外，其他皆依照實施例 4 6 5 - 1所示相同方法使粒狀聚乙烯對苯二甲酸醋和有 機溶劑接觸，再按照實施例4 6 5 - 1所示相同方法測定 乙里之結果爲6 · 8pprn。 〔實施例4 6 5 — 1 C〕 經濟部智慧財產局8工消費合作社印製 使用實施例4 6 5 - 1所採用相同粒狀聚乙烯對苯二 甲酸酯，但不以有機溶劑接觸處理，在7 0 °C下乾燥1 6 小時’再於2 7 0 °C下加熱熔融6分鐘之後，冷卻至室溫 ’由之採取試料所測定乙醛含量之結果爲7 · 3 p p m。 〔實施例4 6 6 — 1〕 固態狀含鈦化合物之調製 1 0 0 Om£之玻璃燒枉中秤取5 0 〇m£之去離子水， 在冰浴中冷卻之後，攪拌下滴加5 g之四氯化鈦。待氯化 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -161 - 585881 A7 B7 五、發明説明（159) (請先閱讀背面之注意事項再填寫本頁) 氫之產生終止後自冰浴中取出’攪拌下滴加2 5 %之氨水 ，調整溶液爲P Η 8 °所產生欽氫氧化物之沈澱物在3 k g / c ηί之壓力下以加壓過濾器過濾分離之。然後’所 得鈦氫氧化物之沈澱物用去離子水洗淨5次。洗淨後之固 液相分離，按照上述相同方法以3 k g / c πί之壓力下進 行加壓過濾。洗淨後之鈦氫氧化物在7 〇 °C ’ 1 〇 T 〇 r r下減壓乾燥1 8小時以去除水分’而得固態狀含 鈦化合物。 所得固態狀含鈦化合物在使用之前’先粉碎成爲1 〇 β m左右之粒狀物。 聚乙烯對苯二甲酸酯之製造 經濟部智¾財/$局員工消費合作社印製 例行操作時，反應液可滯留3 3 5 0 0重量份之反應 容器中，連續供應由混合高純度對苯二甲酸和乙二醇而調 製成之泥漿，攪拌下，氮氣中，260 °C，0 . 9kg/ c rri - G之條件下進行酯化反應。上述高純度對苯二甲酸 和乙二醇之泥漿係由高純度對苯二甲酸和乙二醇分別以 6 4 5 8重量份/小時和2 6 1 5重量份/小時之比率混 合而調製之。 酯化反應中’蒸餾去除水和乙二醇之混合液於反應系 外。酯化反應產物（低聚合物）控制在平均滯留時間爲 3 . 5小時而連續抽出反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲600〜1300(3〜5聚物）° 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）_ 162 - 585881 A7 B7 五、發明説明（16C?) (請先閲讀背面之注意事項再填寫本頁) 按照上述所得低聚合物中，添加固態狀含鈦化合物， 乙酸鎂和三丁基磷酸酯，在285 t：，ITo r I*之條件 下進行液相縮聚合反應’製得固有粘度爲〇 · 6 5 d 1 / g之聚乙烯對苯二甲酸酯。固態狀含鈦化合物之添加量， 對於低聚合物中之對苯二甲酸單位計，欽原子換算爲 0 · 0 2 1莫耳％用量，乙酸鎂之添加量對低聚合物中之 對苯二甲酸單位計，鎂原子換算爲〇 · 〇 2 1莫耳％用量 ，三丁基磷酸酯之添加量，對低聚合物中之對苯二甲酸單 位計，磷原子換算爲0 · 0105莫耳％用量添加之。 然後’再就上述液相縮聚合反應終了之聚乙烯對苯二 甲酸酯進行固相縮聚合反應，而得固有粘度爲〇 · 8 1 d 1/ g ’密度爲1 · 40g/cm3，乙醒含量爲 1 · 0 P pm之粒狀聚乙烯對苯二甲酸酯。 聚乙烯對苯二甲酸酯之處理 將上述粒狀聚乙烯對苯二甲酸酯3 〇 g ，異丙醇6 0 g和三丁基磷酸酯10 . 3g (對異丙醇計，磷原子換算 爲2重量％ )放入2 0 〇 ^之燒瓶中，迴流下加熱4小時 經濟部智慈財產局員工消費合作社印製 。然後，用異丙醇6 0 g洗淨3次。再於7 0 °C下乾燥 1 6小時’然後在2 8 5 °C下加熱熔融1 0分鐘之後，冷 卻至室溫，由之取得試料測定其乙醛含量之結果爲3 0 ppm。 〔實施例4 6 6 - 2〕 本紙張尺度適用中國國家標準（CNS ) A4規格（210x 297公釐） -163- 585881 A7 B7 五、發明説明（161) 代替異丙醇，改用甲醇’代替三丁基磷酸酯10·3 g ’改用5 · 4 g之三丁基磷酸酯（對甲醇計，磷原子換 算仍爲2重量％ )之外，其他皆依照實施例4 6 6 - 1所 示相同使粒狀聚乙烯對苯二甲酸酯和含磷有機溶媒溶液接 觸’再按照實施例4 6 6 - 1所示相同測定乙醛含量之結 果爲2 8 p p m。 〔實施例4 6 6 — 3〕 代替異丙醇，改用丙酮之外，其他皆按照實施例 4 6 6 - 1相同使粒狀聚乙烯對苯二甲酸酯和含磷有機溶 媒溶液接觸，再按照實施例4 6 6 - 1相同測定乙醛含量 之結果爲4 0 ρ ρ ηι。 〔實施例4 6 6 - 4〕 代替異丙醇，改用己烷之外，其他皆依照實施例 4 6 6 - 1相同使粒狀聚乙烯對苯二甲酸酯和含磷有機溶 媒溶液接觸，再按照實施例4 6 6 - 1相同測定乙醛含量 之結果爲3 5 ρ ρ m。 〔實施例4 6 6 — 5〕 代替三丁基磷酸酯10 · 3g，改用3 · 8g之磷酸 (對異丙醇計，磷原子換算爲2重量％ )之外，其他皆依 照實施例4 6 6 - 1所示使粒狀聚乙燃對苯二甲酸醋和含 磷有機溶媒溶液接觸，再按照實施例4 6 6 - 1相同方法 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）„ 164 - (請先閲讀背面之注意事項再填寫本頁) ▼ 訂 經濟部智慧財產局員工消費合作社印製 585881 A7 B7 五、發明説明（162) 測定乙醛含量之結果爲3 6 p p m。 〔實施例4 6 6 — 1 C〕 使用實施例4 6 6 — 1所採用相同粒狀聚乙烯對苯二 甲酸酯，但不施與含磷有機溶媒溶劑接觸處理，在7 〇艽 下乾燥1 6小時，在2 8 5 t下加熱熔融1 〇分鐘之後， 冷卻至室溫，由此採取試料分析乙醛含量之結果爲5 〇 P P m。 〔比較例4 6 6 — 2〕 代替異丙醇而改用水，代替三丁基磷酸酯1 〇 · 3 g 而改用3 · 8 g之磷酸（對水計，磷原子換算爲2重量％ )之外，其他皆按照實施例4 6 6 — 1同樣使粒狀聚乙烯 對苯二甲酸酯和磷酸水溶液接觸，然後再按照實施例 4 6 6 - 1所示，同樣測定乙醛含量之結果爲4 5 p p m 〇 〔實施例4 6 2 — 1〕 聚酯之製造 例行操作時’反應液可滯留3 3 5 0 0重量份之反應 容器中，連續供應由混合6 4 5 8重量份/小時之高純度 對苯二甲酸和2 6 1 5重量份/小時之乙二醇而調製成之 泥漿，攪拌下，氮氣’ 260°c ’ 0 · 9kg/cni—G 之條件下，進行酯化反應。酯化反應之際，再供應實施例 適财_家縣（CNS ) A4規格(210X297公釐）_ 165 - φ_丨 (請先閱讀背面之注意事項再填寫本頁) "口 經濟部智慧財產局員工消費合作社印製 585881 A7 B7 五、發明説明（163) (請先閱讀背面之注意事項再填寫本頁) 4 9 5 - 1所調製之固態狀鈦化合物，以鈦原子計 〇 · 1 8 7重量份/小時，以及乙酸鎂以鎂原子計 〇.1 8 7重量份/小時添加之。該酯化反應中，蒸餾去 除水和乙二醇之混合液於反應系外。 酯化反應產物（低聚合物）控制在平均滯留時間爲 3 . 5小時而連續抽出到反應系外。 上述所得乙二醇和對苯二甲酸酯之低聚合物之數平均 分子量爲600〜1300 (3〜5聚物）。 低聚合物中之液相縮聚合反應在供應0 . 8 3 1重量 份/小時之磷酸三丁酯中，2 8 0 °C，1 T 〇 r r條件下 進行之。 聚乙烯對苯二甲酸酯之固有粘度（IV)達到〇 . 6 5 d 1 / g爲止所需滯留時間（即液相縮聚合反應時間）爲 9 5分鐘。 該液相縮聚合所得聚乙烯對苯二甲酸酯在氮氣中，約 1 7 0 t下進行結晶化2小時之後，塡充於塔型固相聚合 反應機中，氮氣中2 1 0 °C下進行固相縮聚合反應1 4小 時。 經濟部智慧財產局員工消費合作社印製 按照上述所得聚乙烯對苯二甲酸酯之鈦原子含量爲 2 5 p pm，鎂原子含量爲2 5 p pm，鈦原子/鎂原子 莫耳比率爲0 · 5 ，固有粘度爲0 · 85d Ι/g ，密度 爲1 . 40g/cin3，乙酸含量爲1 · Oppm。 將2 · 5 kg之上述聚乙烯對苯二甲酸酯浸漬在容有 0 · 0 6 9 5重量％之磷酸三丁酯水溶液4 k g之不銹鋼 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）-166 - 585881 Λ7 B7 五、發明説明（164) (請先閱讀背面之注意事項再填寫本頁) 容器中，直接保持在室溫下4小時之後，分離粒狀聚乙儲 對苯二甲酸酯和磷酸三丁酯水溶液，排除水分後，在 1 6 0 °C下氮氣流中乾燥5小時。所得聚乙烯對苯二甲酸 酯之乙醛含量爲1 · 0 p pm。該聚乙烯對苯二甲酸酯按 照上述方法成型爲階梯狀矩形成型物，測定其乙醛含爲 9 · Oppm，成型前後之乙醛含量相差8 · Oppm， 固有粘度爲0.821dl/g。 〔實施例4 6 2 — 2〕 使用實施例4 6 2 - 1所採用相同之粒狀聚乙烯對苯 二甲酸酯2 · 5kg ，浸漬於容有〇 · 0695重量％之 磷酸三甲酯水溶液4 k g之不銹鋼容器中。繼之，將容有 聚乙烯對苯二甲酸酯和磷酸三甲酯水溶液之不銹鋼容器， 自外部加熱，控制內溫在9 5 °C，保持4小時而行加熱處 理之後，分離粒狀聚乙烯對苯二甲酸酯和磷酸三甲醋水溶 液’排除水分後’在1 6 0 °C下，氮氣流下乾燥5小時。 使用所得聚乙烯對苯二甲酸酯按照上述方法成型爲階梯狀 矩形成型物。測定其乙醛含量爲9 · 5 p P m，成型前後 經濟部智慧財產局員工消費合作社印製 之乙醛含量之差異爲8 · 5 p Pm，固有粘度爲 0 · 8 0 2 d 1 / g。 〔實施例462 - 1C〕 使用實施例4 6 2 — 1所採用相同粒狀聚乙烯對苯二 甲酸酯，但不跟含磷水溶液接觸處理，按照上述方法成型 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）-167 - 585881 A7 B7 __ 五、發明説明（165) ^ 爲階梯狀矩形成型物，其乙醛含量爲2 0 p p m ’成型前 後之乙醛含量差値爲1 9 P pm ’固有粘度爲〇 · 8 3 3 d 1 / g。 〔比較例4 6 2 — 2〕 代替碟酸三甲醋水溶液’改用相问濃度之碟酸水丨谷液 之外，其他皆按照實施例4 6 2 - 1所示相同方法處理粒 狀聚乙烯對苯二甲酸酯。使用所得聚乙烯對苯二甲酸醋按 照上述方法成型爲階梯狀矩形成型物，測定其乙醛含量爲 1 3 ppm，成型前後之乙醛含量之差値爲1 2PPm ’ 固有粘度爲0.814dl/g° 〔實施例4 6 2 - 3〕 例行操作時，反應液可滯留3 3 5 0 0重量份之反應 容器中，連續供應由混合6 3 2 9重量份/小時之高純度 對苯二甲酸和1 2 9重量份/小時之異苯二甲酸以及 2 6 1 5重量份/小時之乙二醇而調製成之泥漿，攪拌下 ，氮氣中，2 6 0 °C，0 · 9 k g / c m2 _ G之條件下， 進行酯化反應。該酯化反應之際，供應實施例4 6 2 - 1 所調製之固態狀鈦化合物，以鈦原子計0 · 1 1 2重量份 /小時，以及乙酸鎂以鎂原子計，0 · 1 8 7重量份/小 時。該酯化反應中，蒸餾排除水和乙二醇之混合液於反應 系外。 酯化反應產物（低聚合物）控制其平均滯留時間爲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-168 - — (請先閱讀背面之注意事項再填寫本頁)A V. Description of the invention (153) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs O un p inch 〇jp inch · t · iv〇un 〇ψ it < 1 inch O OO oo opi 4 ON un 〇ON inch o r -ow " 丨 崤 o oo CNi csi o CN) VO o oc oi o inch οο o CN 1 c5 cn cn cs τ3 | CN inch · OO o; 〇 \ un inch inch O oo On inch oo η-3 u〇 un 06 un un v〇VO 1 ___H cn wo s MD un ss un υη s υη m 薇 锲 1 1 1 1 1 1 1 un 1 〇un O CN 1 p 〇o4 1 §: i 鎞 ptic7 mu. ΠZΙ cn rsi Sauce 1 o cn oo r—H VsO oov〇1 un 1 1 1 1 1 1 t 1 ί] g 1 '< 锲 τώΊ o wn o un 〇cn p ^ i 1 1 0 01 C ^ * 1 1 1 1 in ii CN 1 < p 1 time < Π B υο Anm 丄 1 wn CXi i Ή HH n 1: 1: ψ 1 in 1: IS: mm N3 wo is called oo < T) csi oo -H a ίϋ ni 1 i El EE fi K < Π CNl OO un csi oo < ίίΙ a ^ ϋ: 1: 1: ni 4 EE 1: fK painting < 111 H 1 csi rn v〇u _ 丨 丨 dragon 1 vxp rp 1 oo On u cn 〇i 1, A ti 1 us § S \ y ^) CN C < l 〇V / ^ J sl / ^ N gg | V ^ vsl / ^ vs 1 / ^ s 1 / ^ S 1 / ^ sssmmm ^) mi ^ J w 1 m ^ iw) mi vr) m capsule mm mm rong mm piano IK u face IS S -¾ -¾ uu IK sn IS -¾ ---------— (Please read the precautions on the back before filling this page) , \ = The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 156-Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Industrial Cooperative Cooperative 585881 A7 B7 V. Description of the invention (154) [Example 4 6 4-1] Granular polyethylene terephthalate 2. 5 kg with an inherent viscosity of 0.85 d I / g, a density of 1.4 g / cm3, and an acetaldehyde content of 1. 5 p pm, impregnated The granular polymer was separated in a stainless steel container containing 4 kg of an aqueous solution of trimethyl phosphate of 0. 0695% by weight (16 1 ppm in terms of phosphorus atom conversion) and kept at room temperature for 4 hours. Alkenyl acid aqueous solution of trimethyl phosphate and, after exclusion of moisture, and dried in a nitrogen stream at 1 6 0 ° C for 5 hours. The obtained polyethylene terephthalate was formed into a step-shaped rectangular shaped article using the aforementioned method, the acetaldehyde content thereof was 7.7 ppm, and the intrinsic viscosity was 0 · 821 dl / g. [Example 4 6 4-2] The same granular polyethylene terephthalate as used in Example 4 6 4-1 was used. 2.5 kg was immersed in a capacity of 0.0695% by weight (the phosphorus atom was converted to 16 1 ppm) trimethyl phosphate aqueous solution in a 4 kg stainless steel container. Next, a stainless steel container containing polyethylene terephthalate and trimethyl phosphate aqueous solution was heated from the outside, and its internal temperature was controlled at 95 ° C. After 4 hours of heat treatment, granular polyethylene was separated. After terephthalic acid and trimethyl phosphate aqueous solution was removed, it was dried in a nitrogen stream at 160 ° C for 5 hours. Using the obtained polyethylene terephthalate, it was formed into a step-shaped rectangular shaped article 'according to the method described above. The acetaldehyde content was 8.5 ppm, and the intrinsic viscosity was 0.802 d I / g. [Example 4 6 4 — 1 C] This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 仂 7------------- Ί--, 玎- ---- «(Please read the precautions on the back before filling out this page} 585881 A7 B7 V. Description of the invention (155) (Please read the precautions on the back before filling out this page) Use Example 4 6 4-1 Using the same granular polyethylene terephthalate:;: Formate, but without contact treatment with phosphorus-containing aqueous solution, directly formed into a step-shaped rectangular shaped article by the above method, the acetaldehyde content is 11 ppm, and the inherent viscosity is 0. 833d 1 / g. [Example 464-2C] Instead of the trimethyl phosphate aqueous solution, the phosphoric acid aqueous solution of the same concentration (0. 0508% by weight, phosphorus atom converted to 161 ppm) was used. -Treat the granular polyethylene terephthalate in the same way as shown in 1. Use the obtained polyethylene terephthalate to form a stepped rectangular shaped article according to the above method, with an acetaldehyde content of 8 · 3ppm and an inherent viscosity It is 0.814 d 1 / g. [Comparative Example 4 6 4 — 3] Employees' cooperation in intellectual property of the Ministry of Economic Affairs Print instead of the trimethyl phosphate aqueous solution, except that the phosphoric acid aqueous solution is used, and the rest are treated in the same manner as shown in Example 4 6 4-2. The granular polyethylene terephthalate is used. The obtained polyethylene terephthalate is used. The ester was formed into a step-shaped rectangular shaped article according to the method described above, with an acetaldehyde content of 10 · 0 PP m and an intrinsic viscosity of 0.788 dl / g. [Example 4 6 5 — 1] Preparation of solid titanium-containing compound 10 5 0 d of deionized water was weighed in a glass sintered glass. After cooling in an ice bath, 5 g of titanium tetrachloride was added dropwise with stirring. The size of the paper to be chlorinated shall comply with Chinese national standards ( CNS) A4 specification (210X297 mm) -158- 585881 A7 B7 V. Description of the invention (156) After the hydrogen generation is terminated, it is taken out from the ice bath, and the 25% ammonia water adjustment solution is added dropwise with stirring to p Η 8. The precipitate of the generated titanium hydroxide was filtered and separated by a pressure filter under a pressure of 3 kg / cm2. Then, the obtained precipitate of the titanium hydroxide was washed 5 times with deionized water. The liquid phase separation was pressurized under the pressure of 3 kg / c m2 in the same manner as above. The titanium hydroxide after washing is dried under reduced pressure at 70 ° C and 10 Torr for 18 hours to remove water to obtain a solid titanium-containing compound. Before the obtained solid titanium-containing compound is shaken, First crush into granules of about 10 # m. During the routine operation of polyethylene terephthalate production, the reaction solution can be retained in a reaction container of 3,500 parts by weight, and continuously supplied by mixing with high purity The slurry prepared from terephthalic acid and ethylene glycol was subjected to an esterification reaction under agitation in nitrogen at 260 ° C and 0.9 kg / c rrf-G. The above-mentioned slurry of high-purity terephthalic acid and ethylene glycol is prepared by mixing high-purity terephthalic acid and ethylene glycol at a ratio of 6 4 5 8 parts by weight / hour and 2 6 15 parts by weight / hour, respectively. . In the esterification reaction, a mixed solution of water and ethylene glycol is distilled out of the reaction system. The esterification reaction product (oligomer) is controlled to keep the average retention time at 3.5 hours and continuously withdraw from the reaction system. The number average molecular weight of the oligomers of the ethylene glycol and terephthalic acid obtained above is 600 to 1300 (3 to 5 polymers). In the above-mentioned low polymer, a solid titanium-containing compound is added, and the acetic acid paper size is in accordance with the Chinese National Standard (CNS) A4 specification (21〇 > < 297 mm) --------- • pack- -(Please read the note on the back before filling this page) Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -159- 585881 A7 _B7____ 5. Description of the invention (157) Magnesium and tributyl phosphate, at 285 ° C Under the conditions of 1 Torr, a liquid phase condensation polymerization reaction was performed to obtain a polyethylene terephthalate having an intrinsic viscosity of 0.65 d Ι / g. The amount of solid titanium-containing compound added, based on the terephthalic acid unit in the low polymer, the titanium atom is converted to 0.02 mol%, the amount of magnesium acetate added, and the amount of p-benzene in the low polymer. Dicarboxylic acid unit, magnesium atom is converted to 0. 002 1 mol% dosage, tributyl phosphate added amount, for terephthalic acid unit in low polymer, phosphorus atom is converted to 0 · 0 1 0 It is added at 5 mol%. Then, 'the polyethylene terephthalate after the above-mentioned liquid phase condensation polymerization reaction is further subjected to solid phase condensation polymerization to obtain an inherent viscosity of 0.81 d 1 / g', and a degree of 1.40g / cm3, Granular polyethylene terephthalate with an acetone content of 1.0 ppm. Treatment of polyethylene terephthalate 10 g of the aforementioned granular polyethylene terephthalate and 40 g of isopropyl alcohol were put in a 100 flask and heated under reflux for 4 hours. Then dried at 70 ° C for 16 hours, heated and melted at 2 70 ° C for 6 minutes, cooled to room temperature, and then took a sample to measure the acetaldehyde content. The result was 5.2 ppm. [Example 4 6 5-2] Instead of isopropyl alcohol and using methanol, the same method as shown in Example 4 6 5-1 was used to contact the granular polyethylene terephthalate with an organic solvent, according to Example 4 6 5 — The same method as shown in 1 is used to determine the paper size of the second paper. It is applicable to the Chinese National Standard (CNS) 8-4 specification (210X297 mm) I ---------- (Please read the precautions on the back before filling this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -160- 8 5 8 A7 B7 ------- ^ V. Description of the Invention (158) The result of the wake content is 6.4 ppm. [Example 4 6 5 — 3] -------- ΦI — (Please read the precautions on the back before filling out this page} Instead of isopropyl alcohol, use acetone, otherwise follow the example 4 6 The granular polyethylene terephthalate was contacted with an organic solvent in the same manner as shown in 5-1, and the content of acetonitrile was measured according to the same method as shown in Example 4 6 5-1. The result was 6.7 p pm. Example 4 6 5-4] Instead of isopropanol 'and using hexane, the same method as in Example 4 6 5-1 was used to contact granular polyethylene terephthalate with an organic solvent, and then Example 4 The result of the measurement of Yili in the same method as shown in Example 6 6-5 was 6. 8pprn. [Example 4 6 5-1 C] Example 4 printed and used by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 6 5-1 The same granular polyethylene terephthalate is used, but it is not treated with organic solvents. It is dried at 70 ° C for 16 hours', and then heated and melted at 270 ° C for 6 minutes, and then cooled to room temperature. As a result, the acetaldehyde content measured from the sample was 7.3 ppm. [Example 4 6 6 — 1] Solid state containing titanium Preparation of the compound: Weigh 500 g of deionized water in a glass burner with a temperature of 100 Om. After cooling in an ice bath, 5 g of titanium tetrachloride was added dropwise with stirring. To be chlorinated The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -161-585881 A7 B7 V. Description of the invention (159) (Please read the precautions on the back before filling this page) After the hydrogen generation is terminated, the ice bath Take out '25% ammonia water dropwise while stirring and adjust the solution to P Η 8 °. The precipitate of hydrazine hydroxide is filtered under a pressure of 3 kg / c η and filtered with a pressure filter. Then 'the obtained titanium The precipitate of the hydroxide was washed 5 times with deionized water. The solid-liquid phase was separated after washing, and the pressure filtration was performed under the pressure of 3 kg / c π in the same manner as above. The washed titanium hydroxide The solid titanium-containing compound was dried under reduced pressure at 70 ° C. for 10 hours to remove water for 18 hours to obtain a solid titanium-containing compound. The obtained solid titanium-containing compound was first pulverized into particles of about 10 μm before use. Manufacturing of polyethylene terephthalate During the routine operation of Fei Co., Ltd., the reaction solution can be retained in a reaction container of 3,500 parts by weight, and a slurry prepared by mixing high-purity terephthalic acid and ethylene glycol can be continuously supplied. The esterification reaction was carried out at 260 ° C and 0.9 kg / crri-G. The above-mentioned slurries of high-purity terephthalic acid and ethylene glycol were prepared from high-purity terephthalic acid and ethylene glycol respectively at 6 4 5 8 parts by weight / hour and 2 6 1 5 parts by weight / hour are mixed and prepared. In the esterification reaction, a mixed solution of water and ethylene glycol is distilled away from the reaction system. The esterification reaction product (oligomer) was controlled to have an average residence time of 3.5 hours while continuously withdrawing from the reaction system. The number average molecular weight of the oligomers of ethylene glycol and terephthalic acid obtained above is 600 ~ 1300 (3 ~ 5 polymers) ° This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) _ 162- 585881 A7 B7 V. Description of the invention (16C?) (Please read the notes on the back before filling this page) Add the solid titanium-containing compound, magnesium acetate and tributyl phosphate to the low polymer obtained above. t: A liquid phase polycondensation reaction was performed under the conditions of ITo r I * to prepare a polyethylene terephthalate having an inherent viscosity of 0.65 d 1 / g. The amount of solid titanium-containing compound added to the terephthalic acid unit in the low polymer is calculated as 0 · 0 2 1 mol%, and the amount of magnesium acetate added to the terephthalic acid in the low polymer. Formic acid units, magnesium atoms are converted to 0.002 mol%, tributyl phosphate is added, and for terephthalic acid units in low polymers, phosphorus atoms are converted to 0. 0105 mol%. Dosage is added. Then 'the solid phase polycondensation reaction is performed again on the polyethylene terephthalate after the above-mentioned liquid phase polycondensation reaction, and the intrinsic viscosity is 0.81 d 1 / g' the density is 1.40g / cm3, and Granular polyethylene terephthalate with an awake content of 1.0 PM. Treatment of polyethylene terephthalate: 30 g of the above-mentioned granular polyethylene terephthalate, 60 g of isopropyl alcohol, and 10.3 g of tributyl phosphate (p-isopropyl alcohol, phosphorus atom) (Converted to 2% by weight.) Put it into a 200 ^ flask, and heat it under reflux for 4 hours. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Then, it was washed 3 times with 60 g of isopropyl alcohol. It was dried at 70 ° C for 16 hours', and then heated and melted at 285 ° C for 10 minutes. After cooling to room temperature, a sample was taken to determine the content of acetaldehyde, which was 30 ppm. [Example 4 6 6-2] This paper size applies the Chinese National Standard (CNS) A4 specification (210x 297 mm) -163- 585881 A7 B7 V. Description of the invention (161) Replace isopropyl alcohol, use methanol 'instead Tributyl phosphate 10 · 3 g 'Change to 5.4 g of tributyl phosphate (to methanol, phosphorus atom conversion is still 2% by weight), the rest are in accordance with Example 4 6 6-1 The results showed that the granular polyethylene terephthalate and the phosphorus-containing organic solvent solution were brought into contact with each other, and then the acetaldehyde content was measured in the same manner as shown in Example 4 6 6-1 to be 28 ppm. [Example 4 6 6 — 3] Instead of isopropyl alcohol and using acetone, the same procedure as in Example 4 6 6-1 was used to contact granular polyethylene terephthalate with a phosphorus-containing organic solvent solution. The acetaldehyde content was measured in the same manner as in Example 4 6 6-1 and found to be 40 ρ ρ η η. [Example 4 6 6-4] Instead of isopropyl alcohol and using hexane, the same procedure as in Example 4 6 6-1 was used to contact the granular polyethylene terephthalate and the phosphorus-containing organic solvent solution. The result of measuring the acetaldehyde content in the same manner as in Example 4 6 6-1 was 3 5 ρ ρ m. [Example 4 6 6-5] Instead of 10 · 3 g of tributyl phosphate, use 3 · 8 g of phosphoric acid (for isopropyl alcohol, the phosphorus atom is converted to 2% by weight). As shown in 6 6-1, the granular polyethylene terephthalate and phosphorus-containing organic solvent solution were brought into contact, and then the same method as in Example 4 6 6-1 was used. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) „164-(Please read the precautions on the back before filling out this page) ▼ Order printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 585881 A7 B7 V. Description of the invention (162) The result of measuring the acetaldehyde content is 3 6 ppm. [Example 4 6 6-1 C] The same granular polyethylene terephthalate as used in Example 4 6 6-1 was used, but without contact treatment with a phosphorus-containing organic solvent. The sample was dried for 16 hours, heated and melted at 285 t for 10 minutes, and then cooled to room temperature. As a result, the sample was analyzed for acetaldehyde content and was 50 ppm. [Comparative Example 4 6 6-2] Water instead of isopropanol, 3 g of tributyl phosphate instead of 3 g Except for 8 g of phosphoric acid (the phosphorus atom is converted to 2% by weight in terms of water), the granular polyethylene terephthalate and phosphoric acid aqueous solution were contacted in the same manner as in Example 4 66-1, and then according to As shown in Example 4 6 6-1, the result of the same measurement of the acetaldehyde content was 4 5 ppm. [Example 4 6 2 — 1] During the routine operation of the production of polyester, the reaction solution can retain 3 3 5 0 0 weight In a reaction container, a slurry prepared by mixing 6 4 5 8 parts by weight per hour of high-purity terephthalic acid and 2 6 1 5 parts by weight per hour of ethylene glycol was continuously supplied, under stirring, nitrogen '260 ° c '0 · 9kg / cni-G, the esterification reaction is carried out. At the time of the esterification reaction, the example is suitable for supply_ 家 县 （CNS） A4 size (210X297mm) _ 165-φ_ 丨(Please read the precautions on the back before filling this page) " Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and Economics 585881 A7 B7 V. Invention Description (163) (Please read the precautions on the back before filling out this page) 9 5-1 solid titanium compound prepared as titanium atom 0.1 8 7 parts by weight / hour And magnesium acetate is added in terms of magnesium atom 0.1 8 parts by weight / hour. In the esterification reaction, the mixed solution of water and ethylene glycol is distilled out of the reaction system. Control of the esterification reaction product (oligomer) The average retention time was 3.5 hours and continuously extracted outside the reaction system. The number average molecular weight of the low polymer of the ethylene glycol and terephthalate obtained above was 600 to 1300 (3 to 5 polymers). The liquid-phase polycondensation reaction in the oligomer was carried out in a supply of 0.831 parts by weight / hour of tributyl phosphate at 280 ° C and 1 T 〇 r r. The retention time (that is, the liquid phase condensation polymerization reaction time) required for the intrinsic viscosity (IV) of polyethylene terephthalate to reach 0.65 d 1 / g is 95 minutes. The polyethylene terephthalate obtained by the liquid phase condensation polymerization was crystallized in nitrogen at about 170 t for 2 hours, and then charged into a tower-type solid phase polymerization reactor in a nitrogen atmosphere at 2 10 ° C. The solid phase condensation polymerization was carried out for 14 hours. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the polyethylene atomic terephthalate obtained in accordance with the above with a titanium atom content of 25 p pm, a magnesium atom content of 2 5 p pm, and a titanium atom / magnesium atom molar ratio of 0. · 5, intrinsic viscosity is 0 · 85d Ι / g, density is 1.40g / cin3, and acetic acid content is 1 · Oppm. 2.5 kg of the above polyethylene terephthalate was impregnated in a stainless steel containing 4 kg of a 0.5% by weight aqueous solution of tributyl phosphate and 4 kg of stainless steel. This paper is sized to Chinese National Standard (CNS) A4 specifications ( 210X 297mm) -166-585881 Λ7 B7 V. Description of the invention (164) (Please read the notes on the back before filling this page) In the container, keep it directly at room temperature for 4 hours, then separate the granular polyethylene storage After terephthalate and tributyl phosphate aqueous solution was removed, the mixture was dried in a nitrogen stream at 160 ° C for 5 hours. The acetaldehyde content of the obtained polyethylene terephthalate was 1.0 p pm. This polyethylene terephthalate was formed into a stepped rectangular shaped article according to the method described above, and its acetaldehyde content was measured to be 9 · Oppm. The acetaldehyde content before and after the molding was different by 8 · Oppm, and the intrinsic viscosity was 0.821 dl / g. [Example 4 6 2-2] The same granular polyethylene terephthalate 2.5 kg as that used in Example 4 6 2-1 was used, and it was immersed in a 0.0695% by weight trimethyl phosphate aqueous solution. 4 kg stainless steel container. Next, a stainless steel container containing polyethylene terephthalate and trimethyl phosphate aqueous solution was heated from the outside, and the internal temperature was controlled at 95 ° C. After being maintained for 4 hours, the granular polymer was separated. Aqueous solutions of ethylene terephthalate and trimethyl phosphate were 'dried out' at 160 ° C for 5 hours under nitrogen flow. Using the obtained polyethylene terephthalate, a step-shaped rectangular shaped article was formed according to the method described above. The acetaldehyde content was determined to be 9 · 5 p P m. The difference in the content of acetaldehyde printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs before and after molding was 8. 5 p Pm, and the inherent viscosity was 0 · 8 0 2 d 1 / g. . [Example 462-1C] The same granular polyethylene terephthalate as used in Example 4 6 2-1 was used, but it was not contacted with the phosphorus-containing aqueous solution. It was formed in accordance with the above method. CNS) A4 specification (210X 297 mm) -167-585881 A7 B7 __ V. Description of the invention (165) ^ is a stepped rectangular shaped product with an acetaldehyde content of 20 ppm. The difference in acetaldehyde content before and after molding is 1 9 P pm 'intrinsic viscosity is 0.83 3 d 1 / g. [Comparative Example 4 6 2-2] Instead of the aqueous solution of trimethyl vinegar, the solution was replaced with the dish acid water of the same concentration, and the grain solution was processed in the same manner as in Example 4 6 2-1 Terephthalate. The obtained polyethylene terephthalate was formed into a stepped rectangular shaped article according to the above method, and its acetaldehyde content was measured to be 13 ppm. The difference between the acetaldehyde content before and after molding was 1 2 PPm. The intrinsic viscosity was 0.814 dl / g. ° [Example 4 6 2-3] During the routine operation, the reaction solution can be retained in a reaction container of 3 3 5 0 0 0 parts by weight, and high purity terephthalic acid mixed by 6 3 2 9 parts by weight / hour is continuously supplied. And 1 2 9 parts by weight of isophthalic acid and 2 6 15 parts by weight of ethylene glycol per hour, and a slurry prepared by stirring under nitrogen at 2 60 ° C and 0 · 9 kg / c m2 _ G, the esterification reaction. In the case of this esterification reaction, a solid titanium compound prepared in Example 4 6 2-1 was supplied, with a titanium atom of 0 · 1 1 2 parts by weight per hour and a magnesium acetate of magnesium atom at 0 · 1 8 7 Parts by weight / hour. In this esterification reaction, a mixed solution of water and ethylene glycol is distilled out of the reaction system. The average retention time of the esterification reaction product (oligomer) is controlled to the paper size of China National Standard (CNS) A4 (210X297 mm) -168--(Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局a(工消費合作社印製 585881 A7 B7 五、發明説明（166) 3 . 5小時而連續抽出到反應系外。 (請先閱讀背面之注意事項再填寫本頁) 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲6〇〇〜1 3 00 (3〜5聚物）。 低聚合物之液相縮聚合反應在供應0 . 8 3 1重量份 /小時之磷酸三丁酯下，於2 8 0 t，1 T 〇 r r之條件 進行。 聚乙烯對苯二甲酸酯之固有粘度（IV)到達〇 · 6 5 d 1 / g爲止所需滯留時間（即液相縮聚合反應時間）爲 1 1 5分鐘。 經液相縮聚合反應而得之聚乙烯對苯二甲酸酯，在氮 氣中約1 7 0 °C下進行2小時之結晶化後，塡充在塔型固 相聚合反應機中，氮氣中2 1 〇 °C下進行1 7小時之固相 聚合反應。 按照上述所得聚乙烯對苯二甲酸酯之鈦原子含量爲 1 5 p pm，鎂原子含量爲2 5 p pm，鈦原子/鎂原子 莫耳比率爲〇 · 3 ，固有粘度爲〇 · 83d Ι/g ，密度 爲1 · 40g/cm3，乙醛含量爲〇 . 9ppm。 經濟部智慧財產局員工消費合作社印製 將2 · 5 kg之上述聚乙烯對苯二甲酸酯浸漬在容有 0 · 0 6 9 5重量％之磷酸三甲酯水溶液4 k g之不銹鋼 容器中，在常溫下保持4小時後，分離粒狀聚乙烯對苯二 甲酸酯和磷酸三甲酯水溶液，排除水分後，在i 6 〇 t， 氮氣流中乾燥5小時。所得聚乙烯對苯二甲酸酯之乙II含 量爲0 · 8 p pm。該聚乙烯對苯二甲酸酯按照上述方法 成型爲階梯狀矩形成型物’測定其乙醛含量爲8 . 2 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） •169- 1 8 8 5 8 5 A71T Intellectual Property Bureau of the Ministry of Economy a (printed by the Industrial and Consumer Cooperatives 585881 A7 B7 V. Invention Description (166) 3.5 hours and continuously withdrawn from the reaction system. (Please read the precautions on the back before filling out this page) The number average molecular weight of the obtained low polymer of ethylene glycol and terephthalic acid is 600 ~ 1 3 00 (3 ~ 5 polymer). The liquid phase polycondensation reaction of the low polymer provides 0.8 3 1 parts by weight Per hour under tributyl phosphate at 280 t, 1 T rr. The inherent viscosity (IV) of the polyethylene terephthalate is required to stay until it reaches 0.65 d 1 / g. The time (that is, the liquid phase condensation polymerization reaction time) is 115 minutes. The polyethylene terephthalate obtained through the liquid phase condensation polymerization is crystallized in nitrogen at about 170 ° C for 2 hours. Then, it was charged in a tower-type solid-phase polymerization reactor and subjected to a solid-phase polymerization reaction at 2 10 ° C. in nitrogen for 17 hours. The titanium atom content of the polyethylene terephthalate obtained according to the above was 15 p pm, magnesium atom content is 2 5 p pm, titanium atom / magnesium atom molar ratio is 0.3, intrinsic viscosity is 0. 83d Ι / g, density 1.40g / cm3, acetaldehyde content 0.9 ppm. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 2.5 kg of the above polyethylene terephthalate was impregnated in the container 0 · 0 6 9 5 wt% trimethyl phosphate aqueous solution in a 4 kg stainless steel container. After keeping at room temperature for 4 hours, the granular polyethylene terephthalate and trimethyl phosphate aqueous solution are separated, and the water is removed. , Dried in a nitrogen stream at i 6 〇t for 5 hours. The ethylene II content of the obtained polyethylene terephthalate was 0 · 8 p pm. The polyethylene terephthalate was formed into a step shape according to the method described above. Rectangular moldings' acetaldehyde content is 8.2. This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) • 169- 1 8 8 5 8 5 A7

五、發明説明（167 ) P P m，成型前後之乙醛含量之差値爲7 〇 4 p p 9 d 1 / g。 有粘度爲Ο . 8 固 經濟部智慈財產局員工消費合作社印製 〔實施例4 6 2 — 4〕 將實施例4 6 2 - 3中行固相聚合之聚乙烯對 酸酯在不銹鋼容器中浸漬於9 5 t之異丙醇，加熱 4小時。 分離聚乙烯對苯二甲酸酯和異丙醇之後，在丨6 〇它 ，氮氣流中乾燥5小時。所得聚乙烯對苯二甲酸酯之乙醛 含量爲0 . 9 p p m。該聚乙烯對苯二甲酸酯按照上述方 法成型爲階梯狀矩形成型物，測定其乙醛含量爲9 · 5 ppm’成型前後之乙醛含量之差値爲8·6ppm，固 有粘度爲0 . 81〇d l/g。 〔實施例4 6 2 — 5〕 實施例4 6 2 - 3中經固相聚合反應之聚乙烯對苯二 甲酸醋在不銹鋼容器中浸漬於含磷酸三丁酯之異丙醇溶液 中（磷酸三丁酯爲〇 · 〇69 5重量，並加熱保持2 小時。 分離聚乙烯對苯二甲酸酯和異丙醇溶液之後，在 1 6 0 °C，氮氣中乾燥5小時，所得聚乙烯對苯二甲酸酯 之乙醛含量爲〇 · 7 p p m。該聚乙烯對苯二甲酸酯按照 上述方法成型爲階梯狀矩形成型物，測定其乙醛含量爲 8.2ppm，成型前後之乙醛含量之差値爲7.5 本紙張尺度適用中國國家標率（CNS ) A4規格（210X 297公釐） ----^---、訂------*f (請先閱讀背面之注意事項再填寫本頁) 二甲 保持 並 -170- 585881 A7 B7____ 五、發明説明（168) ppm，固有粘度爲Ο · 8〇8d 1/g。 (請先閱讀背面之注意事項再填寫本頁) 〔實施例4 6 3 — 1〕 聚酯之製造 例行操作時，反應液可滯留3 3 5 0 0重量份之反應 容器中，連續供應由混合6 4 5 8重量份/小時之高純度 對苯二甲酸和2 9 0 9重量份/小時之乙二醇而調製成之 泥漿，攪拌下，氮氣中，26〇°C ’〇· 9kg / cm2 — G之保持條件下，進行酯化反應。該酯化反應之際，供應 實施例4 9 5 — 1所調製之固態狀鈦化合物以鈦原子計 〇.1 8 7重量份/小時和乙酸鎂以鎂原子計， 0 . 1 8 7重量份/小時。該酯化反應中，蒸餾排除水和 乙二醇之混合液於反應體系外。 酯化反應產物（低聚合物）控制在平均滯留時間爲 3 · 5小時而連續抽出到反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲600〜1300 (3〜5聚物）。 經濟部智慧財產局員工消費合作社印製 低聚合物之液相縮聚合反應在供應0 . 8 3 1重量份 /小時之磷酸三丁酯中，2 8 0 °C，1 Τ ο I· r之條件下 進行。 聚乙烯對苯二甲酸酯之固有粘度（IV)到達〇 . 5 5 d 1 / g爲止所需滯留時間（即液相縮聚合反應時間）爲 8 7分鐘。 然後，經液相縮聚合反應而得聚乙烯對苯二甲酸酯， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -171 - 585881 A7 B7 五、發明説明（169) (請先閲讀背面之注意事項再填寫本頁) 在氮氣中，約1 7 0 °C下進行2小時之結晶化後，塡充在 塔型之固相聚合反應機中，氮氣中，2 1 Ot下進行25 小時之固相聚合反應。 按照上述所得聚乙烯對苯二甲酸酯之鈦原子含量爲 2 4 p p m，鎂原子含量爲2 4 P P m，鈦原子/鎂原子 之莫耳比率爲〇 . 5 ，固有粘度爲0 · 760d Ι/g， 密度爲1 · 40g/cm3，環狀三聚物含量爲0 · 3重量 %。 將2 · 5 kg之上述聚乙烯對苯二甲酸酯在不銹鋼容 經濟部智慈財產局員工消費合作社印製 器中浸漬於0 . 0 6 9 5重量％之磷酸三甲酯水溶液4 k g中。在常溫下保持4小時後，分離聚乙烯對苯二甲酸 酯和磷酸三甲酯水溶液，排除水分之後，在1 6 0 °C，氮 氣中乾燥5小時。所得聚乙烯對苯二甲酸酯之環狀三聚物 含量爲0 · 3 0重量％ (X重量％)。該聚乙嫌對苯二甲 酸酯按照上述方法成型爲階梯狀矩形成型物，測定其環狀 三聚物含量爲〇 · 3 5重量％。成型前後之環狀三聚物含 量之差値爲0 · 05重量％ (y重量％) ，一 〇 · 2x + 〇· 2之値爲〇 · 14 ，固有粘度爲0 · 825d 1/g 〔實施例4 6 3 — 2〕 使用實施例4 6 3 - 1中所採用相同之粒狀聚乙烯對 苯二甲酸2·5kg在不銹鋼容器中浸漬於0·0695 重量％之磷酸三甲酯水溶液4 k g中。然後，將容有聚乙 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -172· 585881 A7 B7 一 - - ....... 五、發明説明（170) (請先閱讀背面之注意事項再填寫本頁) 烯對苯二甲酸酯和磷酸三甲酯水溶液之不銹鋼容器從外部 加熱，控制內溫在9 5 °C，進行加熱處理並保持4小時之 後，分離粒狀聚乙烯對苯二甲酸酯和磷酸三甲醋水溶液· 排除水分之後’在1 6 0 °C，氮氣流中乾燥5小時。所得 聚乙烯對苯二甲酸酯之環狀三聚物含量爲0 · 3 0重量％ (X重量％)。使用該聚乙烯對苯二甲酸酯按照上述方法 成型爲階梯狀矩形成型物之環狀三聚物含量爲0 · 3 3重 量％ ( X重量％)，成型前後之環狀三聚物含量之差値爲 0.03 重量％(y 重量％) ，— 〇·2〇χ + 0·2 之 値爲0 · 134，固有粘度爲〇 · 81 Id Ι/g。 〔實施例4 6 3 — 1 C〕 使用實施例4 6 3 - 1中所採用相同之粒狀聚乙烯對 苯二甲酸酯，但不用含磷水溶液接觸處理。按照上述方法 成型爲階梯狀矩形成型物。該階梯狀矩形成型物之環狀三 聚物含量爲0 · 5 2重量％ ( X重量％)，成型前後之環 狀三聚物含量之差異爲0.22重量％(7重量％)’ 經濟部智慧財4局員工消費合作社印製 一0 · 2〇x + 0 · 2之値爲〇 · 096 ’固有粘度爲 0 · 8 3 3 d 1 / g。 〔實施例463 — 3〕 例行操作時，反應液可滯留3 3 5 0 0重量份之反應 容器中，連續供應由混合6 3 2 9重量份/小時之高純度 對苯二甲酸和1 2 9重量份/小時之異苯二甲酸以及 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -173- 585881 A7 _ B7_ _ 五、發明説明（171) 2 6 1 5重量份/小時之乙二醇而調製之泥漿，攪拌下’ 氮氣中，保持2 6 0 °C，〇 · 9 k g / c nf — G之條件下 (請先閲讀背面之注意事項再填寫本頁) ，進行酯化反應。該酯化反應之際，再供應實施例 4 6 3 - 1中所調製相同固態狀鈦化合物以鈦原子計， 0 · 1 1 2重量份/小時和乙酸鎂，以鎂原子計， 〇· 1 8 7重量份/小時。該酯化反應中，蒸餾排除水和 乙二醇之混合液於反應體系外。 酯化反應產物（低聚合物）控制在平均滯留時間爲 3 · 5小時而連續抽出到反應系外。 上述所得乙二醇和對苯二甲酸之低聚合物之數平均分 子量爲600〜1300(3〜5聚物）。 低聚合物在供應0 . 8 3 1重量份/小時之磷酸三丁 酯中，2 8 0 °C，1 Τ ο I· r之條件下進行液相縮聚合反 應。 聚乙烯對苯二甲酸酯之固有粘度（IV)到達〇 · 5 8 d 1 / g爲止所需滯留時間（即液相聚合反應時間）爲 1 0 0分鐘。 經濟部智慧財產局員工消費合作社印製 經上述液相聚合反應之聚乙烯對苯二甲酸酯，再在氮 氣中，約1 7 0 t下進行2小時之結晶化之後，塡充在塔 型固相聚合反應機中，氮氣中，2 1 下進行2 2小時 之固相聚合反應。 按照上述所得聚乙烯對苯二甲酸酯之鈦原子含量爲 1 5 Ρ ρηι，鎂原子含量爲2 5 p pm，鈦原子/鎂原子 之莫耳比率爲0 · 3 ，固有粘度爲0 · 82d Ι/g，密 -174- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 585881 經濟部智慧財產局員工消費合作社印製 A7 ____B7 五、發明説明（172) 度爲1 · 4〇g/cm3 ’環狀三聚物含量爲〇 · 4〇重量 %。 將上述聚乙烯對苯二甲酸酯2 · 5 kg在不銹鋼容器 中浸漬於0 · 〇 6 9 5重量％之磷酸三甲酯水溶液4 k g 中。在常溫下保持4小時後，分離粒狀聚乙烯對苯二甲酸 酯和磷酸三甲酯水溶液，排除水分之後，在1 6 0 °C，氮 氣流中乾燥5小時。所得聚乙烯對苯二甲酸酯之環狀三聚 物含量爲0 · 40重量％ (X重量％)。該聚乙烯對苯二 甲酸酯經按照上述方法成型爲階梯狀矩形成型物之環狀三 聚物含量爲0 · 4 8重量％，成型前後之環狀三聚物含量 之差値爲0·08重量％(y重量％) ，一〇.2χ+ 〇· 2之値爲0 · 12 ，固有粘度爲0 · 805dl/g 〔實施例4 6 3 - 4〕 經實施例4 6 3 — 3所固相聚合之聚乙烯對苯二甲酸 酯在不銹鋼容器中浸漬於9 5 °C之異丙醇中，並加熱保持 4小時。 分離聚乙烯對苯二甲酸酯和異丙醇之後，在1 6 0°C ，氮氣流中乾燥5小時。所得聚乙烯對苯二甲酸酯之環狀 三聚物含量爲0 · 40重量％ (X重量％)。該聚乙烯對 苯二甲酸酯按照上述方法成型爲階梯狀矩形成型物之環狀 三聚物之含量爲〇 · 4 6重量％ ’成型前後之環狀三聚物 之差値爲0 · 06重量％ (y重量％) ’ — 0 · 20χ + 本纸張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公瘦）· 175 - (請先閱讀背面之注意事項再填寫本頁)5. Description of the invention (167) P P m, the difference between the acetaldehyde content before and after molding is 704 p p 9 d 1 / g. It has a viscosity of 0.8. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Solid Economy [Example 4 6 2 — 4] Example 4 6 2-3 BOC solid phase polymerized polyethylene terephthalate was impregnated in a stainless steel container. Heat at 9 5 t of isopropanol for 4 hours. After the polyethylene terephthalate and isopropyl alcohol were separated, it was dried in a nitrogen stream for 5 hours. The acetaldehyde content of the obtained polyethylene terephthalate was 0.9 p p m. The polyethylene terephthalate was formed into a stepped rectangular shaped article according to the above method, and its acetaldehyde content was measured at 9.5 ppm. The difference between the acetaldehyde content before and after molding was 8.6 ppm, and the intrinsic viscosity was 0. 810 dl / g. [Example 4 6 2-5] The solid phase polymerization of polyethylene terephthalate in Example 4 6 2-3 was immersed in a stainless steel container in an isopropanol solution containing tributyl phosphate (triphosphate The butyl ester was 0.059 weight, and was kept under heating for 2 hours. After separating the polyethylene terephthalate and isopropanol solution, it was dried at 160 ° C for 5 hours under nitrogen to obtain the polyethylene p-benzene. The acetaldehyde content of the diformate was 0.7 ppm. The polyethylene terephthalate was formed into a step-shaped rectangular shaped article according to the method described above. The acetaldehyde content was measured at 8.2 ppm. The rate is 7.5 This paper size is applicable to China National Standards (CNS) A4 specifications (210X 297 mm) ---- ^ ---, order ------ * f (Please read the precautions on the back before Fill in this page) Dimethyl is maintained and -170- 585881 A7 B7____ 5. Description of the invention (168) ppm, inherent viscosity is 0 · 8〇8d 1 / g. (Please read the precautions on the back before filling this page) [Implementation Example 4 6 3 — 1] During the routine operation of the production of polyester, the reaction solution can be retained in a reaction container of 3,500 parts by weight. Continuously supply a slurry prepared by mixing 6 4 5 8 parts by weight per hour of high-purity terephthalic acid and 2 9 9 parts by weight per hour of ethylene glycol. Under stirring, in nitrogen, 26 ° C '. · 9kg / cm2-G, the esterification reaction is carried out. On the occasion of this esterification reaction, the solid titanium compound prepared in Example 4 9 5-1 is supplied as titanium atom 0.1 8 7 parts by weight / Hour and magnesium acetate are based on magnesium atom, 0.187 parts by weight / hour. In this esterification reaction, a mixed solution of water and ethylene glycol is distilled out of the reaction system. Esterification reaction product (oligomer) control Continuous extraction was performed outside the reaction system with an average residence time of 3.5 hours. The number average molecular weight of the low polymer of ethylene glycol and terephthalic acid obtained above was 600 to 1300 (3 to 5 polymers). Intellectual Property of the Ministry of Economic Affairs The liquid phase polycondensation reaction of the printed low polymer by the Bureau's Consumer Cooperative was carried out under the conditions of supplying 0.83 1 parts by weight / hour of tributyl phosphate at 280 ° C and 1 Torr. The intrinsic viscosity (IV) of polyethylene terephthalate reaches 0.5 5 d 1 / g The required residence time (that is, the liquid phase condensation polymerization reaction time) is 87 minutes. Then, the polyethylene terephthalate is obtained through the liquid phase condensation polymerization reaction, and the paper size applies the Chinese National Standard (CNS) A4 specification (210X297). (Mm) -171-585881 A7 B7 V. Description of the invention (169) (Please read the notes on the back before filling this page) After crystallization in nitrogen at about 170 ° C for 2 hours, charge In a tower-type solid-phase polymerization reactor, a solid-phase polymerization reaction was performed in nitrogen at 2 1 Ot for 25 hours. The titanium atom content of the polyethylene terephthalate obtained according to the above was 24 ppm, the magnesium atom content was 24 PP m, the molar ratio of titanium atom / magnesium atom was 0.5, and the intrinsic viscosity was 0. 760d Ι. / g, density is 1.40 g / cm3, and cyclic trimer content is 0.3% by weight. 2.5 kg of the above polyethylene terephthalate was impregnated in a printer of a consumer cooperative of the Employees ’Cooperative of the Intellectual Property Office of the Ministry of Stainless Steel and Economic Affairs in 0.4 kg of a 0.05% by weight trimethyl phosphate aqueous solution. . After keeping it at normal temperature for 4 hours, the polyethylene terephthalate and trimethyl phosphate aqueous solution were separated, and after removing water, it was dried at 160 ° C for 5 hours in nitrogen. The cyclic terpolymer content of the obtained polyethylene terephthalate was 0.30% by weight (X% by weight). This polyethylene terephthalate was formed into a stepped rectangular shaped article according to the method described above, and its cyclic trimer content was measured to be 0.35% by weight. The difference between the content of the cyclic trimer before and after the molding is 0.05% by weight (y% by weight), the ratio of −0.2x + 0.2 is 0.14, and the intrinsic viscosity is 0. 825d 1 / g [Implementation Example 4 6 3 — 2] Using the same granular polyethylene terephthalic acid 2.5 kg as used in Example 4 6 3-1 was immersed in a stainless steel container with a 0.6955% by weight trimethyl phosphate aqueous solution 4 kg in. Then, the paper size containing polyethylene is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -172 · 585881 A7 B7 I--....... V. Description of the invention (170) (Please Read the precautions on the back before filling this page.) The stainless steel container of the terephthalate and trimethyl phosphate aqueous solution is heated from the outside, and the internal temperature is controlled at 95 ° C. After heat treatment and holding for 4 hours, separate Granular polyethylene terephthalate and trimethyl phosphate aqueous solution · After removing the moisture, it was dried at 160 ° C for 5 hours in a nitrogen stream. The cyclic trimer content of the obtained polyethylene terephthalate was 0.30% by weight (X% by weight). The polyethylene terephthalate was used to form a stepped rectangular shaped article according to the above method, and the cyclic trimer content was 0.33% by weight (X% by weight). The difference 値 is 0.03% by weight (y% by weight), 値 of 〇 2〇χ + 0 · 2 is 0 · 134, and the intrinsic viscosity is 0.81 Id Ι / g. [Example 4 6 3-1 C] The same granular polyethylene terephthalate as used in Example 4 6 3-1 was used, but it was not contacted with a phosphorus-containing aqueous solution. According to the method described above, a stepped rectangular shaped article was formed. The cyclic trimer content of the stepped rectangular shaped product was 0.52% by weight (X% by weight), and the difference between the cyclic trimer content before and after molding was 0.22% by weight (7% by weight). The Consumer Cooperative of the 4th Bureau of Finance printed a 0 · 20x + 0 · 2 where 値 is 096. 'Intrinsic viscosity is 0. 8 3 3 d 1 / g. [Examples 463-3] During the routine operation, the reaction solution can be retained in a reaction container of 3,500 parts by weight, and high-purity terephthalic acid and 1 2 by mixing 6 3 2 9 parts by weight / hour are continuously supplied. 9 parts by weight of isophthalic acid / hour and this paper size are applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -173- 585881 A7 _ B7_ _ V. Description of the invention (171) 2 6 1 5 parts by weight The slurry prepared by ethylene glycol / hour, under stirring under the conditions of nitrogen at 260 ° C, 0.9 kg / c nf — G (Please read the precautions on the back before filling this page), An esterification reaction is performed. During the esterification reaction, the same solid titanium compound prepared in Example 4 6 3-1 was further supplied as titanium atoms, 0 · 1 1 2 parts by weight / hour, and magnesium acetate as magnesium atoms. 8 7 parts by weight / hour. In this esterification reaction, a mixed solution of water and ethylene glycol is distilled out of the reaction system. The esterification reaction product (oligomer) is controlled to be continuously extracted out of the reaction system with an average residence time of 3.5 hours. The number average molecular weight of the oligomers of ethylene glycol and terephthalic acid obtained above is 600 to 1300 (3 to 5 polymers). The oligomer was subjected to a liquid phase polycondensation reaction under the conditions of supplying 0.8 3 1 parts by weight / hour of tributyl phosphate at 280 ° C and 1 T ο I · r. The retention time (ie, the liquid phase polymerization reaction time) required for the intrinsic viscosity (IV) of polyethylene terephthalate to reach 0.58 d 1 / g is 100 minutes. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the polyethylene terephthalate after the above-mentioned liquid phase polymerization reaction, and then crystallized in nitrogen at about 170 t for 2 hours. In a solid-phase polymerization reactor, a solid-phase polymerization reaction was performed under nitrogen at 2 1 for 2 2 hours. According to the polyethylene terephthalate obtained above, the titanium atom content is 15 P ρηι, the magnesium atom content is 2 5 p pm, the molar ratio of titanium atom / magnesium atom is 0 · 3, and the intrinsic viscosity is 0 · 82d. Ι / g ， 密 -174- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 585881 Printed by A7 ____B7, Employee Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (172) Degree is 1 · 4 〇g / cm3 'cyclic trimer content was 0.40% by weight. 2.5 kg of the above polyethylene terephthalate was immersed in a stainless steel container in 4 kg of a 0.05% by weight trimethyl phosphate aqueous solution. After keeping it at room temperature for 4 hours, the granular polyethylene terephthalate and trimethyl phosphate aqueous solution were separated, and after removing water, it was dried at 160 ° C for 5 hours in a nitrogen stream. The cyclic trimer content of the obtained polyethylene terephthalate was 0.40% by weight (X% by weight). The polyethylene terephthalate was formed into a step-shaped rectangular shaped article according to the above method, and the cyclic trimer content was 0.48% by weight, and the difference between the cyclic trimer content before and after molding was 0. 08% by weight (y% by weight), 〇0.2 × + 〇 2 is 0 · 12, intrinsic viscosity is 0 · 805dl / g [Example 4 6 3-4] According to Example 4 6 3-3 Solid-phase polymerized polyethylene terephthalate was immersed in isopropanol at 95 ° C in a stainless steel container and heated for 4 hours. After the polyethylene terephthalate and isopropyl alcohol were separated, it was dried at 160 ° C for 5 hours in a nitrogen stream. The cyclic terpolymer content of the obtained polyethylene terephthalate was 0.40% by weight (X% by weight). The content of the cyclic trimer of the polyethylene terephthalate formed into a step-shaped rectangular shaped article according to the method described above was 0.46% by weight. % By weight (y% by weight) '— 0 · 20χ + This paper size applies Chinese National Standard (CNS) Α4 size (210 × 297 male thin) · 175-(Please read the precautions on the back before filling this page)

585881 A7 _B7 五、發明説明（173) 0 · 2〇之値爲0 · 12 ’固有粘度爲0 · 8l〇d 1/ g 0 (請先閱讀背面之注意事項再填寫本頁) 〔實施例4 6 3 — 2 C〕 使用實施例4 6 3 - 2中所採用相同粒狀聚乙烯對苯 二甲酸酯，但不施與磷酸三甲酯水溶液接觸處理，按照上 述方法成型爲階梯狀矩形成型物。該階梯狀矩形成型物之 環狀二聚物含重爲0 · 5 7重量％ ( X重量％)。成型前 後之環狀三聚物含量之差値爲〇·17重量％(y重量％ )，一 0 · 2x + 0 · 2之値爲〇 · 086 ，固有粘度爲 0 · 8 1 1 d 1 / g 。 〔實施例4 6 9 - 1〕 先將7 6 · 8 1莫耳的高純度對苯二甲酸和 8 6 . 0 3莫耳的乙二醇在常壓，1 〇 〇 t下供應到酯化 經濟部智慧財產局8工消費合作社印製 反應槽中，再添加實施例4 9 5 - 1中所調製之固態狀含 駄化合物0·0045莫耳做爲觸媒用途。繼之，提升上 述反應’槽溫至260 °C，在壓力1 · 7kg/cm - G， 氮氣中反應3 4 0分鐘。由該反應所產生水隨時蒸餾排除 反應系外。 然後將酯化反應槽內之總反應產物移到事先加溫到 2 6 0°C之縮聚合反應槽之後，再於常壓下添加溶解有 0 · 007 3莫耳之磷酸三丁酯的乙二醇6 · 44莫耳於 上述反應槽中，使用6 0分鐘時間由2 6 0 t升溫到 -176- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公羞） 585881 B7 五、發明説明（174) 2 8 0 °C，壓力從常壓減壓到2 T o r r 。 (請先閱讀背面之注意事項再填寫本頁) 再於縮聚合反應槽中進行1 〇 8分鐘之反應後，反應 產物以絲狀抽出到縮聚合反應槽外’浸漬水中加以冷卻， 利用切絲刀裁斷而得粒狀聚乙烯對苯二甲酸酯。該聚乙烯 對苯二甲酸酯之固有粘度爲0 · 6 5 d Ι/g，藉原子吸 光分析儀測定含鈦量爲2 8 p P m。 再將經液相聚合而得聚乙烯對苯二甲酸酯移至固相聚 合塔內，氮氣流中，1 7 〇 °C下結晶化2小時後，在 2 1 0 °C下進行固相聚合反應1 3小時’而得粒狀聚乙烯 對苯二甲酸酯。該聚乙烯對苯二甲酸酯之固有粘度爲 0 · 8 2 5 d Ι/g。使用該聚乙烯對苯二甲酸酯按照前 述方法成型爲階梯狀矩形成型物，測定其C處之濁度爲 17.8%。 然後使用該聚乙烯對苯二甲酸酯成型爲下列中空成型 物。 經濟部智慧財產局員工消費合作社印製 使用名機製作所製品之壓注模成型機Μ - 1 0 0 A型 ，以圓筒設定溫度2 6 0 t，模溫1 0 °C之條件下，成型 爲直徑2 8mm之預塑物。該時之壓注模成型溫度爲 2 7 6 t：，成型循環時間爲5 4秒鐘。 繼之，使用吹塑成型機（Corpoplast公司製品’ LB0 1型），在展延溫度爲11 0°C，吹塑模溫爲30 °C條件下，將上述預塑物展延成型而得1 · 5 <之中空成 型物。 就該中空成型物之外觀評估如下： 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -177 - 585881 A 7 B7 五、發明説明（175) (請先閱讀背面之注意事項再填寫本頁) 然後使用名機製作所製品之Μ - 7 Ο B型壓注模成型 機按照下述方法就上述聚乙烯對苯二甲酸酯之流動性（L / Τ )評估之，另行測定所得L / Τ成型片之固有粘度’ 將其結果示於表4 6 9 — 1中。 又，實施例4 6 9 - 1〜4 6 9 — 6 ，比較例4 6 9 一 1〜4 6 9 — 4中所述各種特性乃按照下述方法測定。 固有粘度（IV ) 使用酚和1 ，1 ，2，2 —四氯乙烷之混合溶劑（ 50/50重量比率）調製〇 · 5dl/g之試料溶液， 在2 5 °C下測定成型物之溶液粘度，計算得固有粘度。又 ’粒狀聚乙烯對苯二甲酸酯之固有粘度爲i.2g之聚乙 烯對苯二甲酸酯在1 5 cc之鄰一氯酚中加熱溶解後，冷卻 在2 5 °C下測定溶液粘度而計算之。 濁度 經濟部智慧財產局Μ工消費合作社印製 使用2 k g之粒狀聚乙烯對苯二甲酸酯爲原料，以溫 度1 4 0 °C，壓力1 〇 Τ 〇 r r條件下在層式乾燥機乾燥 1 6小時以上，使粒狀聚乙烯對苯二甲酸酯之含水率保持 在50ppm以下。 然後’將上述乾燥過之粒狀聚乙烯對苯二甲酸酯利用 名機製作所公司製品之Μ - 7 0 A型壓注模成型機，以圓 筒溫度2 7 5 °C，模冷卻水溫度1 5 °C之條件下，壓注模 成型而製成階梯狀矩形成型物。 -178· 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 585881 A7 B7 五、發明説明（176) (請先閲讀背面之注意事項再填寫本頁) 該階梯狀矩形成型物藉計量1 2秒鐘，壓注模爲6 0 秒鐘之條件而調整好之壓注模成型機’由料斗供應乾燥之 粒狀聚乙烯對苯二甲酸酯而成型之。又’成型機內之熔融 樹脂之滯留時間爲約7 2秒鐘。又，階梯狀矩形成型物一 個所使用樹脂重量爲7 5 g。濁度測定用試料採用壓注模 成型開始後第1 1個〜第1 5個之任意一個成型物。另按 實施例4 6 9 - 1所示相同方法成型爲中空成型物評估其 外觀。又，按照實施例4 6 9 - 1所示相同方法測定流動 性（L / T )和L / 丁成型片之固有粘度。其結果示於表 4 6 9 - 1 中。 〔比較例469-3〕 使用聚乙烯對苯二甲酸酯（以原子吸光分析法測定之 固有粘度爲0 . 7 7 8 d 1 / g，觸媒種類爲鍺化合物， 含鍺量爲5 6 p p m )按照實施例4 6 9 - 1所示相同方 法成型爲中空成型物評估其外觀。另，按照實施例4 6 9 一 1所示相同方法測定流動性（L / T )和L / T成型片 之固有粘度。其結果示於表4 6 9 - 1中。 經濟部智慈財產局g(工消費合作社印製 〔比較例4 6 9 - 4〕 使用聚乙烯對苯二甲酸酯（以原子吸光分析法測定之 固有粘度爲0 · 8 2 3 d 1 / g。觸媒種類爲鍺化合物， 含鍺量爲4 2 p pm)按照實施例4 6 9 - 1所示方法成 型爲中空成型物評估其外觀。另，按照實施例4 6 9 — 1 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 585881 A7 B7 五、發明説明（177) 所示相同方法測定流動性（L / T )和L / T成型片之固 有粘度，其結果示於表4 6 9 - 1中。 〔實施例4 6 9 — 6〕 固態狀含鈦化合物之調製 1 ◦ 0 0 m£之玻璃燒枉中秤取5 0 0 m£之去離子水， 加入0 . 1 5 g之無水氫氧化鎂並加以分散。以冰浴冷卻 後’攪拌下滴加5 g之四氯化鈦。溶液呈酸性而氫氧化鎂 溶解其中。待氯化氫之產生終止後自冰浴中取出，攪拌下 滴加2 5 %之氨水，調整溶液爲p Η 8。所產生含鈦複合 氫氧化物之沈澱物利用2 5 0 0旋轉離心1 5分鐘而和上 澄液分離之。然後，用去離子水洗淨所得含鈦複合氫氧化 物之沈澱物5次。洗淨後之固液相分離以2 5 0 0旋轉離 心1 5分鐘而進行。洗淨後之含鈦複合氫氧化物在7 0 °C ’ 1 Ο T 〇 r r之條件下減壓乾燥1 8小時以去除水分， 而得固態狀含鈦化合物。 該固態狀含鈦化合物之鈦和鎂之原子比率，以鈦原子 9 1莫耳比鎂原子9莫耳。所得含鈦化合物在做爲縮聚合 觸媒使用之前，先粉碎成爲1 〇 左右之粒狀物。 實施例4 6 9 - 1中，使用上述方法所調製之固態狀 含鈦化合物做爲縮聚合觸媒之外，其他皆依照實施例 4 6 9 - 1所示相同方法進行縮聚合反應，粒狀化處理和 固相聚合反應。使用所得聚乙烯對苯二甲酸酯按照實施例 4 6 9 — 1所示相同方法成型爲中空成型物評估其外觀。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） #1— (請先閱讀背面之注意事項再填寫本頁) ,11 經濟部智慧財產局員工消費合作社印製 -180- 585881 A7 ___B7 五、發明説明（17δ) 又，按照實施例4 6 9 - 1所示相同方法測定其流動性（ L/丁）和L/T成型片之固有粘度。其結果示於表 二因酸製 苯，甲所 對高二酯 烯性苯酸 乙動對甲 聚流烯二 之其乙苯 關，聚對 有酯之烯 明酸關乙 發甲有聚 本二明之 。 ，苯發往S 示對本已W 所烯由和 h 中乙且也異 1 聚並，優 I 的，物樣 。9 往異型 _ 中 6 已優成物 1 4 之性空型 | 表較型中成 9 如酯成得空 6 酸其所中 4 甲此酯得 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局g(工消費合作社印製 -181 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）585881 A7 _B7 V. Description of the invention (173) 0 · 2〇 where 0 is 12 · 'inherent viscosity is 0 · 8l0d 1 / g 0 (Please read the precautions on the back before filling this page) [Example 4 6 3 — 2 C] The same granular polyethylene terephthalate as used in Example 4 6 3-2 was used, but without contact treatment with a trimethyl phosphate aqueous solution, and formed into a stepped rectangular shape according to the method described above. Thing. The cyclic dimer content of this stepped rectangular shaped product was 0.57 wt% (X wt%). The difference between the content of the cyclic trimer before and after the molding is 1717% by weight (y% by weight), the 値 of 0 · 2x + 0 · 2 is · 086, and the intrinsic viscosity is 0 · 8 1 1 d 1 / g. [Example 4 6 9-1] First, 76.81 mol of high-purity terephthalic acid and 86.03 mol of ethylene glycol were supplied to the esterification under normal pressure at 100t. In the printed reaction tank of the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the solid erbium-containing compound prepared in Example 4 9 5-1 was added as a catalyst. Then, the temperature of the above reaction 'tank was raised to 260 ° C, and the reaction was carried out under nitrogen at a pressure of 1.7 kg / cm-G for 3 to 40 minutes. The water produced by this reaction is distilled off at any time to exclude the reaction system. Then the total reaction product in the esterification reaction tank was moved to a condensation polymerization reaction tank which had been heated to 250 ° C beforehand, and then ethyl acetate in which 0.007 3 mol of tributyl phosphate was dissolved was added under normal pressure. Diol 6.44 mol was placed in the above reaction tank, and the temperature was raised from 260 t to -176 in 60 minutes. This paper size is in accordance with China National Standard (CNS) A4 (210X297). 585881 B7 V. Description of the invention (174) 2 80 ° C, the pressure is reduced from normal pressure to 2 T orr. (Please read the precautions on the back before filling this page.) After reacting in the polycondensation reaction tank for 108 minutes, the reaction product is pulled out in a filament shape and immersed in water to cool it. The knife was cut to obtain granular polyethylene terephthalate. The intrinsic viscosity of this polyethylene terephthalate was 0.65 d Ι / g, and the titanium content was determined by an atomic absorption analyzer to be 2 8 p P m. Then, the polyethylene terephthalate obtained by liquid phase polymerization was moved into a solid-phase polymerization tower. After being crystallized at 170 ° C for 2 hours in a nitrogen stream, the solid phase was performed at 210 ° C. Polymerization was performed for 1 to 3 hours to obtain granular polyethylene terephthalate. The inherent viscosity of this polyethylene terephthalate was 0 · 8 2 5 d Ι / g. This polyethylene terephthalate was used to form a stepped rectangular shaped article according to the method described above, and the turbidity at the C site was measured to be 17.8%. This polyethylene terephthalate was then used to form the following hollow molded article. Printed by a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, using an injection molding machine M-1 0 0 A manufactured by a famous machine manufacturer, molding at a cylinder set temperature of 2 60 t and a mold temperature of 10 ° C. It is a pre-plastic with a diameter of 2 8mm. The injection molding temperature at this time was 2 7 6 t :, and the molding cycle time was 54 seconds. Next, using a blow molding machine (Corpoplast's LB0 type 1), the preform was stretch-formed at a stretch temperature of 110 ° C and a blow mold temperature of 30 ° C to obtain 1 5 < Hollow molding. The evaluation of the appearance of the hollow molded article is as follows: This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -177-585881 A 7 B7 V. Description of the invention (175) (Please read the note on the back first Please fill in this page for details) Then use M- 7 〇 B type injection molding machine manufactured by Mingji to evaluate the above-mentioned polyethylene terephthalate fluidity (L / Τ) according to the following method, separately The intrinsic viscosity of the obtained L / T molded sheet was measured ', and the results are shown in Table 4 6-9-1. Various characteristics described in Examples 4 6 9-1 to 4 6 9-6 and Comparative Examples 4 6 9-1 to 4 6 9-4 were measured by the following methods. Intrinsic viscosity (IV) A sample solution of 0.5 dl / g was prepared using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (50/50 weight ratio), and the molded product was measured at 25 ° C. The viscosity of the solution was calculated as the intrinsic viscosity. Also, the granular polyethylene terephthalate has an inherent viscosity of i.2g, and the polyethylene terephthalate is heated and dissolved in 1 15 cc of o-chlorophenol, and then measured at 25 ° C after cooling. Calculate the solution viscosity. Turbidity Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, M Industrial Consumer Cooperative, using 2 kg of granular polyethylene terephthalate as a raw material, and dried in layers at a temperature of 140 ° C and a pressure of 10 〇 〇rr Machine drying for more than 16 hours to keep the moisture content of granular polyethylene terephthalate below 50 ppm. Then, the above-mentioned dried granular polyethylene terephthalate was manufactured using a M-70 A type injection molding machine made by Mingji Seisakusho Co., Ltd. at a cylinder temperature of 27 5 ° C and a mold cooling water temperature. Under the condition of 15 ° C, it is injection-molded into a step-shaped rectangular shaped article. -178 · This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 585881 A7 B7 V. Description of the invention (176) (Please read the precautions on the back before filling this page) The injection molding machine, which was adjusted for 12 seconds and adjusted to 60 seconds for injection molding, was formed by supplying dry granular polyethylene terephthalate from a hopper. The residence time of the molten resin in the molding machine was about 72 seconds. The weight of the resin used for each of the stepped rectangular shaped articles was 75 g. The sample for turbidity measurement was formed by any one of the eleventh to the fifteenth after the start of molding. In addition, a hollow molded article was molded in the same manner as shown in Example 4 6 9-1 to evaluate its appearance. In addition, the fluidity (L / T) and the intrinsic viscosity of the L / Ding tablet were measured in the same manner as shown in Example 4 6 9-1. The results are shown in Table 4 6 9-1. [Comparative Example 469-3] Using polyethylene terephthalate (inherent viscosity measured by atomic absorption spectrometry was 0.7 7 8 d 1 / g, catalyst type was germanium compound, and germanium content was 5 6 ppm) was molded into a hollow molded article in the same manner as shown in Example 4 6 9-1 to evaluate its appearance. In addition, the fluidity (L / T) and the inherent viscosity of the L / T molded sheet were measured in the same manner as shown in Example 4 6 9-11. The results are shown in Table 4 6 9-1. Ministry of Economic Affairs, Intellectual Property Office, g (printed by Industrial and Consumer Cooperatives [Comparative Examples 4 6 9-4] using polyethylene terephthalate (inherent viscosity measured by atomic absorption spectrometry is 0 · 8 2 3 d 1 / g. The type of catalyst is a germanium compound, and the content of germanium is 4 2 p pm) The shape of the hollow molded article was evaluated according to the method shown in Example 4 6 9-1. In addition, according to Example 4 6 9-1 paper The Zhang scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 585881 A7 B7 V. Description of the invention (177) The same method as shown in Figure 177 is used to determine the fluidity (L / T) and the inherent viscosity of the L / T molded tablets. The results are shown in Table 4 6 9-1. [Example 4 6 9-6] Preparation of solid titanium-containing compound 1 ◦ 0 0 m £ in a glass sintered glass weighed out 5,000 m £ of deionized water, 0.15 g of anhydrous magnesium hydroxide was added and dispersed. After cooling in an ice bath, 5 g of titanium tetrachloride was added dropwise with stirring. The solution was acidic and magnesium hydroxide was dissolved therein. After the generation of hydrogen chloride was terminated, Take out in an ice bath, add 25% ammonia water dropwise while stirring, and adjust the solution to p Η 8. The titanium-containing composite hydroxide produced The precipitate was separated from the supernatant by centrifugation at 2,500 for 15 minutes. Then, the obtained titanium-containing composite hydroxide precipitate was washed 5 times with deionized water. The solid-liquid phase was separated after washing. Centrifugation was performed at 2500 for 15 minutes. After washing, the titanium-containing composite hydroxide was dried under reduced pressure for 18 hours at 70 ° C '10 〇rr to remove water, and a solid was obtained. The titanium-containing compound in a solid state. The atomic ratio of titanium to magnesium in the solid titanium-containing compound is 91 mol of titanium atom to 9 mol of magnesium atom. The obtained titanium-containing compound is pulverized before being used as a condensation polymerization catalyst. Granules of about 10%. In Example 4 6 9-1, the solid titanium-containing compound prepared by the above method was used as the condensation polymerization catalyst, and everything else was the same as that shown in Example 4 6 9-1. Methods Polycondensation, granulation, and solid-phase polymerization were carried out. The obtained polyethylene terephthalate was formed into a hollow molded article in the same manner as shown in Example 4 6 9-1 to evaluate its appearance. Paper size Applicable to China National Standard (CNS) A4 specification (210X297 (Mm) # 1— (Please read the notes on the back before filling this page), 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-180- 585881 A7 ___B7 V. Description of the invention (17δ) Again, according to Example 4 The fluidity (L / D) and the inherent viscosity of L / T molded tablets were measured by the same method as shown in 6-1. The results are shown in Table 2. Due to the production of benzene by acid, methyl ester, ethyl ester of high diester ethylenic benzoic acid, etc. Methyl phenylene has two ethyl benzene compounds, and poly-p-esteryl enosinic acid has two ethyl benzene compounds. Benzene was sent to S, which showed that the alkylene group in h and the ethylene group in h were also different from each other, and I was excellent. 9 dimorphic _ Medium 6 has been superior to 1 1 4 of the nature of the empty type | Table comparison of the intermediate 9 if the ester becomes empty 6 the acid is in its 4 methyl ester (Please read the precautions on the back before filling this page ) Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperatives -181-This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

Claims (1)

585881 A8 Βδ C8 D8 7Τ、申請專利範圍 (請先閱讀背面之注意事項再填寫本頁) 1 · 一種聚酯製造用觸媒，其特徵爲由鹵化鈦化合物 水解而成水解產物，經脫水乾燥而得，其氫氧基（〇 Η ) 和鈦（Ti)之莫耳比率（OH/Ti)爲〇 · 09以上 而4以下之固態狀鈦化合物（I 一 a )所構成。 2 · —種聚酯製造用觸媒，其特徵爲由鹵化鈦化合物 和，選自鈦以外之其他元素中至少一種元素之化合物或該 化合物之前驅物，之混合物經水解而成水解產物，加以脫 水乾燥而得，其氫氧基（0 Η )和鈦（τ i )之莫耳比率 (〇H / T i )爲〇 · 〇 9以上而4以下之固態狀含鈦化 合物（I 一 b )所構成。 3 ·如申§靑專利軺圍弟2項之聚醋製造用觸媒，其中 選自上述鈦以外之其他元素中至少一種元素之化合物或該 化合物之前驅物係選自鈹、鎂、鈣、緦、鋇、銃、釔、鑭 、鉻、給、釩、鈮、鉬、鉻、鉬、鎢、錳、鐵、釕、銘、 錯、鎳、銷、銅、鋅、硼、銘、鎵、砂、鍺、錫、銻和磷 所構成群中至少一種元素之化合物或該化合物之前驅物者 〇 經濟部智慧財產局員工消費合作社印製 4 ·如申請專利範圍第3項之聚醋製造用觸媒，其中 ，選自前述以外之其他元素之至少一種之元素之化合物或 此化合物之前驅物爲，鎂化合物者。 5·—種聚酯製造用觸媒，其特徵爲由（I一a)如 申請專利範圍第1項之固態狀鈦化合物及/或如（I 一 b )申請專利範圍第2項之固態狀含鈦化合物所構成縮聚合 觸媒成分，和 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -183- 585881 經濟部智慧財產局員工消費合作社印製 A8 Βδ C8 D8六、申請專利範圍 (Π )選自鈹、鎂、銘、總、鋇、硼、銘、鎵、I孟、 鈷、鋅、鍺、銻和磷所構成群中之至少一種元素之化合物 所成之輔觸媒成分，如此所構成者。 6 ·如申請專利範圍第5項之聚酯製造用觸媒，其中 上述輔觸媒成分（Π )係鎂化合物者。 7 · —種聚酯製造用觸媒，其特徵爲使鹵化鈦化合物 和水接觸而水解鹵化鈦化合物所得含有鹵化鈦化合物之水 解產物之酸性溶液，以鹼處理成鹼性，再用酸調整爲p Η 2〜6，所產生沈澱物加以脫水乾燥而得之，固態狀含鈦 化合物（I 一 e)，其中之氫氧基（〇H)和鈦（Ti) 之莫耳比率（〇H/T i )爲〇 · 〇 9以上而4以下者。 8 · —種聚酯製造用觸媒，其特徵爲使鹵化鈦化合物 和水接觸而水解鹵化鈦化合物所得含有鹵化鈦化合物之水 解產物之酸性溶液，用鹼調整爲p Η 2〜6，所產生沈澱 物加以脫水乾燥而得固態狀含鈦化合物（I - f )，其中 之氫氧基（〇H)和鈦（T i )之莫耳比率（OH/T i )爲0.09以上而4以下者。 9 · 一種聚酯製造用觸媒，其特徵爲（I )由如申請 專利範圍第7項或第8項之固態狀鈦化合物所構成縮聚合 觸媒成分，和 (Π )選自鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、 鈷、鋅、鍺、銻和磷所成群中至少一種元素之化合物而構 成輔觸媒成分者。 1 〇 ·如申請專利範圍第9項之聚酯製造用觸媒’其 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -184- 585881 A8 B8 C8 D8 々、申請專利範圍 中上述輔觸媒成分（Π )係鎂化合物。 (請先閱讀背面之注意事項再填寫本頁) 11· 一'種聚酯製造用觸媒’其特徵爲由鹵化鈦化合 物和選自欽以外之其他兀素中至少一種元素之化合物或該 化合物之前驅物，之混合物和水接觸，將鹵化鈦化合物加 以水解而得含有鹵化鈦化合物之水解產物之酸性溶液，用 鹼變成鹼性，再用酸調整爲P Η 2〜6，所產生之沈澱物 行脫水乾燥而得之固態狀含鈦化合物（I - g )，其中之 氫氧基（〇H)和鈦（T i )之莫耳比率（〇H/T i ) 爲0 . 0 9以上而4以下者。 1 2 ·如申請專利範圍第1 1項之聚酯製造用觸媒， 其中選自上述欽以外之其他元素中至少一種元素之彳七合物 或該化合物之前驅物係由鈹、鎂、鈣、緦、鋇、銃、釔、 鋼、銷、給、$凡、鍛、組、絡、銷、鶴、猛、鐵、釘、銘 、鍺、鎳、鈀、銅、鋅、硼、鋁、鎵、矽、鍺、錫、銻和 磷所構成群中至少一種元素之化合物或該化合物之前驅物 〇 經濟部智慧財產局員工消費合作社印製 1 3 · —種聚酯製造用觸媒，其特徵爲由鹵化鈦化合 物和選自鈦以外之其他元素中至少一種元素之化合物或該 化合物之前驅物之混合物和水接觸，將鹵化鈦化合物水解 而得含有鹵化鈦化合物之水解產物之酸性溶液，用鹼調整 爲P Η 2〜6 ，所產生沈澱物行脫水乾燥而得固態狀含鈦 化合物（I— h)，其中之氫氧基（〇H)和鈦（Ti) 之莫耳比率（〇Η/Τι)爲0 · 09以上而4以下者。 1 4 ·如申請專利範圍第1 3項之聚酯製造用觸媒， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ _ 585881 A8 Β8 C8 D8 六、申請專利範圍 (請先聞讀背面之注意事項再填寫本頁) 其中選自上述鈦以外之其他元素中至少一種元素之化合物 或該化合物之前驅物係選自鈹、鎂、鈣、總、鋇、钪、金乙 、鑭、鉻、給、釩、銀、鉬、鉻、鉬、鎢、猛、鐵、釕、 銘、錶、錬、銷、銅、辞、硼、銘、錄、砂、鍺、錫、鍊 和隣所構成群中至少一種兀素之化合物或該化合物之前驅 物。 1 5 · —種聚酯製造用觸媒，其特徵爲由（I )如申 請專利範圍第1 1項或第1 3項之固態狀含鈦化合物（I —g )或（I 一 h )所構成縮聚合觸媒成分，和 (Π )選自鈹、鎂、釣、總、鋇、硼、銘、鎵、锰、 銘、鋅、鍺、銻和憐所構成群中至少一種元素之化合物而 構成輔觸媒成分，如此所構成者。 1 6 ·如申請專利範圍第1 5項之聚酯製造用觸媒， 其中上述輔觸媒成分（Π )係鎂化合物。 1 7 · —種聚酯製造用觸媒，其特徵爲由鈦氫氧化物 ，經脫水乾燥而得，其2 0 (衍射角度）爲1 8 °〜3 5。 之範圍的X光衍射象所計算結晶化度在5 0 %以下之固態 狀欽化合物（I 一 i )所構成。 經濟部智慧財產局員工消費合作社印製 1 8 · —種聚酯製造用觸媒，其特徵爲由（I )如申 請專利範圍第1 7項之固態狀鈦化合物（I 一 i )所構成 縮聚合觸媒成分，和 (Π )選自鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、 鈷、鋅、鍺、銻和磷所構成群中至少一種元素之化合物而 成輔觸媒成分所構成。 本紙張尺度適用中國國家樣準（CNS ) A4規格（210 X 297公釐） -186 - 585881 A8 B8 C8 D8 六、申請專利範圍 19·一種聚酯製造用觸媒，其特徵爲（A—1) ’ (請先閱讀背面之注意事項再填寫本頁) 由（I 一 j )鈦化合物行水解而成水解產物或（I 一 k ) 鈦化合物和選自鈦以外之其他元素中至少一種元素之化合 物或該化合物之前驅物，之混合物行水解而成水解產物’ 和 鹼性化合物（B )，以及 脂肪族二元醇（C )，如此所成之混合物經加熱而成 泥漿所構成， 前述水解物之氫氧基（〇Η )和鈦（T i )之莫耳比率（ 〇H/Ti )爲0 · 09以上而4以下者。 2 〇 ·如申請專利範圍第1 9項之聚酯製造用觸媒， 其中前述鹼性化合物（B )係選自四乙銨氫氧化物，四甲 銨氫氧化物，氨水，氫氧化鈉，氫氧化鉀，N -乙基嗎啉 ，N —甲基嗎啉中至少一種化合物而成。 2 1 .如申請專利範圍第1 9項之聚酯製造用觸媒， 其中，前述脂肪酸二元醇（C )係乙二醇者。 22·—種聚酯製造用觸媒，其特徵爲， 經濟部智慧財產局員工消費合作社印製 (A — 2 )，由（I 一 m )鹵化鈦化合物水解而成水 解產物或（I 一 η )鹵化鈦化合物，和選自鈦以外之其他 元素中至少一種元素之化合物或該化合物之前驅物，之混 合物經水解而成水解產物，和 (D )含選自鈹、鎂、鈣、緦、硼、鋁、鎵、錳、鈷 和鋅中至少一種元素之磷酸金屬鹽所構成 前述水解物之氫氧基（Ο Η )和鈦（T i )之莫耳比率（ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -187 - 5B588l A8 B8 C8 D8 六、申請專利範圍 〇H/T 1 )爲Ο · 09以上而4以下者。 (請先閱讀背面之注意事項再填寫本頁) 2 3 ·如申請專利範圍第2 2項之聚酯製造用觸媒， 其中上述磷酸金屬鹽（D )係磷酸氫鎂或二磷酸三鎂。 2 4 · —種聚酯製造用觸媒’其特徵爲， (Α — 2 )，由（I 一 m )鹵化鈦化合物行水解而成 水解產物，或（I 一 ri )鹵化鈦化合物，和選自鈦以外之 其他元素中至少一種元素之化合物或該化合物之前驅物， 之混合物經水解而成水解產物，和 (E )含有選自由鈹、鎂、鈣、緦、硼、鋁、鎵、錳 、鈷和鋅中至少一種元素之金屬化合物，和 (F )選自磷酸和磷酸酯中至少一種之磷化合物，和 (G )脂肪族二元醇，如此所成之混合物經加熱而得 泥漿所構成， 前述水解物之氫氧基（〇 Η )和鈦（T i )之莫耳比率（ 〇H/T i )爲〇 · 09以上而4以下者。 經濟部智慧財產局員工消費合作社印製 2 5 ·如申請專利範圍第2 4項之聚酯製造用觸媒， 其中上述金屬化合物（E )係鎂化合物，上述磷化合物（ F )係磷酸或三甲基磷酸酯，上述脂肪族二元醇（G )係 乙二醇所構成。 2 6 ·如申請專利範圍第2 4項之聚酯製造用觸媒， 其中，上述（A— 2) ，( E ) ， （F)和（G)，之混 合物之加熱溫度在1 0 0〜2 0 0 °C，加熱時間爲3分鐘 至5小時者。 2 7 · —種聚酯之製造方法，其特徵爲在如申請專利 本紙張尺度適用中國國家標率（CNS ) A4規格（210X297公釐） -188 - 585881 A8 B8 C8 D8 六、申請專利範圍 範圍第1項至第2 6項中任一項之觸媒存在下，將芳香族 二羧酸或其酯形成性衍生物和脂肪族二元醇或其酯形成性 衍生物加以縮聚合而成者。 28·—種聚酯之製造方法，在包括：由芳香族二羧 酸或其酯形成性衍生物，和脂肪族二元醇或其酯形成性衍 生物，加以酯化而形成低聚合物之酯化步驟；和縮聚合觸 媒之存在下，將該低聚合物縮聚合成爲高分子化之縮聚合 步驟，之聚酯之製造方法中，其爲， 縮聚合觸媒係使用， (Γ ) ( I 一 ])使鈦化合物行水解而成氫氧基（ 〇H)和鈦（Tl)之莫耳比率（〇H/Ti)爲 0 · 0 9以上而4以下之水解產物，或（I 一 k )鈦化合 物，和選自鈦以外之其他元素中至少一種元素之化合物或 該化合物之前驅物，之混合物行水解而成氫氧基（◦ Η ) 和鈦（Ti)之莫耳比率（〇H/Ti)爲〇 · 09以上 而4以下之水解產物所構成縮聚合觸媒成分，和 运自皴、錢、錦、總、鎖、棚、銘、嫁、猛、銘、鲜 、鍺、銻和磷所構成群中至少一種元素之化合物而構成輔 觸媒成分所構成之觸媒，並且 在酯化反應開始前或酯化反應開始之後，將上述縮聚 合觸媒成分（I )添加於酯化反應容器者。 2 9 ·如申請專利範圍第2 8項之聚酯之製造用觸媒 ，其中，上述輔觸媒成分（Π )係鎂化合物。 3 0 · —種聚酯之製造方法，其特徵爲將芳香族二羧 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ---------— (請先閱讀背面之注意事項再填寫本頁) 、π 經濟部智慧財產局員工消費合作社印製 -189- 585881 Α8 Β8 C8 D8 六、申請專利範圍 酸或其酯形成性衍生物和脂肪族二元醇或其酯形成性衍& 物，在選自下列（1 )至（3 )項之縮聚合觸媒以及磷酸 酯之存在下，予以縮聚合而製造聚酯之方法； ί請先閱讀背面之注意事項再填寫本頁) (1 )，由鹵化鈦化合物水解而成，氫氧基（ο Η ) 和鈦（T i )之莫耳比率（〇H/T i )爲0 · 09以上 而4以下之水解產物（I 一 m )所構成縮聚合觸媒， (2 )由鹵化鈦化合物，和選自鈦以外之其他元素ψ 至少一種元素之化合物或該化合物之前驅物，之混合物$ 水解而成，氫氧基（〇Η )和鈦（T i )之莫耳比率（ 〇H / T i )爲0 · 0 9以上而4以下之水解產物（I ^ η)所構成縮聚合觸媒， (3)，上述（1— m)或（I 一 η)和 選自鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷、_ 、鍺、銻和磷所構成群中至少一種元素之化合物或磷酸_ ，或亞磷酸鹽所構成縮聚合觸媒。 3 1 ·如申請專利範圍第3 0項之聚酯之製造方法， 其中，上述磷酸酯係三丁基磷酸酯，三辛基磷酸酯或三苯 基磷酸酯。 經濟部智慧財產局員工消費合作社印製 3 2 · —種聚酯之製造方法，其特徵爲將芳香族二羧 酸或其酯形成性衍生物，和脂肪族二元醇或其酯形成性衍 生物’在選自下列（1 )至（3 )項之縮聚合觸媒，以及 選自環狀內酯系化合物和受阻S分系化合物中之至少一種化^ 合物之存在下予以縮聚合者； (1 )由鹵化鈦化合物行水解而成，氫氧基（〇 Η ) 本紙張尺度適用中國國家標準（CNS ) Α4規格（21 Οχ297公釐） _ 19〇 585881 Α8 Β8 C8 D8 六、申請專利範圍 和鈦（Ti )之莫耳比率（ΟΗ/Τι )爲〇 · 〇9以上 而4以下之水解產物（I - m )所構成縮聚合觸媒， ---------— (請先閲讀背面之注意事項再填寫本頁) (2 )由鹵化鈦化合物，和選自鈦以外之其他元素中 至少一種元素之化合物或該化合物之前驅物，之混合物行 水解而成，氫氧基（〇Η )和鈦（T i )之莫耳比率（ 〇H/Ti )爲0 · 09以上而4以下之水解產物（ η)所構成縮聚合觸媒， (3)由上述（I 一 m)或（I— η)，和 選自鈹、鎂、鈣、鋸、鋇、硼、鋁、鎵、錳、站、鋅 、鍺、銻所成群中至少一種元素之化合物或磷酸鹽，或亞 磷酸鹽所成之縮聚合觸媒。 3 3 ·如申請專利範圍第3 2項之聚酯之製造方法， 其進而倂用選自磷酸和磷酸酯中至少一種磷化合物者。 經濟部智慧財產局員工消費合作社印製 3 4 ·如申請專利範圍第3 2項或第3 3項之聚酯之 製造方法，其中，選自上述環狀內酯系化合物和受阻酚系 化合物中至少一種化合物係5 ，7 —二第三丁基—3 —( 3 , 4 —二甲苯基）—3 H -苯駢d夫喃—2 -酮和四個（ 亞甲基一 3 — （3 ，5 -二第三丁基—4 一羥基苯基）丙 酸酯）甲烷以及三個（2，4 —二第三丁基苯基）亞磷酸 酯之混合物。 3 5 · —種聚酯之製造方法，其含芳香族二羧酸或其 酯形成性衍生物，和脂肪族二元醇或其酯形成性衍生物， 加以酯化成爲低聚合物之酯化步驟，以及在縮聚合觸媒之 存在下’將該低聚合物再行縮聚合而高分子量化之縮聚合 -191 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210><297公釐） 585881 A8 B8 C8 D8 六、申請專利範圍 步驟之聚酯之製造方法中’其特徵爲’ 縮聚合觸媒係使用， (請先閲讀背面之注意事項再填寫本頁) (I )(〗一 m )由鹵化鈦化合物行水解而成’氣氧 基（〇H)和鈦（T i )之莫耳比率（〇H/T 1 )爲 〇 · 0 9以上而4以下之水解物或（1 一 η )鹵化欽化合 物和選自鈦以外其他元素中至少一種元素之化合物或該化 合物之前驅物，之混合物，加以水解而成’氫氧基（〇Η )和鈦（Ti )之莫耳比率（〇H/Ti)爲0 · 09以 上而4以下之水解產物所成縮聚合觸媒成分’以及 (Π )選自由鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳 、鈷、鋅、鍺、銻和磷所成群中至少一種元素之化合物而 成輔觸媒成分所成觸媒，並且 在上述酯化步驟或縮聚合步驟之任一步驟中添加色相 調整劑者。 3 6 ·如申請專利範圍第3 5項之聚酯之製造方法， 其中，上述色相調整劑係選自藍色溶劑1 0 4，紅色素 2 6 3，紅色溶劑1 3 5，藍色素2 9，藍色素1 5 : 1 ，藍色素15 : 3，紅色素187，紫色素19中至少一 經濟部智慧財產局員工消費合作社印製 種者。 3 7 ·如申請專利範圍第3 5項之聚酯之製造方法， 其中，上述輔觸媒成分（Π )係鎂化合物。 3 8 · —種聚酯之處理方法，其特徵爲使用鈦化合物 觸媒而得，且反應終結之聚酯以磷原子換算濃度爲1 〇 P P m以上之亞磷酸水溶液，次磷酸水溶液，磷酸酯水溶 •192- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 585881 A8 Β8 C8 D8 六、申請專利範圍 液，亞磷酸酯水溶液或次磷酸酯水溶液，接觸處理者。 3 9 ·如申請專利範圍第3 8項之聚酯之處理方法， 其中上述聚酯係固有粘度爲0 · 5 0 d l/g以上，密度 (請先閱讀背面之注意事項再填寫本頁) 爲1.3 7忌/〇1113以上，且乙醛含量在5 0 0111以下者 〇 4 0 ·如申請專利範圍第3 8項或第3 9項之聚酯之 處理方法，其中使用鈦化合物觸媒而得，且反應終結之聚 乙烯對苯二甲酸酯予以處理者。 4 1 · 一種聚酯之處理方法，其特徵爲使用鈦化合物 觸媒而得，且反應終結之聚酯以選自醇類，飽和烴，酮類 之有機溶媒溶液，接觸處理者。 4 2 ·如申請專利範圍第4 1項之聚酯之處理方法， 其中，上述聚酯係固有粘度爲0 · 50dl/g以上，密 度爲1.3 7忌/〇1113以士，且乙醛含量爲5??111以下 者。 4 3 ·如申請專利範圍第4 1或4 2項之聚酯之處理 方法，其中上述有機溶劑係異丙醇或丙酮者。 4 4 ·如申請專利範圍第4 1項或第4 2項之聚酯之 經濟部智慧財產局員工消費合作社印製 處理方法，其係使用鈦化合物觸媒而得，且反應終結之聚 乙烯對苯二甲酸酯予以處理者。 4 5 · —種聚酯之處理方法，其特徵爲將使用鈦化合 物觸媒而得，且反應終結之聚酯，與以磷原子換算濃度爲 1 0 p p m以上之選自磷酸，磷酸酯，亞磷酸，次磷酸， 亞磷酸酯或次磷酸酯之醇類，飽和烴，酮類之有機溶媒溶 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） · 193 - 585881 A8 B8 C8 D8 六、申請專利範圍 液，予以接觸處理者。 4 6 ·如申請專利範圍第4 5項之聚酯之處理方法， 其中上述聚酯係固有粘度爲〇·50dΙ/g以上，密度 (請先閱讀背面之注意事項再填寫本頁) 爲1·37g/cm3以上，且乙醛含量爲5ppm以下者 〇 4 7 ·如申請專利範圍第4 5項之聚酯之處理方法， 其中上述磷酸酯係三丁基磷酸酯，三苯基磷酸酯或三甲基 磷酸酯者。 4 8 ·如申請專利範圍第4 5項之聚酯之處理方法， 其中上述有機溶媒係異丙醇或丙酮者。 4 9 ·如申請專利範圍第4 5項至第4 8項中任一項 之聚酯之處理方法，其爲使用鈦化合物觸媒所得，且反應 終結之聚乙烯對苯二甲酸酯予以處理者。 經濟部智慧財產局員工消費合作社印製 50· —種聚酯（P — 1)，其特徵爲在如申請專利 範圍第4項或第6項之聚酯製造用觸媒之存在下，將芳香 族二羧酸或其酯形成性衍生物，和脂肪族二元醇或其酯形 成性衍生物，加以縮聚合而得之聚酯，其含鈦量爲1〜 lOOppm，含鎂量爲1〜200ppm，該聚酯中所 含鈦和鎂之重量比率（M g / T i )係0 · 0 1以上者。 5 1 ·如申請專利範圍第5 0項之聚酯（P — 1 )， 其中該聚酯係聚乙烯對苯二甲酸酯者。 52. —種聚酯（P — 2)，其特徵爲含有鈦原子 0 · 1 〜200ppm 量， 含有選自鈹、鎂、錦、總、鋇、硼、銘、鎵、锰、鈷 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公嫠）-194 - 585881 A8 B8 C8 D8 7T、申請專利範圍 (請先閱讀背面之注意事項再填寫本頁) 、鋅和銻中之金屬原子（Μ) 0 · 1〜500ppm量， 前述鈦原子和前述金屬原子（M)之莫耳比率（鈦原 子/金屬原子（M)在1/5 0〜5 0/1範圍，且 含有0 · 0 1〜lOOppm量之色相調整劑者。 53. —種聚酯（P - 3)，其特徵爲 固有粘度在0.50dl/g以上， 含鈦原子爲0 . 1〜2〇〇ppm量， 含有選自鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷 、鋅和銻中之金屬原子（M)量爲0·1〜500ppm 上述鈦原子和上述金屬原子（Μ)之莫耳比率（鈦原 子/金屬原子（Μ)在0 · 05〜50範圍， 乙醛含量在4 p pm以下，且以該含量爲WQp pm， 加熱至2 7 5 °C熔融而成型爲階梯狀矩形成型物後之乙醛 含量爲Wip pm時，Wi— W。在1 〇 p pm以下者。 5 4 .如申請專利範圍第5 3項之聚酯（P — 3 )， 其中，上述鈦原子係來源於鹵化鈦化合物水解而得縮聚合 觸媒者。 經濟部智慧財產局員工消費合作社印製 5 5 .如申請專利範圍第5 3項或第5 4項之聚酯（ P — 3 )，其中，該聚酯係聚乙烯對苯二甲酸酯者。 56. —種聚酯（P - 4)，其特徵爲， 固有粘度係0.50dl/g以上， 含鈦原子爲0 . 1〜2〇〇ppm量， 含有選自鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳、鈷 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -195 - 585881 A8 B8 C8 D8 六、申讀專利範圍 、鋅和銻中之金屬原子（Μ) 0 · 1〜500ppm量， 上述鈦原子和上述金屬原子（M)之莫耳比率（鈦原 孑/金屬原子（M)在0 · 05〜50範圍， 環狀三聚物含量在0 · 5重量％以下，且以該含量爲 x重量％，而加熱至2 9 0 °C溫度熔融成型爲階梯狀矩形 成型物後之環狀三聚物含量之增加量爲y重量％時，X和 y能滿足下式關係’ 0 · 2x + 0 · 2 者 5 7 ·如申請專利範圍第5 6項之聚酯（P - 4 )， 其中，上述鈦原子係來源於鹵化鈦化合物之水解而得縮聚 合觸媒者。 5 8 .如申請專利範圍第5 6項之聚酯（P — 4 )， 其中，該聚酯係聚乙烯對苯二甲酸酯者。 59. —種聚酯（P — 5)，其特徵爲， 在2 9 0 °C壓注模成型之際，其流動長度（L )和流 動厚度（T)之比率（L/T)做爲Y時，上述壓注模成 製所得成型物之固有粘度爲X ( d 1 / g )時，前述X和 Y之關係下式所示者， 經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁} γ^647-500χ 。 6 0 ·如申請專利範圍第5 9項之聚酯（P — 5 ) ’ 其中，在將鹵化鈦化合物行水解而成水解產物（I - m ) 所成之縮聚合觸媒之存在下，將芳香族二羧酸或其酯形成 性衍生物，和脂肪族二元醇或其酯形成性衍生物’加以縮 聚合而得者。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -196 - 585881 A8 B8 C8 D8 六、申請專利範圍 6 1 ·如申請專利範圍第5 9項之聚酯（P — 5 ) ’ (請先閱讀背面之注意事項再填寫本頁) 其中，將鹵化鈦化合物和選自鈦以外之其他元素中至少一 種元素之化合物或該化合物之前驅物，，之混合物加以水 解而成水解產物（I - η )所構成縮聚合觸媒之存在下’ 將芳香族二羧酸或其酯形成性衍生物，和脂肪族二元醇或 其酯形成性衍生物，進行縮聚合而得者。 6 2 ·如申請專利範圍第6 1項之聚酯（Ρ - 5 )， 其中，選自上述鈦以外之其他元素中至少一種元素之化合 物或該化合物之前驅物係選自鈹、鎂、鈣、緦、鋇、钪、 ί乙、鋼、銷、給、飢、銀、組、絡、組、錫、鐘、鐵、釘 、姑、錯、錬、iG、銅、鲜：、棚、銘、録：、砂、錯、錫、 銻和磷所成群中至少一種元素之化合物或該化合物之前驅 物者。 6 3 ·如申請專利範圍第5 9項之聚酯（ρ — 5 )， 其中在（I )如申請專利範圍第6 0項至第6 2項中任意 一項之縮聚合觸媒， 經濟部智慧財產局員工消費合作社印製 和（Π )選自鈹、鎂、鈣、緦、鋇、硼、鋁、鎵、錳 、銘、辞、錯、鍊和憐所成群中至少~1種元素之化合物所 成輔觸媒成分， 之存在下，將芳香族二羧酸或其酯形成性衍生物與，脂肪 族二元醇或其酯形成性衍生物，加以縮聚合而得者。 6 4 ·如申請專利範圍第6 3項之聚酯（ρ 一 5 )， 其中，上述輔觸媒成分（Π )係鎂化合物。 6 5 ·如申請專利範圍第6 4項之聚酯（ρ __ 5 )， ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) -- 585881 A8 B8 C8 D8 ____ 六、申請專利範圍 其中，鈦原子含量爲1〜1 〇 〇 p pm範圍，鎂原子含量 爲1〜2 0 〇 p pm範圍，前述鈦原子和鎂原子之重量比 率（Mg/Ti)在〇·〇1以上者。 (請先閱讀背面之注意事項再填寫本頁) 6 6 ·如申請專利範圍第5 9項之聚酯（P 一 5 )， 其中該聚酯係聚乙烯對苯二甲酸酯。 6 7 ·如申請專利範圍第6 3項之聚酯（P — 5 )， 其中該聚酯係聚乙烯對苯二甲酸酯。 6 8 ·如申請專利範圍第5 0項或第5 1項之聚酯（ p-1)其爲用於成型體者。 6 9 ·如申請專利範圍第6 8項之聚酯（P — 1 )， 其中上述成型物係中空成型物。 7 0 ·如申請專利範圍第6 8項之聚酯（P — 1 )， 其中上述成型物係薄膜或片狀物。 7 1 ·如申請專利範圍第6 8項之聚酯（P — 1 )， 其中上述成型物係纖維。 7 2 ·如申請專利範圍第5 6至5 8項中任一項之聚 酯（P - 4)，其爲使用於環狀三聚物含量在0.6重量 %以下之中空成型物者。 經濟部智慧財產局員工消費合作社印製 7 3 ·如申請專利範圍第5 9項之聚酯（P — 5 )， 其爲使用於中空成型物用預塑物者。 7 4 ·如申請專利範圍第6 3項之聚酯（P — 5 )， 其爲使用於中空成型物用預塑物者。 7 5 ·如申請專利範圍第5 9項之聚酯（P — 5 )， 其爲使用於中空成型物者。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -198- 一 585881 A8 B8 C8 D8 六、申請專利範圍 7 6 .如申請專利範圍第6 3項之聚酯（P — 5 )， 其爲使用於中空成型物者。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -199 -585881 A8 Βδ C8 D8 7T, scope of patent application (please read the precautions on the back before filling this page) 1 · A catalyst for polyester production, which is characterized by the hydrolysis of titanium halide compounds into hydrolysates, which are dehydrated and dried. Thus, a solid titanium compound (I-a) having a molar ratio (OH / Ti) of hydroxyl group (〇Η) and titanium (Ti) of 0.09 or more and 4 or less was obtained. 2. A catalyst for polyester production, characterized in that a mixture of a halogenated titanium compound and a compound of at least one element selected from elements other than titanium or a precursor of the compound is hydrolyzed to form a hydrolysate, and It is obtained by dehydration and drying, and the molar ratio (OH / Ti) of the hydroxyl group (0 和) and titanium (τ i) of the solid titanium-containing compound (I-b) of not less than 0.99 and not more than 4 Made up. 3. The catalyst for the production of polyacetic acid according to item 2 of Rushen § Patent, in which the compound selected from at least one element of other elements other than titanium or the precursor of the compound is selected from beryllium, magnesium, calcium, Hafnium, barium, thorium, yttrium, lanthanum, chromium, feed, vanadium, niobium, molybdenum, chromium, molybdenum, tungsten, manganese, iron, ruthenium, inscription, wrong, nickel, pin, copper, zinc, boron, inscription, gallium, Compounds of at least one element in the group consisting of sand, germanium, tin, antimony, and phosphorus or the precursors of the compounds. 0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The catalyst, in which the compound of at least one element selected from the elements other than the foregoing or the precursor of the compound is a magnesium compound. 5 · —A catalyst for manufacturing polyester, characterized by (Ia) a solid titanium compound as described in the first patent application scope and / or (Iab) a solid state titanium application as described in the patent application scope Polycondensation catalyst composition composed of titanium compounds, and this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -183- 585881 Printed by A8 Βδ C8 D8 The scope of the patent application (Π) is formed from a compound of at least one element selected from the group consisting of beryllium, magnesium, ming, total, barium, boron, ming, gallium, Iman, cobalt, zinc, germanium, antimony and phosphorus. Auxiliary catalyst components, so constituted. 6 · The catalyst for polyester production as claimed in item 5 of the patent application, wherein the auxiliary catalyst component (Π) is a magnesium compound. 7 · A catalyst for polyester production, characterized in that an acidic solution containing a hydrolysate of a titanium halide compound obtained by contacting the titanium halide compound with water to hydrolyze the titanium halide compound is treated with alkali to become alkaline, and then adjusted with an acid to p Η 2 ~ 6, obtained by dehydration and drying of the produced precipitate, solid titanium-containing compound (I-e), in which the molar ratio of hydroxyl group (〇H) to titanium (Ti) (〇H / T i) is 9.0 or more and 4 or less. 8 · A catalyst for polyester production, characterized in that an acidic solution containing a hydrolyzate of a titanium halide compound obtained by contacting the titanium halide compound with water to hydrolyze the titanium halide compound is adjusted to p Η 2 ~ 6 with an alkali. The precipitate is dehydrated and dried to obtain a solid titanium-containing compound (I-f), in which the molar ratio (OH / T i) of the hydroxyl group (OH) and titanium (T i) is 0.09 or more and 4 or less . 9. A catalyst for polyester production, characterized in that (I) is a polycondensation catalyst component composed of a solid titanium compound such as item 7 or 8 of the scope of patent application, and (Π) is selected from beryllium and magnesium Compounds of at least one element of the group consisting of calcium, osmium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, germanium, antimony, and phosphorus to form a secondary catalyst component. 1 〇 · If you apply for polyester manufacturing catalyst in item 9 of the scope of patent application (these (please read the precautions on the back before filling this page)) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)- 184-585881 A8 B8 C8 D8 々 The above mentioned auxiliary catalyst component (Π) is a magnesium compound in the scope of the patent application. (Please read the precautions on the back before filling in this page) 11. A 'catalyst for polyester manufacture', which is characterized by a compound consisting of a titanium halide compound and at least one element selected from other elements other than chitin or the compound The precursor, the mixture is in contact with water, and the titanium halide compound is hydrolyzed to obtain an acidic solution containing the hydrolyzate of the titanium halide compound, which is made alkaline with an alkali, and then adjusted to P 为 2 ~ 6 with an acid. The solid titanium-containing compound (I-g) obtained by dehydration and drying, in which the molar ratio (OH / T i) of the hydroxyl group (OH) and titanium (Ti) is 0.99 or more And less than 4. 1 2 If the catalyst for polyester production is the item 11 in the scope of patent application, wherein the heptahydrate of at least one element selected from the elements other than the above-mentioned elements or the precursor of the compound is made of beryllium, magnesium, calcium , Scandium, barium, scandium, yttrium, steel, pin, feed, $, van, forged, group, pin, crane, ferrous, iron, nail, inscription, germanium, nickel, palladium, copper, zinc, boron, aluminum, Compounds of at least one element in the group consisting of gallium, silicon, germanium, tin, antimony, and phosphorus, or precursors of the compounds. 0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. A type of polyester manufacturing catalyst. It is characterized by contacting water with a titanium halide compound and a compound of at least one element selected from elements other than titanium or a precursor of the compound and water, and hydrolyzing the titanium halide compound to obtain an acidic solution containing a hydrolyzate of the titanium halide compound, It is adjusted to P Η 2 ~ 6 with a base, and the resulting precipitate is dehydrated and dried to obtain a solid titanium-containing compound (I-h), in which the molar ratio of hydroxide (OH) to titanium (Ti) ( Η / Τι) is 0 · 09 or more and 4 or less. 1 4 · For polyester manufacturing catalysts in item 13 of the scope of patent application, the paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 585881 A8 Β8 C8 D8 6. Scope of patent application (please First read the notes on the back and then fill out this page) Among them, the compound selected from at least one of the above elements other than titanium or the precursor of the compound is selected from beryllium, magnesium, calcium, total, barium, thallium, and gold. , Lanthanum, chromium, feed, vanadium, silver, molybdenum, chromium, molybdenum, tungsten, ferrous, iron, ruthenium, inscription, watch, thorium, pin, copper, rhenium, boron, inscription, record, sand, germanium, tin, chain A compound or a precursor of at least one element in a group formed by neighbors. 1 5 · A kind of catalyst for polyester production, characterized by (I) a solid titanium-containing compound (I -g) or (I -h) A polycondensation catalyst component, and (Π) a compound of at least one element selected from the group consisting of beryllium, magnesium, fishing, total, barium, boron, indium, gallium, manganese, indium, zinc, germanium, antimony, and phosphorus The auxiliary catalyst component is constituted, and thus constituted. 16 · The polyester manufacturing catalyst according to item 15 of the patent application scope, wherein the auxiliary catalyst component (Π) is a magnesium compound. 17. A kind of catalyst for polyester production, which is characterized in that it is obtained by dehydration drying of titanium hydroxide, and its 20 (diffraction angle) is 18 ° ~ 35. The X-ray diffraction image in this range is composed of a solid compound (I-i) having a crystallinity of 50% or less. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 18 types of catalysts for polyester manufacturing, characterized by (I) a solid titanium compound (I-i) as described in item 17 of the scope of patent application. Polymerization catalyst component, and (Π) is supplemented by a compound of at least one element selected from the group consisting of beryllium, magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, germanium, antimony and phosphorus Catalyst components. This paper size is applicable to China National Sample Standard (CNS) A4 (210 X 297 mm) -186-585881 A8 B8 C8 D8 6. Application for patent scope 19 · A catalyst for polyester manufacturing, which is characterized by (A-1 ) '(Please read the notes on the back before filling this page) The hydrolysis product of (I-j) titanium compound or (I-k) titanium compound and at least one element selected from other elements than titanium The compound or its precursor, the mixture is hydrolyzed to form a hydrolysate 'and the basic compound (B), and the aliphatic diol (C). The mixture thus formed is heated to form a slurry. The aforementioned hydrolysis The molar ratio (OH / Ti) of the hydroxyl group (〇Η) and titanium (Ti) of the material is 0. 09 or more and 4 or less. 20. The catalyst for polyester production according to item 19 of the scope of patent application, wherein the basic compound (B) is selected from tetraethylammonium hydroxide, tetramethylammonium hydroxide, ammonia water, sodium hydroxide, At least one compound selected from potassium hydroxide, N-ethylmorpholine and N-methylmorpholine. 2 1. The polyester manufacturing catalyst according to item 19 of the patent application scope, wherein the fatty acid diol (C) is ethylene glycol. 22 · —A kind of catalyst for polyester manufacturing, characterized by (A-2) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and hydrolyzed by (I-m) titanium halide compound to produce (I-η ) A titanium halide compound, a compound of at least one element selected from elements other than titanium, or a precursor of the compound, a mixture of which is hydrolyzed to form a hydrolysate, and (D) containing a compound selected from beryllium, magnesium, calcium, scandium, Molar ratio of hydroxide (0 Η) to titanium (T i) of the aforementioned hydrolysate composed of a phosphate metal salt of at least one element of boron, aluminum, gallium, manganese, cobalt, and zinc (This paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm) -187-5B588l A8 B8 C8 D8 6. The scope of patent application 0H / T 1) is 0 · 09 or more and 4 or less. (Please read the precautions on the back before filling out this page) 2 3 · If the catalyst for polyester production is No. 22 in the scope of patent application, the above-mentioned metal phosphate (D) is magnesium hydrogen phosphate or trimagnesium diphosphate. 2 4 · A catalyst for the manufacture of polyesters, characterized in that (A-2) is a hydrolysate formed by hydrolysis of (I-m) titanium halide compound, or (I-ri) titanium halide compound, and A compound of at least one element from the elements other than titanium or a precursor of the compound, a mixture of which is hydrolyzed to a hydrolysate, and (E) containing a compound selected from the group consisting of beryllium, magnesium, calcium, scandium, boron, aluminum, gallium, and manganese Metal compound of at least one element of cobalt, cobalt and zinc, and (F) a phosphorus compound selected from at least one of phosphoric acid and phosphate ester, and (G) an aliphatic diol, and the resulting mixture is heated to obtain a slurry. In the composition, the molar ratio (OH / Ti) of the hydroxyl group (〇 （) and titanium (Ti) of the hydrolysate is 0.09 or more and 4 or less. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 5 If the catalyst for polyester manufacturing is No. 24 in the scope of patent application, the metal compound (E) is a magnesium compound, and the phosphorus compound (F) is phosphoric acid or Methyl phosphate is composed of the above-mentioned aliphatic diol (G) -based ethylene glycol. 2 6 · The catalyst for polyester manufacturing as described in item 24 of the scope of patent application, wherein the heating temperature of the mixture of (A-2), (E), (F) and (G) above 100 ~ 2 0 0 ° C, heating time of 3 minutes to 5 hours. 2 7 · — A method of manufacturing polyester, which is characterized in that if the paper size of the patent is applied, the Chinese national standard (CNS) A4 specification (210X297 mm) is applied -188-585881 A8 B8 C8 D8 6. Scope of patent application A catalyst obtained by condensation-polymerizing an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof in the presence of the catalyst of any one of items 1 to 26 . 28. A method for producing a polyester comprising: esterifying an aromatic dicarboxylic acid or an ester-forming derivative thereof with an aliphatic diol or an ester-forming derivative thereof to form an oligomer; Esterification step; in the presence of a polycondensation catalyst, the oligomer is polycondensed into a polymerized polycondensation step. In the method for producing a polyester, the polycondensation catalyst is used, (Γ) (I a)) hydrolysis of a titanium compound to produce a hydrolysate having a molar ratio (OH / Ti) of hydroxide (OH) and titanium (Tl) of 0. 0 to 9 and 4 or less, or (I 1) a titanium compound, and a compound of at least one element selected from elements other than titanium or a precursor of the compound, the mixture is hydrolyzed to form a molar ratio of hydroxyl (◦ 氧基) to titanium (Ti) ( 〇H / Ti) is a polycondensation catalyst component composed of hydrolysates above 0.9 and below 4, and is transported from 皴, Qian, Jin, Total, Lock, Shed, Ming, Married, Meng, Ming, Fresh, Germanium A compound of at least one element in the group consisting of antimony, antimony and phosphorus to form a catalyst composed of auxiliary catalyst components, and Before beginning the esterification reaction, or after the esterification reaction, the above-described engagement polycondensation catalyst component (I) are added to the esterification reaction vessel. 29. The catalyst for manufacturing polyesters according to item 28 of the patent application scope, wherein the auxiliary catalyst component (Π) is a magnesium compound. 3 0 · — A method for producing polyester, characterized in that the size of the aromatic dicarboxy paper is applied to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ---------— (Please read first Note on the back, please fill out this page again), π Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -189-585881 Α8 Β8 C8 D8 6. Application for patent scope Acid or its ester-forming derivative and aliphatic diol or its The ester-forming derivative is a method for producing a polyester by polycondensation in the presence of a polycondensation catalyst selected from the following items (1) to (3); and phosphate esters; please read the precautions on the back first (Fill in this page again) (1), which is obtained by hydrolysis of titanium halide compounds. The molar ratio (OH / T i) of hydroxide (ο Η) and titanium (T i) is 0 · 09 or more and 4 or less. A polycondensation catalyst composed of a hydrolysate (I-m), (2) a mixture of a halide compound and at least one element selected from the group consisting of titanium other than ψ or a precursor of the compound, hydrolyzed, Molar ratio of hydroxide (〇Η) and titanium (T i) (〇H / T i ) Is a polycondensation catalyst composed of a hydrolysate (I ^ η) of 0 · 0 9 to 4; (3), the above (1-m) or (I-η) and selected from the group consisting of beryllium, magnesium, calcium, A compound of at least one element in the group consisting of scandium, barium, boron, aluminum, gallium, manganese, cobalt, cobalt, germanium, antimony, and phosphorus, or phosphoric acid, or a polycondensation catalyst composed of phosphite. 31. The method for producing a polyester according to item 30 of the scope of patent application, wherein the phosphate is a tributyl phosphate, a trioctyl phosphate or a triphenyl phosphate. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 2 · A method for producing polyesters, which is characterized in that an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof are produced A substance which is polycondensed in the presence of a polycondensation catalyst selected from the following items (1) to (3), and at least one compound selected from the group consisting of a cyclic lactone-based compound and a hindered S-type compound ; (1) Hydrolyzed by titanium halide compound, hydroxyl group (〇Η) This paper size is applicable to Chinese National Standard (CNS) A4 specification (21 〇χ297mm) _ 19〇585881 Α8 Β8 C8 D8 6. Apply for patent The range and the molar ratio (0 钛 / Τι) of titanium (Ti) are from 0.09 to 4 and the hydrolysis products (I-m) constitute a condensation polymerization catalyst, ---------- ( (Please read the precautions on the back before filling this page) (2) Hydrolyzed by a mixture of titanium halide compounds, compounds of at least one element selected from elements other than titanium, or precursors of the compounds. Molar ratio of radical (〇Η) and titanium (Ti) (〇H / Ti ) Is a polycondensation catalyst composed of a hydrolysate (η) of 0. 09 to 4; (3) is selected from the above (I-m) or (I-η), and is selected from beryllium, magnesium, calcium, saw, Compounds or phosphates of at least one element in the group consisting of barium, boron, aluminum, gallium, manganese, station, zinc, germanium, antimony, or condensation polymerization catalysts made of phosphite. 3 3 · The method for producing a polyester according to item 32 of the scope of patent application, which further uses at least one phosphorus compound selected from phosphoric acid and phosphate ester. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 4 · If the method of manufacturing polyesters in the scope of patent application No. 32 or No. 33 is selected from the above-mentioned cyclic lactone compounds and hindered phenol compounds At least one compound is 5,7-di-tert-butyl-3— (3,4-xylyl) -3 H-benzopyridan-2-one and four (methylene-3— (3 , 5-Di-tertiary-butyl-4 monohydroxyphenyl) propionate) methane and three (2,4-tertiary-butylphenyl) phosphite. 3 5 · —A method for producing a polyester, which comprises an aromatic dicarboxylic acid or an ester-forming derivative thereof, and an aliphatic diol or an ester-forming derivative thereof, and is esterified to form an oligomer. Steps, and in the presence of a polycondensation catalyst, 'condensate the low polymer and polymerize the polycondensation with high molecular weight -191-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 > < 297 G (Centi) 585881 A8 B8 C8 D8 VI. In the manufacturing method of the patent application process, the polyester is characterized by the use of polycondensation catalyst (please read the precautions on the back before filling this page) (I) (〗 1 m) Hydrolysate obtained by hydrolyzing a titanium halide compound to a 'mole ratio (〇H / T 1) of oxygen gas (OH) and titanium (Ti) of 0.09 or more and 4 or less ( 1 η) a mixture of a halogenated compound and a compound selected from at least one element other than titanium or a precursor of the compound, and hydrolyzed to form a mole of hydroxy (〇Η) and titanium (Ti) Hydrolysate with ratio (〇H / Ti) of 0.09 to 4 Polycondensation catalyst components' and (Π) are selected from compounds of at least one element in the group consisting of beryllium, magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, germanium, antimony and phosphorus A catalyst formed by a secondary catalyst component, and a hue adjusting agent is added to any of the esterification step or the condensation polymerization step. 3 6 · The method for producing a polyester according to item 35 of the scope of patent application, wherein the hue adjusting agent is selected from the group consisting of blue solvent 104, red pigment 2 6 3, red solvent 1 3 5, blue pigment 2 9 , Blue pigment 15: 1, blue pigment 15: 3, red pigment 187, purple pigment 19. At least one of the employees of the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives printed seeds. 37. The method for producing a polyester according to item 35 of the scope of patent application, wherein the auxiliary catalyst component (Π) is a magnesium compound. 38. — A method for treating polyester, which is characterized by using a titanium compound catalyst, and the polyester at the end of the reaction is a phosphorous acid aqueous solution, a hypophosphorous acid aqueous solution, and a phosphate ester with a phosphorus atom-concentrated concentration of 10 ppm or more. Water soluble • 192- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 585881 A8 B8 C8 D8 6. Application scope of patent solution, phosphite solution or hypophosphite solution, contact the processor. 3 9 · If the method of processing polyester in item 38 of the scope of patent application, where the inherent viscosity of the polyester is above 0 · 50 dl / g, the density (please read the precautions on the back before filling this page) is 1.3 7 bogey / 〇1113 or more, and the content of acetaldehyde is less than 50 0111 〇 0 0, such as the application method of the polyester scope of the 38th or 39th method of treatment, which uses titanium compound catalyst obtained And the polyethylene terephthalate whose reaction is terminated is treated. 4 1 · A method for treating polyester, which is characterized in that it is obtained by using a titanium compound catalyst, and the polyester at the end of the reaction is contacted with an organic solvent solution selected from the group consisting of alcohols, saturated hydrocarbons and ketones. 4 2 · The processing method of polyester according to item 41 of the scope of patent application, wherein the above-mentioned polyester series has an inherent viscosity of 0.550 dl / g or more, a density of 1.37 bogey / 0.111 liters, and an acetaldehyde content of 5 ?? 111 or less. 4 3 · The method for treating polyesters according to item 41 or 42 of the scope of patent application, wherein the organic solvent is isopropyl alcohol or acetone. 4 4 · If the application scope of the patent scope of item 41 or item 42 is polyester, the method of printing and processing by the consumer property cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is obtained by using a titanium compound catalyst, and the reaction is terminated. Phthalate esters are treated. 4 5 · A method for treating polyester, characterized in that a polyester obtained by using a titanium compound catalyst and the reaction is terminated is selected from phosphoric acid, phosphate ester, Phosphoric acid, hypophosphorous acid, phosphite or hypophosphite alcohols, saturated hydrocarbons, ketones, organic solvents, etc. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) · 193-585881 A8 B8 C8 D8 6. Those who apply for patent scope should contact the handler. 4 6 · If the method for processing polyester according to item 45 of the scope of patent application, where the inherent viscosity of the polyester is 0.550 d / g or more, and the density (please read the precautions on the back before filling this page) is 1 · 37 g / cm3 or more, and acetaldehyde content of 5 ppm or less 0 4 7 The processing method of polyester as described in claim 45 of the patent application scope, wherein the above-mentioned phosphate is tributyl phosphate, triphenyl phosphate or triphenyl phosphate Methyl phosphate. 4 8 · The processing method of polyester according to item 45 of the scope of patent application, wherein the organic solvent is isopropyl alcohol or acetone. 4 9 · The method for treating polyesters according to any of claims 45 to 48 in the scope of patent application, which is a polyethylene terephthalate obtained by using a titanium compound catalyst and the reaction is terminated By. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 50 · —polyesters (P—1), which are characterized by the presence of a catalyst for polyester manufacturing such as the scope of patent application for item 4 or item 6. A polyester obtained by polycondensation of a dicarboxylic acid or an ester-forming derivative thereof with an aliphatic diol or an ester-forming derivative thereof, the content of titanium is 1 to 100 ppm, and the content of magnesium is 1 to 200 ppm, the weight ratio (M g / T i) of titanium and magnesium contained in the polyester is one that is greater than or equal to 0 · 01. 5 1 · The polyester (P — 1) according to item 50 of the patent application scope, wherein the polyester is polyethylene terephthalate. 52. A kind of polyester (P-2), which is characterized by containing titanium atoms in an amount of 0.1 to 200 ppm, and contains a material selected from the group consisting of beryllium, magnesium, brocade, total, barium, boron, Ming, gallium, manganese, and cobalt. Paper size Applicable to China National Standard (CNS) A4 specification (210X297 cm) -194-585881 A8 B8 C8 D8 7T, patent application scope (please read the precautions on the back before filling this page), metal atoms in zinc and antimony (M ) 0 · 1 to 500 ppm, the molar ratio of the titanium atom and the metal atom (M) (the titanium atom / metal atom (M) is in the range of 1/5 0 to 5 0/1, and contains 0 · 0 1 to lOOppm amount of hue adjuster. 53.-a kind of polyester (P-3), characterized by an inherent viscosity of 0.50dl / g or more, containing titanium atoms in an amount of 0.1 ~ 2000ppm, containing beryllium The amount of metal atoms (M) in magnesium, calcium, scandium, barium, boron, aluminum, gallium, manganese, cobalt, zinc, and antimony is from 0.1 to 500 ppm. The molar ratios of the above titanium atoms to the above metal atoms (M) (The titanium atom / metal atom (M) is in the range of 0.05 to 50, the acetaldehyde content is below 4 p pm, and the content is WQp pm, and it is heated to melt at 2 7 5 ° C. When the acetaldehyde content after molding into a step-shaped rectangular shaped article is Wip pm, Wi-W. Is less than 10 p pm. 5 4. For example, the polyester (P-3) in the 53rd scope of the patent application, where The above-mentioned titanium atom is derived from the condensation polymerization catalyst obtained by hydrolysis of the titanium halide compound. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 5. For example, the polyester (P — 3), wherein the polyester is a polyethylene terephthalate. 56. A polyester (P-4), characterized in that the intrinsic viscosity is 0.50 dl / g or more, and the titanium atom is 0. 1 ~ 200ppm, containing selected from beryllium, magnesium, calcium, thorium, barium, boron, aluminum, gallium, manganese, cobalt This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -195 -585881 A8 B8 C8 D8 6. Scope of patent application, metal atom (M) in zinc and antimony 0 · 1 ~ 500ppm, Molar ratio of the above titanium atom and the above metal atom (M) (titanium hafnium / metal The atom (M) is in the range of 0.05 to 50, the content of the cyclic trimer is 0.5 to 5 wt%, and the content is x When the cyclic trimer content is increased by y weight% after melting to form a step-shaped rectangular shaped article after heating to 290 ° C, X and y can satisfy the relationship of the following formula: '0 · 2x + 0 · 2 of 5 7 · The polyester (P-4) according to item 56 of the patent application scope, wherein the titanium atom is derived from the hydrolysis of a titanium halide compound to obtain a condensation polymerization catalyst. 58. The polyester (P-4) according to item 56 of the patent application scope, wherein the polyester is polyethylene terephthalate. 59. A kind of polyester (P-5), which is characterized by the ratio (L / T) of the flow length (L) to the flow thickness (T) when it is injection-molded at 290 ° C. At Y, when the intrinsic viscosity of the molded product obtained by the above injection molding is X (d 1 / g), the relationship between the foregoing X and Y is shown by the following formula, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please first Read the notes on the back and fill in this page} γ ^ 647-500χ. 6 0 · As for the polyester (P-5) in the scope of patent application No. 59, where the titanium halide compound is hydrolyzed to produce a hydrolysate ( I-m) in the presence of a polycondensation catalyst formed by polycondensing an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -196-585881 A8 B8 C8 D8 VI. Application for patent scope 6 1 · If you apply for the polyester scope of the patent scope No. 5 9 (P-5) (Please read the notes on the back before filling out this page.) Among them, titanium halide compounds and In the presence of a polycondensation catalyst composed of a compound of at least one element of the other element or a precursor of the compound, or a mixture thereof, which is hydrolyzed to form a hydrolysate (I-η), the aromatic dicarboxylic acid or its ester can be formed. Derivatives obtained by polycondensation with an aliphatic diol or an ester-forming derivative thereof. 6 2 · The polyester (P-5) as claimed in item 61 of the patent application scope, wherein it is selected from the above-mentioned titanium A compound of at least one element other than the element or the precursor of the compound is selected from the group consisting of beryllium, magnesium, calcium, scandium, barium, osmium, B, steel, pin, supply, starvation, silver, group, network, group, A compound of at least one element in the group consisting of tin, bell, iron, nails, iron, copper, copper, iG, copper, fresh: shed, inscription, record: sand, copper, tin, antimony, and phosphorus or before the compound Excavator. 63. For example, the polyester (ρ-5) of item 59 in the scope of patent application, in which (I) the condensation polymerization reaction in any one of the scope of the patent application scope 60 to 62 Media, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and (Π) selected from beryllium and magnesium , Calcium, thorium, barium, boron, aluminum, gallium, manganese, inscriptions, words, errors, chains, and philosophies in the group of at least one element of the auxiliary catalyst component, in the presence of aromatic two It is obtained by polycondensation of a carboxylic acid or its ester-forming derivative and an aliphatic diol or its ester-forming derivative. 6 4 · Polyester (ρ-5) as claimed in item 63 of the scope of patent application Among them, the above-mentioned auxiliary catalyst component (Π) is a magnesium compound. 6 5 · If the polyester (ρ __ 5) of item 64 of the patent application scope, ^ paper size applies Chinese National Standard (CNS) A4 specification (210X297) (Centi)-585881 A8 B8 C8 D8 ____ VI. The scope of the patent application, among which the titanium atom content is in the range of 1 ~ 100p pm, the magnesium atom content is in the range of 1 ~ 2 00p pm. The weight ratio (Mg / Ti) is 0.001 or more. (Please read the precautions on the back before filling out this page) 6 6 · If you apply for a polyester (P-5) under the scope of patent application No. 59, the polyester is polyethylene terephthalate. 67. The polyester (P-5) according to item 63 of the patent application scope, wherein the polyester is polyethylene terephthalate. 6 8 · If the polyester (p-1) of the 50th or 51st scope of the patent application is used for moldings. 6 9 · The polyester (P-1) according to item 68 of the scope of patent application, wherein the above-mentioned molded article is a hollow molded article. 70. The polyester (P-1) according to item 68 of the scope of patent application, wherein the molded article is a film or sheet. 7 1 · The polyester (P — 1) according to item 68 of the scope of patent application, wherein the above-mentioned molded product is a fiber. 7 2 · The polyester (P-4) according to any one of claims 56 to 58 of the scope of patent application, which is used for a hollow molded product having a cyclic trimer content of 0.6% by weight or less. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 7 3 · If the polyester (P-5) in the scope of patent application No. 59 is used, it is a pre-plastic used for hollow molding. 7 4 · If the polyester (P-5) of item 63 of the scope of patent application is applied, it is used for pre-molded articles for hollow moldings. 7 5 · If the polyester (P-5) in the scope of patent application No. 59 is used, it is used for hollow moldings. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -198- one 585881 A8 B8 C8 D8 VI. Application scope of patent 7 6. For example, the polyester scope of the patent scope No. 63 (P-5) It is used for hollow moldings. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -199-